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THELETTERATUITO US 20170326536A1 METRO ( 19) United States (12 ) Patent Application Publication (10 ) Pub. No. : US 2017/ 0326536 A1 JIMOH et al. ( 43 ) Pub . Date: Nov . 16 , 2017

(54 ) METAL ORGANIC FRAMEWORKS AS C07C 51/ 285 (2006 .01 ) CATALYSTS AND HYDROCARBON C07C 45 /29 (2006 .01 ) OXIDATION METHODS THEREOF C07C 27 / 16 ( 2006 .01 ) B01J 35 / 10 ( 2006 .01 ) (71 ) Applicant: KING FAHD UNIVERSITY OF B01J 35 / 10 ( 2006 . 01 ) PETROLEUM AND MINERALS , B01J 35 / 10 ( 2006 .01 ) Dhahran (SA ) CO7F 15 /02 (2006 .01 ) B01J 35 / 10 (2006 . 01 ) ( 72 ) Inventors : Abiola Azeez JIMOH , Dhahran (SA ) ; (52 ) U . S . CI. Abdul Malik Peedikakkal, Dhahran CPC ...... B01J 31/ 123 (2013 .01 ); CO7F 15 /025 ( SA ) ( 2013 .01 ) ; CO7F 3 / 06 (2013 .01 ) ; CO7F 1/ 08 ( 2013 . 01 ) ; C07C 51/ 285 (2013 .01 ); B01J (73 ) Assignee : KING FAHD UNIVERSITY OF 35 / 1023 ( 2013 .01 ) ; C07C 27 / 16 (2013 . 01 ) ; PETROLEUM AND MINERALS , B01J 35 / 1061 ( 2013 .01 ) ; B01J 35 / 1057 Dhahran (SA ) (2013 . 01 ) ; B01J 35 / 1028 ( 2013 .01 ); C07C (21 ) Appl . No. : 15/ 458 ,437 45/ 294 ( 2013 .01 ) (22 ) Filed : Mar. 14 , 2017 (57 ) ABSTRACT A metal organic framework comprising zinc ( II ) ions and Related U .S . Application Data second metal ions , such as iron ( II ) ions, cobalt ( II ) ions, and copper ( II ) ions as nodes or clusters and coordinated 1 ,3 , 5 ( 60 ) Provisional application No. 62/ 335 , 954 , filed on May benzenetricarboxylic acid struts or linkers between them 13 , 2016 . forming a porous coordination network in the form of polyhedral crystals that are isostructural to HKUST - 1. Publication Classification Transmetallation processes for producing the metal organic (51 ) Int. Ci. frameworks , as well as methods for applications of the metal B01J 31 / 12 ( 2006 .01 ) organic frameworks as catalysts , specifically catalysts for CO7F 3 / 06 ( 2006 .01 ) the oxidation of cyclic hydrocarbons, such as toluene , cyclo CO7F 1 / 08 ( 2006 . 01 ) hexane , and methylcyclohexane . Patent Application Publication Nov . 16 , 2017 Sheet 1 of 34 US 2017 /0326536 Al

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METAL ORGANIC FRAMEWORKS AS 1999 , 9 , 105 .; and Eddaoudi, M .; Moler, D . B .; Li, H . ; Chen , CATALYSTS AND HYDROCARBON B . ; Reineke, T . M . ; O 'Keeffe , M .; Yaghi, O . M . Acc. Chem . OXIDATION METHODS THEREOF Res . 2001 , 34 , 319 . — each incorporated herein by reference in its entirety ) . This involves the use of multiple organic CROSS REFERENCE TO RELATED ligands and linkers and metal ions or clusters (secondary APPLICATIONS building units, SBUS) as nodes. FIG . 2 shows a schematic illustration of this MOF synthesis and structure . Most often , [0001 ] This application claims the benefit of priority from MOFs are easily synthesized by means of hydrothermal or U . S . Provisional Application No . 62 / 335 , 954 filed May 13 , solvothermal synthesis which involve high temperature self 2016 , the entire contents of which are herein incorporated by assembly in a high boiling organic solvent or water in closed reference . vessels [ Yaghi, O . M . ; O ' Keeffe, M . ; Ockwig , N . W .; Chae , H K . ; Eddaoudi, M . ; Kim , J . M Nature 2003 , 423 , 705 - 714 . ; BACKGROUND OF THE INVENTION and Stock , N . ; Biswas, S . Chem . Rev. , 2012 , 112 , 933 - 969 . ; and Yaghi, O . M . ; Li, H . L . J . Am . Chem . Soc ., 1995 , 117 , Technical Field 10401 - 10402 . ; and Lin , W . B . ; Wang , Z . Y . ; Ma, L . J . Am . [0002 ] The present disclosure relates to metal organic Chem . Soc. , 1999 , 121, 11249 - 11250 . , and Chui, S . S . Y . ; frameworks comprising zinc ( II ) ions and second metal ions, Lo , S . M . F . ; Charmant, J . P . H . ; Orpen , A . G . ; Williams, I . such as iron ( II ) ions, cobalt ( II ) ions, and copper ( II ) ions D . Science, 1999, 283 , 1148 - 1150 . — each incorporated as nodes or clusters and coordinated 1 , 3 , 5 - benzenetricar herein by reference in its entirety ) . However , these methods boxylic acid struts or linkers between them . Additionally , the typically require long reaction times, from several hours up present disclosure relates to processes for producing the to several days , depending upon the nature of the ligand , the metal organic frameworks and their application as catalysts reaction solvent , reagent concentrations and reaction tem in methods for the oxidation of cyclic hydrocarbons , such as perature . They can also be produced using the microwave toluene , cyclohexane , and methylcyclohexane . assisted process which allows the large scale synthesis of MOFs in a few minutes [Feldblyum , J . ; Liu , M . ; Gidley , D . ; Description of the Related Art Matzger , A . J. Am . Chem . Soc. 2011, 133 , 18257 - 18263 . ; [ 0003 ] The “ background ” description provided herein is and Dybtsev , D . N . ; Nuzhdin , A . L .; Chun , H . ; Bryliakov , K . for the purpose of generally presenting the context of the P . ; Talsi, E . P . ; Fedin , V . P . ; Kim , K . Angew . Chem . , Int. Ed . , disclosure. Work of the presently named inventors , to the 2006 , 45 , 916 - 920 . ; and Ni, Z . ; Masel, R . I . ; J . Am . Chem . extent it is described in this background section , as well as Soc ., 2006 , 128 , 12394 - 12395 . — each incorporated herein aspects of the description which may not otherwise qualify by reference in its entirety ) . as prior art at the time of filing, are neither expressly or 10006 ) MOF - 5 is one of the first series of MOFs to be impliedly admitted as prior art against the present invention . reported and fully characterized . It consists of an octahedral 00041 Metal organic frameworks (MOFs ) are crystalline , secondary building unit (SBU ) which is made from Zn _ highly porous coordination polymers which are comprised (CO2 ) . as an inorganic unit which is comprised of four Zn04 of inorganic units ( i. e . metals ) coordinated to rigid organic tetrahedra with a common vertex and six carboxylate fragments . They were built by a node linker approach that groups . These octahedral SBUS are joined together by was first described by Robson [Hoskins , B . F . ; Robson , R . J . benzene linkers [ Chalati , T . ; Horcajada, P .; Gref, R .; Cou Am . Chem . Soc. 1990 , 112 , 1546 . — incorporated herein by vreur, P . ; Serre , C . J . Mater . Chem ., 2011 , 21 , 2220 - 2227 . reference in its entirety ] . This method uses metal ions as incorporated herein by reference in its entirety ]. These nodes and organic ligands as linkers . In this case, a metal ion unique units lead to a perfect cubic network whose vertices with a preferred coordination number and geometry com comprise the SBUs and the edges of which are made up of bines with divergent ligand molecules to form an extended the benzene linkers . FIG . 3A shows the structure of MOF - 5 1D , 2D or 3D network or networks. The metal linker in an extended 3D cubic framework . This compound was interactions vary widely and have included ion - ion interac synthesized from Zn ( II) and 1 , 4 -benzenedicarboxylic acid tions, ion - dipole , dipole -dipole , hydrogen bonding , anion - it (BDC ) under organic conditions predetermined to form the interactions , J - n interactions, as well as van - der Waals SBU in situ . FIG . 3B shows the topology of the MOF interactions [Burrows , A . D . ; Chan , C . W . ; Chowdhry, M . structure as a ball - and - stick model. FIG . 3C shows the M . ; McGrady , J . E . ; Mingos , D . M . P . Chem . Soc. Rev. 1995 , structure represented by (OZn , )012 clusters (tetrahedrons ) 329 ; and Classens, C . G .; Stoddart , J . F . J. Phys . Org . Chem . joined by BDC ions ( connectors ) . Since the benzene links 1997 , 10 , 254 . - each incorporated herein by reference in its and the SBUs appear to be relatively rigid and large entities , entirety ) . The strength of these interactions has been proven the resulting structure has exceptionally high porosity (as to directly influence the overall stability of the resulting indicated by its sorption ) and stability [ Yaghi, O . M . , Sun , framework [ Braga , D . Chem . Comm . 2003 , 2751 - 2754 . — Z ., Richardson , D . A . & Groy, T . L J . Am . Chem . Soc. 1994 , incorporated herein by reference in its entirety ] . Extended 116 , 802- 808 . — incorporated herein by reference in its networks can be developed from the basic principles guiding entirety ] . the formation of coordination complexes . FIG . 1 shows a [00071 MOFs have been found to possess unique proper representation of the formation of these coordination net ties like high surface areas (up to 10400 m²/ g ) and tunable works . Hence , the choice ofmetal center affects the resulting pores that can be used in various potential applications such framework structure because a given metal has preference as gas storage, catalysis , separation , and drug delivery ( Li, for a specific geometry and coordination environment. H . , Eddaoudi, M ., O 'Keeffe , M . & Yaghi, O . M Nature 1999 , [0005 ] A second approach to the synthesis of MOFs was 402 , 276 - 279 . , and Silva , P .; Valente , A . A . ; Rocha, J. ; Paz , described by Yaghi [ Eddaoudi, M .; Li, H .; Reineke , T . ; Fehr, F . A . A . Cryst. Growth Des. , 2010 , 10 , 2025 - 2028 . ; and M . ; Kelley, D . ; Groy, T . L . ; Yaghi, O . M . Topics in Catalysis Wang , Z . ; Chen , G . ; Ding , K . Chem . Rev. , 2009 , 109, 322 . ; US 2017 /0326536 A1 Nov . 16 , 2017 and Corma, A . ; Garci' a , H .; Xamena , F . X . Chem . Rev. , for accessing new MOFs when conventional synthesis at 2010 , 23 , 1126 .; and Li, J. R .; Kuppler , R . J. ; Zhou , H . C . high temperature fails [Wang , Z . ; Cohen , S Chem . Soc .Rev . , Chem . Soc. Rev. , 2009 , 38 , 1477 . — each incorporated herein 2009 , 38 , 1315 - 1329 . — incorporated herein by reference in by reference in its entirety ) . They have also been found to be its entirety ). This substitution occurs at the metal nodes , candidates for other applications like microelectronics , sens often called the inorganic clusters or secondary building ing , optics , micromotors , molecular rotors , and bioreactors units ( SBUS) . Although the metal ions are integral parts of [Horcajada , P .; Chalati , T .; Serre , C . ; Gillet , B . ; Sebrie , C . ; the MOFs ' structures, they can be replaced either completely Baati, T .; Eubank , J. F .; Heurtaux , D .; Clayette , P . ; Kreuz , or partially within hours or days without necessarily affect C . ; Chang , J . S . ; Hwang , Y . K .; Marsaud , V . ; Bories , P . N . ; ing the MOFs ' structures Dinca , M . ; Long , J . R . J . Am . Cynober , L .; Gil , S .; Fe ’ rey, G .; Couvreur, P .; Gref, R . Nat. Chem . Soc. , 2007 , 129 , 11172 - 11176 . - incorporated herein Mater. , 2010 , 9 , 172 - 178 .; and Talin , A . A . ; Centrone , A . ; by reference in its entirety ] . Transmetallation changes the Ford , A . C .; Foster, M . E . ; Stavila , V .; Haney , P . ; Kinney, R . properties of the MOFs and also makes them useful for other A .; Szalai, V . ; Gabaly , F. E .; Yoon , H . P. ; Le ’onard , F .; important applications especially in catalysis . The transmet Allendorf , M . D . Science, 2014 , 343 , 66 .; and Kreno , L . E .; allated MOFs have multiple properties having separate Leong , K . ; Farha , O . K .; Allendorf , M . ; Van Duyne , R . P .; metal sites that can be utilized for specific catalytic conver Hupp , T . Chem . Rev . , 2012 , 112 , 1105 . ; and Cui, Y . ; Yue , Y . ; sions of organic molecules . Qian , G . ; Chen , B . Chem . Rev. , 2012 ,112 , 1126 .; and Ikezoe, [0009 ] The development of efficient new catalysts is still Y .; Washino , G .; Uemura , T .; Kitagawa, S .; Matsui, H . Nat. a serious challenge in chemical research . Hence the increas Mater. , 2012 , 11 , 1081. , and Comotti, A . ; Bracco , S . ; Ben , ing demand for safer and energy saving reaction routes T . ; Qiu S . ; Sozzani , P . Angew . Chem . , Int. Ed ., 2014 , 53 , promotes the need to develop new materials towards the 6655 . — each incorporated herein by reference in its global aim of combating serious environmental challenges entirety ] . Presently , the most highly recognized applications that stem from several industrial processes . Hence , catalyst ofMOFs , however , have been in the areas of gas storage and development is an ever growing area of research . Recently , separation . The strong interest in this research area stems chemists have endorsed MOFs as viable heterogeneous from the urgent need to develop viable technologies for catalysts to channel the course of new and existing chemical hydrogen fuel storage for commercial use as well as to reactions to reduce industrial wastes and enable greener control the concentration of CO2 in the atmosphere . chemical processes . This work facilitates better understand [0008 ] High surface area and the possibility of varied ing of physical and chemical processes such as surface structural modification amongst other desirable physical and interactions and facilitates novel concepts and ideas for the chemical properties make it possible for MOFs to efficiently next generation of catalysts . The role of heterogeneous catalyze a broad range of reactions. The MOFs are usually catalysts either in chemical or petrochemical industries modified by a method that is broadly known as post cannot be overemphasized . They reduce the enormous synthetic - modification (PSM ) . PSM makes it possible to wastes that are associated with homogeneous catalysts and incorporate a highly diverse range of different functional also reduce cost due to their reusability . These heteroge groups making it largely free of the restrictions resulting neous catalysts occur in a different phase from the substrates from the synthetic conditions of the MOFs. PSM also allows and predominantly work base on an adsorption mechanism . the introduction of multiple metal ions into a single frame The heterogeneous catalysts are mostly solids on which work in a combinatorial manner, enabling an effective way liquid or gaseous reaction mixtures are adsorbed . The active to systematically fine tune and optimize MOF properties site may be either a planar exposed metal surface, a crystal [ Doherty , C . M . ; Grenci, G .; Riccoo , R .; Mardel, J . I. ; edge with imperfect metal valence or a complicated com Reboul, J . ; Furukawa, S .; Kitagawa, S .; Hill , A . J .; Falcaro , bination of the two . Thus , not only most of the volume, but P . Adv. Maater. , 2013 , 25 , 4701 . — incorporated herein by also most of the surface of a heterogeneous catalyst may be reference in its entirety ). The process in which new metal catalytically inactive . The dependence of catalytic activity sites are incorporated into a MOF framework is known as on surface area and pore volume makes MOF catalysts a transmetallation or post- synthetic metal exchange and the viable area of chemical research . Investigating the nature of MOFs produced by this method can be described as iso the active sites requires technically challenging research . structural MOFs with similar structural frameworks but Thus , studies relating to new metal and ligand combinations different metal ions . FIG . 4 illustrates a general scheme for for catalysis continue. the post -synthetic modification of MOFs . This synthetic [0010 ] These highly porous, crystalline MOFs have some method can be used to obtain certain MOFs that cannot be of the catalytically important properties of zeolites like obtained via conventional synthetic methods . Cation uniform cavity and pore sizes as well as medium to large exchange also helps to enhance the properties of some internal surface areas Wang , L , J .; Deng , H . ; Furukawa, H . ; MOFs by making it possible to incorporate a more useful Gandara , F . ; Cordova , K . E .; Peri, D . ; Yaghi, O . M . Inorg. metal site thereby improving some of their physical and Chem . 2014 , 53 , 5881 -5883 . — incorporated herein by ref chemical properties hence giving them more interesting erence in its entirety ]. Unlike zeolites, vast chemical vari applications . For example , HKUST- 1 has a surface area of eties of MOFs can be synthesized due to the presence of about 1500 m²/ g and it contains Cu2 + but the isostructure infinite organic linkers. This suggests that the catalytic niche can be made by substituting the Cu2 + with other metals . A of MOFs is likely to be high value added reactions such as unique property of transmetallation lies in the fact that new production of specific enantiomers , sensitive molecules , as MOFs can be obtained by complete or partial substitution of well as production of fine chemicals , which require specific metal ions within the framework without altering the mor and tunable catalytic sites [ Furukawa , H . ; Ko , N .; Go , Y . B . ; phology of the MOFs . FIG . 5 shows a schematic represen Aratani, N . ; Choi, S . B . ; Choi , E . ; Yazaydin , A . ; Snurr, R . Q . ; tation for post synthetic metal exchange or transmetallation . O 'Keeffe , M .; Kim , J .; Yaghi, O . M . Science , 2010 , 329 , This process serves as an alternative , typically milder route 424 .; and Pan , L .; Adams, K . M .; Hernandez , H . E .; Wang , US 2017 /0326536 A1 Nov . 16 , 2017

X ., Zheng , C . ;Hattori , Y . , Kaneko , K . J . Am . Chem . Soc . (where R is an aromatic ring) , C18H12015Cuz . It creates a 2003 , 125 , 3062 . — each incorporated herein by reference in 3 - dimensional system of channels with a pore size of its entirety ) . Despite the various interesting and compelling approximately 1 nm and an accessible porosity of about 40 % recent developments in MOF catalysis , the area of MOF in the solid . The single crystal structural analysis of catalysis is still in an immature phase . Many researchers HKUST- 1 revealed that the polymer framework is com have likened MOF catalysis to enzyme catalysis , aiming posed of dimeric cupric tetracarboxylate building units , with towards the development of catalytic chemistry in the direc a Cu - Cu inter- nuclear separation of 2 .628 ( 2 ) A . FIG . 6 tion of an " artificial enzyme” . Overall , the uniqueness of shows the crystal structure of the dicopper ( II) tetracarboxy MOFs over other materials is yet to be fully illustrated since late building block containing two axial aqua ligands. The they have been reported to be of use as catalysts in the framework was found to be neutral because the twelve chemical or petrochemical industries. carboxylate oxygens from the two BTC ligands bind to four [ 0011] Oxidation reactions are among the most important coordination sites for each of the three Cu2 + ions of the chemical conversions in industries and laboratories . Con formula unit. Hence each Cu atom completes is pseudo version of abundant and cheap hydrocarbons like toluene , octahedral coordination sphere with the presence of axial cycloalkanes and methylcyclohexane into more valuable aqua ligands opposite to the Cu - Cu dimer. The tetracar chemicals like aldehydes , ketones and acids stands as a boxylate unit provides a structural motif with potential significant process for consideration [Hayashi , H . ; Cote, A . four -fold symmetry , and the trimesic acid provides a three P . ; Furukawa, H .; O 'Keeffe , M . ; Yaghi, O . M . Nat. Mater . fold symmetry element . FIG . 7 shows a HKUST - 1 second 2007 , 6 , 501 . — incorporated herein by reference in its ary building unit ( SBU ) demonstrating the tbo net topology entirety ] . Among these useful transformations, the direct and the paddlewheel structure . The origin of the nanochan oxidation of toluene to produce benzaldehyde is an attractive nels can be clearly considered to arise from the formation of process. Toluene oxidation gives a mixture of oxygenated larger octahedral secondary building units (SBUS ) . The main products like benzoic acid , benzyl alcohol, benzaldehyde SBU in HKUST - 1 is the octahedral unit with Cu , at its 6 and cresols . Commercially , benzaldehyde is mainly pro vertices and 4 trimesate ions tetrahedrally disposed as “ pan duced by the chlorination of toluene followed by the hydro els ” for four of the eight triangular faces of the octahedron . lysis process , which generates large amounts of toxic acidic / FIG . 8 shows the [Cuz ( TMA ) 2 (H2O )3 ] unit viewed along the basic discard solutions, leading to equipment corrosion and cell body diagonal, demonstrating a hexagonal- n shaped environmental pollution . Furthermore, the benzaldehyde window at the intersection of the nanopores . FIG . 9 shows produced by this route is not qualified to synthesize some the polymer framework and nanochannels with four - fold high quality compounds such as perfumes or pharmaceuti symmetry. cals because the product contains chlorine [ Friedrich Brihne [0014 ] The Zn - HKUST - 1 that contains Zn2 + ions is analo and Elaine Wright “ Benzaldehyde ” in Ullmann ' s Encyclo gous to HKUST- 1 . Analysis of Zn -HKUST - 1 by powder pedia of Industrial Chemistry, 2002 , Wiley - VCH , Wein X -ray diffraction and gas sorption shows the retention of heim . — incorporated herein by reference in its entirety ). crystalline structure but negative nitrogen uptake at 77 K Therefore , there is a clear need to develop new materials to due to a dense surface layer that prevents the passage of improve the selective oxidation of toluene as an alternative small molecular species into the crystal framework [ Bhunia , route to produce benzaldehyde and consequently benzoic M . K , Hughes, J . T . Fettinger , J . C . and Navrotsky , A . acids . Langmuir 2013 , 29 , 8140 -8145 . — incorporated herein by [0012 ] Alkanes are naturally abundant and cheap carbon reference in its entirety ] . The prevalence of zinc paddle containing raw material which serve as attractive substrates wheels in a variety of MOFs, such as the previously dis for the production of value added organic chemicals ( alco cussed HKUST- 1 suggests that Zn I a promising metal with hols , ketones , aldehydes and carboxylic acids ) [ B . Retcher, which an isostructural analog to Cu -HKUST - 1 can be con J . S . Costa , J . Tang, R . Hage , P . Gamez , J . Reedijk , J . Mol. structed . Catal. A . 2008 , 286 , 1 - 5 . — incorporated herein by reference [0015 ] The application of metal organic frameworks has in its entirety ] . Unfortunately , the chemical inertness of been investigated . Over the past decades , transition metal these compounds is a considerable limitation towards their complexes comprising mainly phosphine ligands, salen or vast application for direct syntheses of oxygenated products salophen ligands , pincer ligands and N -heterocyclic car under relatively mild conditions. However, a proper metal benes (NHCs ) have had a remarkable impact on catalysis . catalyst and an appropriate oxidizing agent, as well as Examples include the Nobel prize winning Noyori asym properly controlled reaction conditions , can lead to the metric hydrogenation , Sharpless oxidations (Sharpless development of a cleaner and more efficient chemical indus epoxidation , Sharpless asymmetric dihydroxylation , and try. Today, over a billion tons of cyclohexanone and cyclo Sharpless oxyamination , as well as Jacobsen epoxidation hexanol are produced every year and they are mostly used [Noyori , R Adv. Synth . Catul 2003 , 345 , 12 , 15 -41 . , and for the synthesis of Nylon -66 and Nylon - 6 [ M . Musser Katsuki, T .; Sharpless, K . BJ Am . Chem . Soc . , 1980 , 102 , " Cyclohexanol and Cyclohexanone ” in Ullmann ' s Encyclo 5974 -5976 . ; and Jacobsen , E . N .; Marko , T. ; Mungall, W . S .; pedia of Industrial Chemistry, Wiley - VCH , Weinheim , Schroeder, G .; Sharpless , K . B . J . Am . Chem . Soc . , 1988 , 110 2005 . — incorporated herein by reference in its entirety ]. 1968 - 1970 . ; and Sharpless , K . B ; Patrick , D . W . ; Truesdale , [0013 ] The structure of HKUST- 1 and Zn -HKUST - 1 L . K .; Biller, S . A . J . Am . Chem . Soc. , 1975 , 97 , 2305 2307 . ; metal organic frameworks has been investigated . Chui and and Zhang , W . ; Loebach , J . L . ; Wilson , S . R . ; Jacobsen , E . coworkers were the first to synthesize HKUST- 1 at the Hong N . J . Am . Chem . Soc. , 1990 , 112 , 7 , 2801 - 2803 . — each Kong University of Science and Technology. HKUST - 1 was incorporated herein by reference in its entirety ) . Most of discovered to be a highly porousmetal coordination polymer these metal complexes have only been successful as homo Cuz (BTC ) , ( H , O ) , (where BTC is benzene - 1 , 3 , 5 - tricar - geneous catalysts which have significant disadvantages like boxylate ) which has interconnected [Cuz (02CR )4 units the difficulty of product separation , poor reusability and US 2017 /0326536 A1 Nov . 16 , 2017 toxicity . Relatively insoluble and stable materials like zeo rials. 2004 , 73 : 81- 85 . ; and Lien T . L . Nguyen , Tung T . lites , metals and metal oxides are widely used as heteroge Nguyen, Khoa D . Nguyen, Nam T . S . Phan Applied Cataly neous catalyst on the industrial scale . Notable conversions sis A : General, 2012 , 425 , 44 -52 . — each incorporated herein like the Harber- Bosch , Contact process, Ostwald process , by reference in its entirety ) . Schlichte , et al . first reported the steam reforming , petrochemical reactions Ziegler Natta catalytic activity of HKUST- 1 when they used the HKUST- 1 polymerization make use of these insoluble materials . In MOF for the trimethylcyanosilation of benzaldehyde. The terms of easy post reaction separation , these materials have open framework of this MOF was activated by removing the largely been successful. However, there is still an urgent two water molecules from axial positions in the octahedral need for the development of new materials that will be more framework . The activated MOF afforded up to 57 % conver energy efficient, more tunable, and more environmentally sion of benzaldehyde reaching a selectivity of 89 % at 313 K . friendly . Nguyen , et al. studied the activity of HKUST- 1 for the [0016 ] MOFs have shown great catalytic prospects for a aza -michael reaction in which amines were reacted with wide range of reactions due to the diversity in their struc a , ß - unsaturated carbonyl groups to prepare ß -amino carbo tures , low toxicity , reusability and cost effectiveness . In fact nyl compounds and their derivatives . They achieved excel MOFs are among the best candidates in bridging the gap lent conversions up to 100 % under relatively mild condi between homogeneous and heterogeneous catalysis . The tions in the presence of 5 mol % activated catalyst . Fourier metals in the MOF structure often act as Lewis acids transform infrared spectroscopy (FT - IR ) and powder X -ray especially when the frameworks are activated by removing diffraction (PXRD ) analysis revealed that the catalyst could the coordinated labile solvent molecules or counter ions be reused several times without a significant reduction in its [ Han , J. W .; Hill , C . L . ; J . Am . Chem . Soc. , 2007, 129 , catalytic potency . Atomic absorption spectroscopy showed 15094 . — incorporated herein by reference in its entirety ). that the reaction was not influenced by homogeneous cataly Fujita , et al . first reported the catalytic activity of a 2D Cd ( II ) sis resulting from leached active species. based MOF for the cyanosilylation of aldehydes . Thy [0018 ] Using the same material , Phan , et al. was able to obtained the unsaturated metal cluster by removing two react phenols and aryl iodides to form diaryl ethers in an water molecules from the octahedral structure of [Cd ( 4 , 4 ' Ullman - type coupling reaction . The heterogeneous reaction bpy ) 2 (H2O ) 2 ]. (NO3 ) 2. 4H20 [ Fujita , M . ; Kwon , Y . J. ; leads to high conversion using 5 mol % catalyst in the Washizu , S . ; Ogura , K . J . Am . Chem . Soc. 1994 , 116 , presence ofMeONa as a base . The used catalyst was facilely 1151 - 1152. — incorporated herein by reference in its recovered from the reaction mixture using simple filtration entirety ] . Fe (BTC ) has also been used as a heterogeneous and could be reused without significant degradation [Nam T . catalyst for the selective methylation of primary aromatic S . Phan, Tung T . Nguyen , Chi V . Nguyen , Thao T . Nguyen amines using dimethyl carbonate , efficient oxidation of Applied Catalysis A : General. , 2013 , 457 , 69 -77 . — incorpo benzylic compounds using t -butyl - hydroperoxide as oxidiz rated herein by reference in its entirety ] . Phan , et al . also ing agent, and oxidation of thiols to disulfides [Dhakshi reported the highly efficient activity of HKUST- 1 for the namoorthy, A . , Alvaro , M . ; Garcia , H . Appl . Catal. A : C -arylation of acetylacetone in the presence of aryl iodides General 2010 , 378 , 19 - 25 . , and Dhakshinamoorthy, A . ; to obtain aryl ketones as major products . HKUST- 1 was Alvaro , M . ; Garcia, H . J . Catal. 2009, 267 , 1 - 4 .; and confirmed to be a true heterogeneous catalyst as there was no Dhakshinamoorthy, A .; Alvaro , M .; Garcia , H . Chem . Com effect of homogeneous catalysis of active species leaching mun ., 2010 , 46 , 6476 -6478 . each incorporated herein by into the reaction mixture [Nam T . S . Phan , Tung T . Nguyen , reference in its entirety ] . Seo , et al. first reported asymmetric Phuong Ho , and Khoa D . Nguyen ChemCatChem. 2013 , 5 , catalysis using a homochiral MOF, [Zn (uz -0 ) ( 1 - H ) 6 .2H2O . 1822 - 1831 . - incorporated herein by reference in its 12H , O ] for transesterification reactions. It was also the first entirety ] . Dang , et al . studied the catalytic activity of MOF demonstrating that the organic linker embedded into a HKUST- 1 for the synthesis of propargylamine via direct pore can catalyze an asymmetric reaction [Seo , J. S .; Whang , oxidative C — C coupling reaction using C — H functional D .; Lee, H . ; Jun , S . I . ; Oh , J . ; Jeon , Y . J . ; Kim , K . Nature , ization between phenylacetylene and N , N -dimethylaniline 2000 , 404 , 982 - 986 . — incorporated herein by reference in its to give N -methyl - N -( 3 -phenylprop - 2 - ynyl) benzenamine as entirety ] . Lin , et al . also reported the activity of a homochiral the principal product [ Giao H. Dang , Duy T. Nguyen, Dung non - interpenetrating MOF which was constructed in finite T. Le, Thanh Truong , Nam T . S . Phan Journal of Molecular 1 - dimensional (Cd ( p -C1 ) . ] , zigzag chains with axial bipyri Catalysis A , 2014 , 300 , 306 . — incorporated herein by ref dine bridging ligands containing orthogonal secondary func erence in its entirety ] . The copper catalyzed reaction tional groups Wu, C . , Hu, A . ; Zhang , L . , Lin , W . J . Am . afforded 96 % conversion after 180 minutes at 120° C . in the Chem . Soc. , 2005, 127 , 8940 -8941 . — incorporated herein by presence of 5 mol % copper- based catalyst . The used cata reference in its entirety ] . The chiral secondary functional lyst was recovered from the reaction medium by filtration groups were used to generate a heterogeneous asymmetric and reused for the coupling reaction . Similarly , HKUST- 1 catalyst for the addition of diethyl zinc to aromatic alde has been used as a catalyst for the direct oxidative amination hydes to afford chiral secondary alcohols at up to 93 % of sp2 C - H bonds. The reaction involves the use of enantiomeric excess (ee ) . N -methylmorpholine oxide (NMO ) as oxidizing agent in the [0017 ] More specifically , the catalytic activity of presence of primary or secondary amine as coupling pairs HKUST- 1 has been investigated . HKUST- 1 has been par with DMF as solvent at 90 - 100° C . [ Nga T . T . Tran , Quan H . ticularly well recognized for its high catalytic activity espe Tran , Thanh T . Journal of Catalysis , 2014 , 320 , 9 - 15 . cially when the axial aqua ligands are removed via activa incorporated herein by reference in its entirety ). tion . FIG . 10 illustrates schematically the activation of [0019 ] In view of the forgoing, one object of the present HKUST- 1 . Activation gives unsaturated metal sites without disclosure is to provide relatively cheap and environmen affecting the rigid framework of the MOF (Schlichte , K . ; tally friendly metal organic framework catalysts designed Kratzke , T . ; Kaskel, S .; Microporous and Mesoporous Mate towards laboratory and industrial scale catalytic applications US 2017 /0326536 A1 Nov . 16 , 2017 as opposed to uses in gas storage and carbon capture . Metal hydrate in a solvent at a temperature greater than 25° C . to organic framework catalysts provide great potential for new form a zinc modified metal organic framework and ii ) and existing chemical reactions for shortest route organic transmetallating at least a portion of the zinc modified metal conversions that reduce industrial wastes and enable greener organic framework by immersing in a solution of a salt or chemical processes through their high tunability , high sur hydrate of the second metal ions . face area , stability , and reusability . Specifically , this disclo [0029 ] According to a third aspect, the present disclosure sure is focused on isostructural HKUST- 1 metal organic relates to a method for an oxidation of a cyclic hydrocarbon frameworks comprising zinc ( II) metal ions and second comprising contacting the cyclic hydrocarbon with the metal metal ions, such as iron ( II ) ions, cobalt ( II ) ions, and copper organic framework catalyst in any of its embodiments in the ( II ) ions linked by 1 , 3 , 5 -benzentricarboxylic acid to form a presence of a solvent and an oxidizing agent to form an porous coordination network as polyhedral crystals. This oxidized cyclic hydrocarbon . disclosure provides the transmetallation preparation of these [0030 ] In one embodiment, the cyclic hydrocarbon is at metal organic frameworks by post -synthetic metallic least one selected from the group consisting of toluene, exchange of the solvothermally synthesized Zn -HKUST - 1 cyclohexane , and methylcyclohexane. metal organic framework . An additional aspect of the pres [0031 ] In one embodiment, the solvent is acetonitrile and ent disclosure is application of these metal organic frame the oxidizing agent is hydrogen peroxide . works as catalysts in methods for the liquid phase oxidation [0032 ] In one embodiment, the contacting is performed at of cyclic hydrocarbons , such as, toluene , cyclohexane, and a temperature in the range of 40 - 100° C . for a time period methylcyclohexane . It is envisioned that the metal organic of 2 - 36 hours . frameworks of the present disclosure will exhibit strong [ 0033 ] In one embodiment, the cyclic hydrocarbon is activity in terms of conversion of the cyclic hydrocarbon , toluene and 15 - 80 % of the toluene is converted to the selectivity for a desired oxidized cyclic hydrocarbon prod oxidized cyclic hydrocarbon at a reaction time of greater uct, and reusability . Overall, the metal organic frameworks than 6 hours . are envisaged to exhibit strong potential utility as catalysts [0034 ] In one embodiment, the cyclic hydrocarbon is that aid the increasing demand for safer and energy saving toluene and the method has a benzaldehyde selectivity in the reaction routes that additionally reduce and minimize the range of 15 - 70 % relative to a total amount of oxidized cyclic adverse environmental impact of industrial wastes . hydrocarbon products . [0035 ] In one embodiment , the cyclic hydrocarbon is BRIEF SUMMARY OF THE INVENTION toluene and the method has a benzaldehyde selectivity [ 0020 ] According to a first aspect , the present disclosure relative to a total amount of oxidized cyclic hydrocarbon relates to a metal organic framework catalyst comprising i ) products greater than or equal to a benzaldehyde selectivity zinc ( II ) ions, ii ) second metal ions which are not zinc ( II ) relative to a total amount of oxidized cyclic hydrocarbon ions , and iii ) benzene - 1 , 3 , 5 - tricarboxylic acid ligands, products of a substantially similar method performed in a wherein the benzene - 1 , 3 , 5 - tricarboxylic acid ligands com substantially similar manner with a substantially similar prise carboxylate groups, each carboxylate group forming a metal organic framework catalyst lacking the zinc ( II ) ions , coordinative bond to the zinc ( II ) ions or the second metal the second metal ions, or both . ions to form a coordination network in the form of porous [0036 ] In one embodiment, the cyclic hydrocarbon is polyhedral crystals that are isostructural to an HKUST- 1 toluene and the second metal ions are iron ( II ) ions and the metal organic framework . oxidation has a benzaldehyde selectivity of greater than 55 % 10021 ] In one embodiment, the second metal ions are at relative to a total amount of oxidized cyclic hydrocarbon least one selected from the group consisting of iron ( II ) ions, products . cobalt (II ) ions, and copper (II ) ions . [0037 ] In one embodiment, the cyclic hydrocarbon is at [0022 ] In one embodiment, the ratio of zinc (II ) ions to the least one selected from the group consisting of cyclohexane additional metal ions is in the range of 0 .01 to 5 . 0 . and methylcyclohexane and 10 -60 % of the cyclic hydrocar [0023 ] In one embodiment, the porous polyhedral crystals bon is converted to the oxidized cyclic hydrocarbon at a have pores with an average diameter of 0 . 2 - 2 . 0 nm and a reaction time of greater than 12 hours . BET surface area in the range of 500 - 3000 mº/ g . [0038 ] In one embodiment, the cyclic hydrocarbon is [0024 ] In one embodiment, the porous polyhedral crystals cyclohexane and the method has a cyclohexane selectivity in are octahedral or cubic with an average longest linear the range of 45 - 80 % relative to a total amount of oxidized dimension in the range of 2 - 20 um . cyclic hydrocarbon products . [0025 ] In one embodiment , the metal organic framework [0039 ] In one embodiment, the method further comprises catalyst has a larger unit cell dimension a than the HKUST- 1 recovering and reusing the metal organic framework catalyst metal organic framework . in at least 2 reaction iterations with a less than 20 percentage 100261 In one embodiment, the second metal ions are point decrease in conversion , selectivity , or both . copper ( 11) ions and the ratio of zinc ( II ) ions to copper ( II ) [0040 ] The foregoing paragraphs have been provided by ions is in the range of 0 .01 to 1 . 0 . way of general introduction , and are not intended to limit the [0027 ] In one embodiment, the second metal ions are at scope of the following claims. The described embodiments , least one selected from the group consisting of iron ( 11 ) ions together with further advantages, will be best understood by and cobalt ( 11) ions and the ratio of zinc ( 11) ions to the reference to the following detailed description taken in second metal ions is in the range of 0 .5 - 5 . 0 . conjunction with the accompanying drawings . [0028 ] According to a second aspect, the present disclo sure relates to a process for producing the metal organic BRIEF DESCRIPTION OF THE DRAWINGS framework in any of its embodiments comprising i ) reacting (0041 ] A more complete appreciation of the disclosure and 1 ,3 , 5 -benzenetricarboxylic acid with a zinc (II ) salt or many of the attendant advantages thereof will be readily US 2017 /0326536 A1 Nov . 16 , 2017 obtained as the same becomes better understood by refer - [0056 ] FIG . 13 is a Fourier transform infrared (FT - TR ) ence to the following detailed description when considered spectrum of 1 , 3 , 5 -benzenetricarboxylic acid (BTC ) . in connection with the accompanying drawings , wherein : [0057 ] FIG . 14 is a FT- IR spectrum of the prepared [0042 ] FIG . 1 is a schematic representation demonstrating HKUST- 1 metal organic framework . the extension of the principles guiding the formation of [0058 ] FIG . 15 is a FT - IR spectrum of the prepared metal coordination complexes to metal organic framework Zn2 . -HKUST - 1 metal organic framework . (MOF ) coordination networks [0059 ] FIG . 16 is a FT - IR spectrum of the prepared [0043 ] FIG . 2 is a schematic illustration of the synthesis Fe - Zn -HKUST - 1 metal organic framework after transmet and structure of metal organic frameworks (MOFs ) from allation . organic linkers and secondary building units (SBUs ) com [0060 ] FIG . 17 is a FT- IR spectrum of the prepared prising metal ions or clusters . Co - Zn -HKUST - 1 metal organic framework after transmet [ 0044 ] FIG . 3A is a schematic representation of MOF -5 allation . represented as ZnO , tetrahedra linked by benzene dicar 10061 ] FIG . 18 is a FT- IR spectrum of the prepared boxylate (BDC ) organic linkers to form an extended 3D Cu - Zn -HKUST - 1 metal organic framework after transmet cubic framework with interconnected pores of approxi allation mately 8 A aperture width and approximately 12 A pore 10062 ] FIG . 19 is a scanning electron microscopy (SEM ) diameter as represented by the sphere . image of the prepared HKUST- 1 metal organic framework at [0045 ] FIG . 3B is a schematic representation of the topol a magnified view . ogy of the MOF - 5 structure shown as a ball - and - stick model [ 0063] FIG . 20 is a SEM image of the prepared HKUST- 1 with (OZn , )012 clusters as balls and benzene dicarboxylate metal organic framework . ( BDC ) connectors as sticks . [0064 ] FIG . 21 is a SEM image of the prepared Zn [0046 ] FIG . 3C is a schematic representation of the topol HKUST- 1 metal organic framework at a magnified view . ogy of the MOF - 5 structure shown with tetrahedra repre [0065 ] FIG . 22 is a SEM image of the prepared Zn senting (OZn , ) 0 , 7 clusters and connections representing HKUST- 1 metal organic framework . benzene dicarboxylate (BDC ) ions where opposing lines are [0066 ] FIG . 23 is a powder X - ray diffraction (PXRD ) all at exactly 90°. pattern for the simulated HKUST- 1 metal organic frame [0047 ] FIG . 4 is a general scheme for the post synthetic work and the prepared experimental HKUST- 1 metal modification of MOFs. organic framework . [ 0048 ] FIG . 5 is a general schematic diagram for post [0067 ] FIG . 24 is a PXRD pattern for the simulated synthetic metal exchange of a MOF structure , or transmet Zn -HKUST - 1 metal organic framework and the prepared allation of a MOF structure . experimental Zn - HKUST - 1 metal organic framework . [0049 ] FIG . 6 is a single crystal structural analysis of a [0068 ] FIG . 25 is a comparative PXRD analysis showing HKUST- 1 dicopper ( II) tetracarboxylate building block con PXRD patterns of the prepared FeZn -HKUST - 1 metal taining two axial aqua ligands. organic framework after transmetallation and the prepared [0050 ] FIG . 7 is a schematic representation of a secondary Zn -HKUST - 1 metal organic framework . building unit (SBU ) of HKUST- 1 showing the tbo net 10069 ) FIG . 26 is a comparative PXRD analysis showing topology and paddlewheel structure where the tetracarboxy PXRD patterns of the prepared Co - Zn -HKUST - 1 metal late unit provides a structural unit with four- fold symmetry organic framework after transmetallation and the prepared and the trimesic acid provides a three - fold symmetry ele Zn -HKUST - 1 metal organic framework . ment. [0070 ] FIG . 27 is a comparative PXRD analysis showing [0051 ] FIG . 8 is a schematic representation of the larger PXRD patterns of the prepared Cu — Zn -HKUST - 1 metal main octahedral secondary building unit (SBU ) of organic framework after transmetallation and the prepared HKUST- 1 [ Cuz ( TMA ) 2 (H2O ) 3 ] viewed along the cell body Zn -HKUST - 1 metal organic framework . diagonal, showing a hexagonal- n shaped window at the [ 0071 ] FIG . 28 is the chemical equation and general intersection of the nanopores and giving rise to the nano scheme for the oxidation of toluene . channels . [0072 ] FIG . 29 is the chemical equation and general [0052 ] FIG . 9 is a schematic representation of the scheme for the oxidation of cyclohexane . HKUST- 1 polymer framework nanochannels with four - fold 10073 ] FIG . 30 is the chemical equation and general symmetry, formed from an octahedral secondary building scheme for the oxidation of methylcyclohexane. unit (SBU ) with Cu , at its 6 vertices and 4 trimesate ions [00741 . FIG . 31 is a comparative PXRD analysis showing tetrahedrally disposed as “ panels ” for four of the eight PXRD patterns of the unused prepared HKUST- 1 metal triangular faces of the octahedron organic framework and the used prepared HKUST- 1 metal [ 0053 ] FIG . 10 is a general schematic representation of the organic framework after use as a catalyst in the oxidation of activation of the HKUST- 1 metal organic framework by a cyclic hydrocarbon . removal of axial aqua ligands to give unsaturated metal sites [0075 ] FIG . 32 is a graph showing the percent conversion without affecting the rigid framework of the MOF . and the percent benzaldehyde selectivity of the prepared [0054 ] FIG . 11 is the general scheme and procedure for the HKUST- 1 metal organic framework after a single and mul synthesis of the prepared HKUST- 1 metal organic frame tiple runs as a catalyst in the oxidation of toluene . work from Cu (NO3 ) 2 -3H20 and 1 , 3 , 5 - benzenetricarboxylic acid (BTC ) . DETAILED DESCRIPTION OF THE [0055 ] FIG . 12 is the general scheme and procedure for the EMBODIMENTS synthesis of the prepared Zn -HKUST - 1 metal organic frame [0076 ] Referring now to the drawings , wherein , like ref work from Zn ( NO3) 2 6H20 and 1 , 3 , 5 - benzenetricarboxylic erence numerals designate identical or corresponding parts acid (BTC ) . throughout the several views. Embodiments of the present US 2017 /0326536 A1 Nov . 16 , 2017 disclosure will now be described more fully hereinafter with phase of the catalyst differs from that of the reactants or reference to the accompanying drawings, in which some, but substrates . As used herein , homogeneous catalyst refers to not all of the embodiments of the disclosure are shown . catalysts where the phase of the catalyst is the same as that [0077 ] Within the description of this disclosure , where a of the reactants . In terms of the present disclosure , the metal numerical limit or range is stated , the endpoints are included organic framework in any of its embodiments may function unless stated otherwise . Also , all values and subranges as a heterogeneous catalyst, a homogeneous catalyst , or have within a numerical limit or range are specifically included as components that function and have properties of both a if explicitly written out . As used herein , the words " a " and heterogeneous catalyst and a homogeneous catalyst . In a “ an ” and the like carry the meaning of “ one or more ” . The preferred embodiment, the metal organic framework catalyst phrases " selected from the group consisting of” , “ chosen of the present disclosure in any of its embodiments functions from " , and the like include mixtures of the specified mate as a heterogeneous catalyst . Preferably the metal organic rials . Terms such as “ contain (s ) ” and the like are open terms framework catalyst composition is employed in at least one meaning " including at least” unless otherwise specifically chemical transformation , preferably an oxidation , preferably noted . a selective oxidation [0078 ] According to a first aspect , the present disclosure [0082 ] Metal organic frameworks (MOFs ) may often be relates to a metal organic framework catalyst comprising i) employed as heterogeneous catalysts . Their high surface zinc (II ) ions , ii ) second metal ions which are not zinc (II ) area, tunable porosity , diversity in metal and functional ions, and iii ) benzene- 1 , 3 , 5 - tricarboxylic acid ligands, groups make them especially attractive for use as catalysts . wherein the benzene - 1 , 3 , 5 - tricarboxylic acid ligands com Similarly , zeolites are often employed in catalysis ; however, prise carboxylate groups, each carboxylate group forming a zeolites are limited by the fixed tetrahedral coordination of coordinative bond to the zinc ( II) ions or the second metal the Si/ Al connecting points and the two - coordinated oxide ions to form a coordination network in the form of porous linkers and only approximately 200 zeolites are known . In polyhedral crystals that are isostructural to an HKUST- 1 contrast with this limited scope , MOFs exhibit more diverse metal organic framework . coordination geometries , polytopic linkers , and ancillary [0079 ] As used herein , a metal organic framework (MOF ) ligands ( i. e . F - , OH®, H , O among others) . It is also chal refers to compounds consisting of metal ions or clusters lenging to obtain zeolites with pore sizes larger than 1 nm , coordinated to organic ligands to form one , two , or three which limits the catalytic applications of zeolites to rela dimensional structures . They are a subclass of coordination tively small organic molecules ( typically no larger than polymers and are often porous. The organic ligands included xylenes ). Furthermore , mild synthetic conditions typically are sometimes referred to as “ struts ” , one preferable employed for MOF synthesis allow direct incorporation of example being trimesic acid or benzene - 1, 3 ,5 -tricarboxylic delicate functionalities into the framework structures. Such acid ( C , H 00) . More formally , a metal organic framework a process would not be possible with zeolites or other is a coordination network with organic ligands containing microporous crystalline oxide- based materials because of potential voids. As used herein , a coordination network is a the harsh conditions typically used for their synthesis ( e . g . coordination compound extending , through repeating coor calcination at high temperatures to remove organic tem dination entities , in one dimension , but with cross - links plates ) . between two or more individual chains, loops , or spirolinks , [0083 ] Additionally , zeolites still cannot be obtained in or a coordination compound extending through repeating enantiopure form , which precludes their applications in coordination entities in two or three dimension ; and finally catalytic asymmetric synthesis, essential for use in the a coordination polymer is a coordination compound with pharmaceutical, agrochemical and fragrance industries . repeating coordination entities extending in one , two or Enantiopure chiral ligands or their metal complexes have three dimensions. In most cases, the pores are stable during been incorporated into MOFs leading to efficient asymmet elimination of the guest molecules (often solvents ) and ric catalysts. Even someMOF materials may bridge the gap metal organic frameworks find use for the storage of gases between zeolites and enzymes when they combine isolated such as hydrogen and carbon dioxide , gas purification , gas polynuclear sites , dynamic host - guest responses, and a separation , catalysis , sensors , and supercapacitors . hydrophobic cavity environment. Theoretical calculations [0080 ] Generally, metal organic frameworks (MOFs ) are show that MOFs are semiconductors or insulators with band composed of two major components , ( i ) a metal ion or gaps between 1 . 0 and 5 . 5 eV which can be altered by cluster of metal ions and ( ii ) an organic molecule called a changing the degree of conjugation in the ligands indicating linker. These materials may often be referred to as hybrid the further possibility of their use as photocatalysts . Like organic - inorganic materials . The organic units are typically other heterogeneous catalysts , MOFs may allow for easier mono - , di- , tri- , or tetravalent ligands . The choice of metal post- reaction separation and recyclability than homoge and linker dictates the structure and hence properties of the neous catalysts . In several cases , they also give highly MOF. For example , the metal' s coordination preference enhanced catalyst stability . Further , MOFs typically offer influences the size and shape of pores by dictating how many substrate -size selectivity . ligands can bind to the metal and in which orientation . [0084 ] Generally, the metal ions , preferably transition 10081 ] As used herein , catalysis is an increase in the rate metal ions , used can generate a wide range of structures. The of a chemical reaction due to the participation of an addi properties of these metals, including the oxidation state and tional substance termed a catalyst . Reactions tend to occur coordination number, preferably 2 to 7 , produce a linear, faster with a catalyst because the reaction requires less trigonal, square planar, tetrahedral, trigonal pyramidal, activation energy . Furthermore , since they are not consumed trigonalbipyramidal, octahedral, and pentagonal bipyrami in the catalyzed reaction , catalysts can continue to act dal geometries as well as some distorted forms. In a pre repeatedly , and often only tiny amounts are require . As used ferred embodiment, the metal organic framework of the herein , heterogeneous catalyst refers to catalysts where the present disclosure in any of its embodiments comprises zinc US 2017 /0326536 A1 Nov . 16 , 2017

( II ) ions and second metal ions which are not zinc ( II ) ions. C2H3N2 ) , and the like . Exemplary suitable neutral ligands Exemplary suitable second metal ions include, but are not included , but are not limited to , piperazine and 4 , 4 '- bipyri limited to , Ag , Ca , K , Zn , Na , Pb , Mn , Fe, Co , Ni, Al, Cu , dine . Sn , Cd , Hg, Cr, Fe , Bi, Ga , Ge , Au , In , TI, Rb , Cs, As, Sb , [0086 ] In a preferred embodiment, 5 - 80 % of the total Cr, Zn , V, Pt, Pd , Rh , and mixtures thereof. Further , these metal ions present in the metal organic framework catalyst metal ions may be of any oxidation state M + 1, M +2 , M + 3, of the present disclosure in any of its embodiments are zinc etc . , preferably M2. In a preferred embodiment , the second ( II ) ions, preferably 6 -75 % , preferably 7 - 70 % , preferably metal ions are at least one selected from the group consisting 8 -68 % , preferably 10 - 66 % , preferably 15 - 50 % , preferably of Ag+ , A1 - , Bi3 + , Ce + + , Cr3 + , Co2 + , Cu² + , Fe3 + , Mn2+ , 20 - 40 % of the total metal ions present in the metal organic Mg2 +, Pd2 +, Sc3+ , v4 + , Zn2+ , and Zr+ + . In a most preferred framework catalyst of the present disclosure in any of its embodiment the second metal ions are at least one selected embodiments are zinc (II ) ions . In a preferred embodiment, from the group consisting of iron (II ) ions, cobalt ( II ) ions, 20 - 95 % of the total metal ions present in the metal organic and copper ( II ) ions . It is equally envisaged that the metal framework catalyst of the present disclosure in any of its organic framework of the present disclosure may be adapted embodiments are not zinc ( II) ions , preferably 25 - 94 % , to further comprise one or more additional metal ions in preferably 30 - 92 % , preferably 32 -91 % , preferably 34 - 90 % , addition to or in lieu of the zinc ( II) metal ions and second preferably 50 - 85 % , preferably 60 - 80 % of the total metal metal ions. Exemplary additional metal ions include, but are ions present in the metal organic framework catalyst of the not limited to , an alkali metal (Li , Na , K , etc . ) , an alkaline present disclosure in any of its embodiments are not zinc ( II ) earth metal (Mg , Ca , Sr, etc . ) a lanthanide metal (La , Ce, Eu , ions. In a preferred embodiment, the second metal ions are Yb , etc .) , an actinide metal ( Ac, Th , etc . ), or a post - transition copper ( II ) ions and 60 - 95 % of the total metal ions present metal ( Al, Sn , Pb , In , etc . ) . in the metal organic framework catalyst of the present [0085 ] In the formation of a metal organic framework , the disclosure in any of its embodiments are copper ( II ) ions, organic linkers must meet certain requirements to form preferably 65 -94 % , preferably 70 - 93 % , preferably 75 - 92 % , coordination bonds , primarily being multidentate, having at preferably 80 -91 % , preferably 85 - 90 % of the total metal least two donor atoms ( i. e . N -, O - , and / or S - ) and being ions present in the metal organic framework catalyst of the neutral and being neutral or anionic . The structure of the present disclosure in any of its embodiments are copper ( II ) metal organic framework is also affected by the shape , ions . In a preferred embodiment, the second metal ions are length , and functional groups present in the organic linker. at least one selected from the group consisting of iron ( II ) In certain embodiments, the metal organic framework of the ions and cobalt ( II) ions and 5 - 60 % of the total metal ions present disclosure comprises anionic ligands as organic present in the metal organic framework catalyst of the linkers , preferably polycarboxylates including , but not lim present disclosure in any of its embodiments are at least one ited to , di- , tri - , tetra - , and/ or hexacarboxylates . In a pre selected from the group consisting of iron ( II) ions and ferred embodiment, the metal organic framework of the cobalt ( II ) ions, preferably 10 -55 % , preferably 15 - 50 % , present disclosure in any of its embodiments comprises preferably 20 - 45 % , preferably 25 -40 % , preferably 30 - 38 % , benzene - 1 , 3 , 5 - tricarboxylic acid (trimesic acid , C . H 06 ) preferably 32 - 36 % of the total metal ions present in the ligands as the ligands, linkers, or struts . The benzene - 1 , 3 , metal organic framework catalyst of the present disclosure 5 - tricarboxylic acid ligands comprise carboxylate groups, in any of its embodiments are at least one selected from the with each carboxylate groups forming a coordinative bond group consisting of iron ( II ) ions and cobalt ( II ) ions. to the zinc ( II ) metal ions or the second metal ions as the [0087 ] In a preferred embodiment, the ratio of zinc ( II ) nodes , metal ions , or clusters of metal ions to form a ions to the additionalmetal ions is in the range of 0 .01 to 5 . 0 , coordination network . It is equally envisaged that the metal preferably 0 .02 to 4 . 0 , preferably 0 .04 to 3 . 5 , preferably 0 . 06 organic framework of the present disclosure may be adapted to 3. 0 , preferably 0. 08 to 2. 5 , preferably 0 . 1 to 2. 0 . In a to further comprise one or more additional organic ligands preferred embodiment, the second metal ions are copper ( II ) in addition to or in lieu of the benzene- 1 , 3 , 5 - tricarboxylic ions and the ratio of zinc ( II ) ions to copper ( II ) ions is in the acid ligands including , but not limited to , bidentate carbox range of 0 .01 to 1 . 0 , preferably 0 .02 to 0 . 9 , preferably 0 .03 ylics , tridentate carboxylates , azoles , neutral ligands , and to 0 .8 , preferably 0 .04 to 0 .7 , preferably 0 .05 to 0 .6 , pref squaric acid ( 3 ,4 - dihydroxy - 3 - cyclobutene- 1 , 2 - dione, erably 0 . 06 to 0 . 5 , preferably 0 . 07 to 0 . 4 , preferably 0 .08 to C2H ,02 ) . Exemplary suitable bidentate carboxylics include , 0 . 3 , preferably 0 .09 to 0 . 2 , preferably 0 .095 to 0 . 15 , pref but are not limited to oxalic acid ( ethanedioic acid , HOOC erably 0 . 1 to 0 . 125 . In a preferred embodiment, the second COOH ), malonic acid (propanedioic acid , HOOC metal ions are at least one selected from the group consisting (CH , ) – COOH ) , succinic acid ( butanedioic acid , HOOC of iron ( II ) ions and cobalt ( II) ions and the ratio of zinc ( II ) (CH2 ) 2 – COOH ), glutaric acid (pentanedioic acid , ions to the second metal ions is in the range of 0 . 5 to 5 . 0 , HOOC - (CH2 ) 2 – COOH ), phthalic acid (benzene - 1, 2 -di preferably 0 . 75 to 4 . 5 , preferably 1 . 0 to 4 . 0 , preferably 1 . 25 carboxylic acid , O -phthalic acid , C6H (COOH ) 2 ) , to 3 . 5 , preferably 1 . 5 to 3 . 0 , preferably 1 . 75 to 2 . 5 , prefer isophthalic acid (benzene - 1, 3 -dicarboxylic acid , m -phthalic ably 1 .8 to 2 .25 , preferably 1. 9 to 2 .20 . acid , CH (COOH ) , ) , terephthalic acid (benzene - 1 , 4 - dicar [0088 ] In a preferred embodiment, the benzene - 1 ,3 , 5 boxylic acid , BDC , p -phthalic acid , C6H (COOH ) 2 ) , biphe tricarboxylic acid ligands comprise carboxylate groups , with nyl- 4 , 4 ' - dicarboxylic acid , BPDC , HOOC — ( C6H4) 2 — each carboxylate groups forming a coordinative bond to the COOH ) , and the like . Exemplary tridentate carboxylates zinc ( 11 ) metal ions or the second metal ions to form a include , but are not limited to , citric acid (2 -hydroxy - 1 ,2 , 3 coordination network in the form of porous polyhedral propanetricarboxylic acid , (HOOC )CH C (OH (COOH ) CH2 crystals that are isostructural to an HKUST- 1 metal organic ( COOH ) , trimesic acid , and the like . Exemplary azoles framework . As used herein , isostructural refers to chemical include, but are not limited to , 1 , 2 , 3 - triazole ( 1H - 1 , 2 , 3 compounds having similar chemical structures . As used triazole , C2H2N3) , pyrrodiazole ( 1H - 1 , 2 ,4 - triazole , herein , isomorphous when used in relation to crystal struc US 2017 /0326536 A1 Nov . 16 , 2017 tures is essentially synonymous . Two crystals are said to be romethane ormethanol resulting in the chemically activated isostructural if they have the same structure , but not neces metal organic framework catalyst with exposed M2+ sites. sarily the same cell dimensions not the same chemical [0090 ] In certain embodiments , the metal organic frame composition , and with a “ comparable ” variability in the work of the present disclosure may be considered a Lewis atomic coordinates to that of the cell dimensions and chemi acid solid or to possess Lewis character , especially at the cal composition . Isostructural may further refer to isostruc metal sites M2+ of the trinuclear networks. The structure of tural series of isostructural polymorphs or isostructural such metal organic frameworks is composed of the second phase transitions .Many minerals are isostructural when they ary building unit with tetracoordinate metal centers in axial differ only in the nature of a cation . The term isotypic may position of easy access offering a high concentration of be used as synonymous with isostructural. For example , Lewis acidic sites and M2+ ions that are exposed ont eh borazine is isostructural with benzene , indium ( 1 ) bromide is surface of the framework and might serve as potent Lewis isostructural with P -thallium ( I) iodide , and I -Gold ( 1) bro acids. As used herein , a Lewis acid catalyst or Lewis acid mide is isostructural with gold ( I) chloride. Additionally, catalysis refers to organic reactions wherein a metal- based isostnructural may further refer to compounds which are Lewis acid acts as an electron pair acceptor to increase the isoelectronic which usually have similar chemical struc reactivity of a substrate . Common Lewis acid catalyst are tures , such as , for example methane , CH . , and the ammo based on main group metals including , but not limited to , nium ion , NH4, which are both isoelectric and isostructural aluminum , boron , silicon , and tin , as well as many early ( i . e . as both have a tetrahedral structure , the C - H and N - H titanium , zirconium ) and late (i . e . iron , copper, zinc ) d -block bond lengths are different and crystal structures are different. metals . Generally , the metal atom forms an adduct with a [0089 ] In a preferred embodiment, the metal organic lone - pair bearing electronegative atom in the substrate such framework forms a highly porous metal - coordination poly as oxygen (both sp or sp ) , nitrogen , sulfur, and / or halo mer [ M (BTC ) , ( H ,Ozl , (wherein BTC is benzene - 1 , 3 , 5 gens . The complexation generally has partial charge - transfer tricarboxylate and M is zinc ( II ) and / or the second metal, character and makes the lone - pair donor effectively more preferably iron ( II ) , copper ( II ) , and cobalt ( II ) 0 which has electronegative , activating the substrate toward nucleophilic interconnected [M2 ( 02CR ) 4 ] units , C18H / 2015M3( wherein attack , heterocyclic bond cleavage , or cycloaddition . Many R is an aromatic ring ) . Preferably, this creates a 3 -dimen reactions, such as for example , selective oxidation , involv sional system of channels with a pore size of 0 . 2 - 2 .0 nm , ing carbon - carbon or carbon -heteroatom bond formation can preferably 0 . 3 - 1 . 9 nm , preferably 0 . 4 - 1 . 8 nm , preferably be catalyzed by Lewis acids. 0 . 5 - 1 . 7 nm , preferably 0 .6 - 1 . 8 nm , preferably 0 . 7 - 1 . 6 nm , [ 0091 ] In a preferred embodiment, the metal organic preferably 0 .8 - 1 . 5 nm , preferably 0 . 9 - 1 .4 nm , preferably framework of the present disclosure forms porous polyhe 1 . 0 - 1 . 3 nm , preferably 1 . 1 - 1 . 2 nm and an accessible porosity dral crystals , the polyhedral crystals are preferably octahe of greater than 30 % in the solid . The polymer framework is dral or cubic in shape with an average diameter or longest composed of dimeric metallic tetracarboxylate building linear dimension of 2 - 20 um , preferably 4 - 18 um , preferably units with a metal ion inter nuclear separation of 2 - 3 Å , 6 - 16 um , preferably 8 - 14 um , preferably 9 - 13 um , preferably preferably 2 .2 - 2. 8 Å , preferably 2 .4 - 2. 7 Å , preferably 2 . 5 10 - 12 um , preferably 11 . 1 - 11. 9 um . 2 .65 Å . The framework is preferably neutral because the [ 0092 ] In crystallography, crystal structure is a description twelve carboxylate oxygens from the two BTC ligands bind of the ordered arrangement of atoms, ions or molecules in a to four coordination sites for each of the three MP+ ions of crystalline material. Ordered structures occur from the the formula unit. Hence teach metal atom completes its intrinsic nature of the constituent particles to form symmet pseudo -octahedral coordination sphere with the presence of ric patterns that repeat along the principal directions of three axial aqua ligands opposite to the M - M dimer. The tetrac dimensional space in matter . The smallest group of particles arboxylate unit provides a structural motif with potential in the material that constitutes the repeating pattern is the four - fold symmetry , and the trimesic acid provides a three unit cell of the structure . The unit cell completely defines the fold symmetry element . The origin of the nano -challels can symmetry and structure of the entire crystal lattice , which is be considered to arise from the formation of larger octahe built up by repetitive translation of the unit cell along its dral secondary building units (SBU ) . Preferably , the main principal axes . The repeating pattern is said to be located at SBU in the metal organic framework catalyst of the present the points of the Bravais lattice . The lengths of the principal disclosure is the octahedral unit with M , at its 6 vertices and axes , or edges, of the unit cell and the angles between them 4 trimesate ions tetrahedrally disposed as " panels” for four are the lattice constants , or lattice parameters , the symmetry of the eight triangular faces of the octahedron . The frame properties of the crystal are described by the concept of work may be composed of an array of 32 M -M paddlewheels space groups . The crystal structure and symmetry play a per crystallographic unit cell, connected in three dimensions critical role in determining many physical properties . Sub by 1 , 3 , 5 -benzene tricarboxylate . This ligand arrangement units ofmetal organic frameworks , termed secondary build results in two coordinatively unsaturated M sites per paddle ing units (SBU ) can be described by topologies common to wheel which polar molecules can interact with . The paddle several structures . Each topology , also called a net, is wheels are preferably stable in both the coordinatively assigned a symbol, consisting of three lower - case letters. In saturated and unsaturated arrangements . It is possible to a preferred embodiment, the metal organic framework cata prepare the metal organic framework of the present disclo lyst of the present disclosure in any of its embodiments sure that crystallizes with stoichiometric amounts of water crystallizes with a structural topology referred to as the tbo coordinated to each M2+ ion . Anhydrous ( or " activated ) type in space group Fm3m which relates to " twisted ” metal organic framework catalyst where the axial aqua boracite . ligands are removed giving unsaturated metal sites by gentle [0093 ] The crystal structure of a material ( the arrangement heating under low pressure and or by soaking in a polar of atoms within a given type of crystal) can be described in protic solvent or non - polar solvent, preferably dichlo terms of its unit cell . The unit cell is a box containing one US 2017 /0326536 A1 Nov . 16 , 2017 or more atoms arranged in three dimensions. The unit cells surface and serves as the basis for an important analysis stacked in three dimensional space describe the bulk technique for themeasurement of the specific surface area of arrangement of atoms of the crystal. The unit cell is repre a material. Specific surface area is a property of solids which sented in terms of its lattice parameters, which are the is the total surface area of a material per unit of mass , solid lengths of the cell edges ( a , b , and c ) and the angles between or bulk volume, or cross sectional area . In a preferred them (alpha , beta and gamma) , while the positions of the embodiment the metal organic framework catalyst of the atoms inside the unit cell are described by the set of atomic present disclosure in any of its embodiments has a BET positions ( X ; , Y ; , z ; ) measured from a reference lattice point. surface area in the range of 500 - 3000 m - / g , preferably Commonly atomic positions are represented in terms of 750 - 2500 m²/ g , preferably 1000 -2000 m²/ g , preferably fractional coordinates, relative to the unit cell lengths. In a 1250 - 1750 m²/ g , preferably 1400 - 1600 m²/ g , or about 1500 preferred embodiment , the metal organic framework catalyst m²/ g . of the present disclosure in any of its embodiments has a 0098 ). According to a second aspect, the present disclo larger unit cell dimension a ( length of cell edge ) than the sure relates to a process for producing the metal organic HKUST- 1 metal organic framework , preferably at least a framework in any of its embodiments comprising i) reacting 0 .025 Å larger unit cell dimension a, preferably at least 0 .05 1 , 3 , 5 - benzenetricarboxylic acid with a zinc ( II ) salt or A larger, preferably at least 0 .075 A larger , preferably at least hydrate in a solvent at a temperature greater than 25° C . to 0 . 10 A larger, preferably at least 0 .125 A larger, preferably form a zinc modified metal organic framework and ii ) at least 0 . 15 A larger, preferably at least 0 . 175 A larger , transmetallating at least a portion of the zinc modified metal preferably at least 0 . 2 A larger , preferably at least 0 . 25 A organic framework by immersing in a solution of a salt or larger , preferably at least 0 . 3 A larger unit cell dimension a . hydrate of the second metal ions . [ 0094 ] Porosity is defined as the percentage of void space [0099 ] The physicochemical characteristics of metal in a solid . As used herein , porous materials are those where organic frameworks can be modulated and many of these the void space is deliberately introduced to fulfill certain properties can be modified in the material from the synthesis functions. Total porosity (volume fraction of pores) is process . In a preferred embodiment, the metal organic defined as o = 1 - P ., , where pr = plp , and is the relative density framework of the present disclosure is produced by a of the solid phase matrix or skeleton ( p = bulk density and solvothermal method . Typically the solvothermal synthesis Pe = theoretical density ) . It is expressed as a percentage of the comprises the reaction of one or more metal salts and one or theoretical density ( TD ) of the solid as a whole . In a more organic ligands in the presence of preferably organic preferred embodiment, themetal organic framework catalyst solvents or mixtures, preferably involving formamide, alco of the present disclosure has a percent porosity of at least hols , or pyrrolidones . Important parameters in the solvother 30 % , preferably at least 35 % , preferably at least 40 % , mal synthesis include , but are not limited to , temperature , preferably at least 45 % , preferably at least 50 % , preferably concentration of reactants (which can be varied over a wide at least 55 % , preferably at least 60 % , preferably at least range ) and pH of the reaction solution . It is equally envis 65 % , preferably at least 70 % . aged that the present process in any of its embodiments may [0095 ] In a preferred embodiment , the metal organic be adapted to produce the metal organic framework of the framework catalyst of the present disclosure in any of its present disclosure in any of its embodiments by other embodiments forms porous polyhedral crystals having pores methods of synthesis which may be used to tailor the with an average diameter or aperture of 0 . 2 - 2 . 0 nm , prefer properties of the metal organic framework . Exemplary suit ably 0 . 3 - 1 . 9 nm , preferably 0 . 4 - 1 . 8 nm , preferably 0 . 5 - 1 . 7 able methods that may be used in addition to or in lieu of a nm , preferably 0 . 6 - 1 . 8 nm , preferably 0 . 7 - 1 . 6 nm , preferably solvothermalmethod include , but are not limited to , mecha 0 . 8 - 1 .5 nm , preferably 0 . 9 - 1. 4 nm , preferably 1 .0 - 1 . 3 nm , nochemical methods, electrochemistry methods , assisted preferably 1 . 1 - 1 . 2 nm . In certain embodiments , the metal synthesis methods ( i . e . by ultrasound or microwave ) , and organic framework catalyst of the present disclosure features subcritical water methodsW . three distinct internal pores , two of comparable size ( 0 . 8 - 1 . 6 [0100 ] In one step of the process, 1 , 3, 5 -benzentricarbox nm , preferably 0 . 9 - 1 . 4 nm ) and a smaller pore ( 0 . 2 - 1 . 4 nm , ylic acid is reacted with a zinc ( II ) salt or hydrate in a solvent preferably 0 . 8 - 1 . 2 nm , or about) . One of the two larger pores at a temperature greater than 25° C . to form a zinc modified preferably features metal ion bonds to metal ions ( M - M ) metal organic framework . directed into the pores . In certain embodiments , the metal [0101 ] As used herein , the term " solvent” refers to and organic framework may comprise square shaped pores of includes, but is not limited to , water ( e . g . tap water , distilled 0 .2 - 2 . 0 nm by 0 . 2 - 2 .0 nm . water , deionized water , deionized distilled water ) , organic [ 0096 ] As used herein , bulk density is a property of solvents , such as ethers ( e . g . diethyl ether , tetrahydrofuran , powders , granules and other “ divided ” solids , especially 1 ,4 -dioxane , tetrahydropyran , t- butyl methyl ether , cyclo used in reference to mineral components and chemical pentyl methyl ether, di- iso - propyl ether) , glycol ethers ( e . g . substances or any other masses of corpuscular or particulate 1 , 2 - dimethoxyethane , diglyme, triglyme ) , alcohols ( e . g . matter. It is defined as the weight of many particles of the methanol, ethanol, trifluoroethanol , n -propanol , i- propanol, material divided by the total volume they occupy. The total n -butanol , i- butanol , t- butanol , n -pentanol , i- pentanol , volume includes particle volume, inter -particle void volume, 2 -methyl - 2 - butanol, 2 - trifluoromethyl- 2 - propanol , 2 , 3 - dim and internal pore volume. In a preferred embodiment, the ethyl- 2 -butanol , 3 -pentanol , 3 -methyl - 3 - pentanol, 2 -methyl metal organic framework of the present disclosure in any of 3 - pentanol, 2 -methyl - 2 -pentanol , 2 , 3 - dimethyl- 3 -pentanol , its embodiments has a bulk density of 0 . 1 - 1 . 0 g / cm " , pref 3 - ethyl- 3 - pentanol, 2 -methyl - 2 -hexanol , 3 -hexanol , cyclo erably 0 . 15 - 0 . 8 g / cm " , preferably 0 . 2 - 0 .6 g / cm " , preferably propylmethanol, cyclopropanol, cyclobutanol, cyclopenta 0 . 25 - 0 . 4 g / cm , preferably 0 . 3 - 0 .35 g / cmº. nol, cyclohexanol) , aromatic solvents ( e . g . benzene , 0 - xy [0097 ) The Brunauer- Emmet- Teller (BET ) theory aims to lene , m -xylene , p - xylene , mixtures of xylenes , toluene , explain the physical adsorption of gas molecules on a solid mesitylene, anisole , 1, 2 - dimethoxybenzene , 2 , 0 , - trifluo US 2017 /0326536 A1 Nov . 16 , 2017 romethylbenzene , fluorobenzene ) , chlorinated solvents ( e . g . well as inorganic molecules, form crystals that incorporate chlorobenzene , dichloromethane , 1 , 2 -dichloroethane , 1 , 1 water into the crystalline structure without chemical altera dichloroethane , chloroform ) , ester solvents ( e . g . ethyl tion of the organic molecule . In inorganic chemistry , acetate , propyl acetate ), amide solvents ( e . g . dimethylfor hydrates are inorganic salts containing water molecules mamide , dimethylacetamide , N -methyl - 2 -pyrrolidone ), urea combined in a definite ratio as an integral part of the crystal solvents , ketones ( e . g . acetone , butanone ) , acetonitrile , pro that are either bound to a metal center or that have crystal pionitrile, butyronitrile , benzonitrile , dimethyl sulfoxide , lized with the metal complex . The notation of a hydrated ethylene carbonate , propylene carbonate , 1 , 3 - dimethyl- 3 , 4 , compound ( n -H2O ) where n is a number of water molecules 5 ,6 -tetrahydro - 2 ( 1H ) - pyrimidinone, and mixtures thereof. per formula unit of the salt is commonly used to show that As used herein solvent may refer to non -polar solvents ( e . g . a salt is hydrated . The n is usually a low integer, though it hexane , benzene , toluene , diethyl ether, chloroform , 1 , 4 - is possible for fractional values to occur. dioxane ) , polar aprotic solvents ( e. g . ethyl acetate , tetrahy [0105 ] Exemplary zinc salts or hydrates include , but are drofuran , dichloromethane, acetone, acetonitrile , dimethyl not limited to , zinc nitrate (Zn (NO3 ) 2 ), zinc chlorate formamide, dimethyl sulfoxide ) and polar protic solvents Zn (C102 ) 2, zinc sulfate (ZnSO2 ) , zinc phosphate (Znz ( POA) ( e. g . acetic acid , n -butanol , isopropanol, n -propanol , etha 2 ) zinc molybdate ( ZnM004) , zinc chromate (ZnCrO2 ) , zinc nol, methanol, formic acid , water ) and mixtures thereof. arsenite ( Zn (Aso , ) , ) , zinc arsenate octahydrate ( Zn (AsO2 ) [0102 ] In a preferred embodiment, the reacting is per 2 .8H2O ) , zinc acetate (Zn (OCCH3 ) 2 ) , zinc bromide , zinc formed in a non -polar solvent. Exemplary suitable non -polar bromide dehydrate , zinc chloride, zinc citrate dihydrate , zinc solvents include , but are not limited to , pentane , cyclopen cyanide, zinc fluoride, zinc hexafluorosilicate , zinc iodide, tane , hexane , cyclohexane , benzene , toluene , 1 , 4 - dioxane , zinc methacrylate, zinc nitrate hydrate , zinc oxalate hydrate , chloroform , diethyl ether, dichloromethane and mixtures zinc perchlorate hexahydrate , zinc selenite , zinc sulfate thereof, preferably the solvent is dichloromethane . It is heptahydrate , zinc tetrafluoroborate hydrate , zinc p - toluene equally envisaged that the present process may be adapted to sulfonate hydrate , and the like . In a preferred embodiment, incorporate polar protic solvent including , but not limited to , the zinc ( II ) salt or hydrate is Zn (NO3 )2 .6H20 . formic acid , n - butanol , isopropanol, n - propanol, ethanol, f0106 ] In a preferred embodiment, the zinc (II ) salt or methanol, acetic acid , and water , as well as polar aprotic hydrate is the limiting reagent in the process . In certain solvents including, but not limited to , tetrahydrofuran , ethyl embodiments , an amount of the zinc (II ) salt or hydrate is in acetate , acetone , dimethylformamide , acetonitrile , dimethyl a range of 0 . 01 - 100 mmol, preferably 0 . 1 - 20 mmol, prefer sulfoxide , nitromethane , propylene carbonate and mixtures ably 0 . 15 - 10 mmol, preferably 0 . 175 - 5 mmol. thereof. [0107 ] In a preferred embodiment, the zinc ( II ) salt or [ 0103 ] As used herein , a salt refers to an ionic compound hydrate is present at a concentration of 0 .001 - 10 M in the resulting from the neutralization reaction of an acid and a solvent of the reaction mixture , preferably 0 .01 - 5M , pref base . Salts are composed of related numbers of cations erably 0 . 1 - 1 M in the solvent of the reaction mixture . In a (positively charged ions ) and anions (negative ions) such preferred embodiment, the 1 , 3 , 5 - benzenetricarboxylic acid that the product is electrically neutral (without a net charge ) . may be present in an excess of 1 . 5 - 20 molar equivalents of These component ions can be inorganic ( i. e . chloride , Cl- ) the zinc (11 ) salt or hydrate , preferably 2 - 15 molar equiva or organic (i . e . acetate , CH3CO2 ) and can be monoatomic lents , preferably 4 - 12 molar equivalents , preferably 6 - 10 ( i . e . fluoride , F ) or polyatomic ( i . e . sulfate , SO22 ) . Exem molar equivalents of the zinc ( II ) salt or hydrate . plary conventional salts include, but are not limited to , those [0108 ] In a preferred embodiment the reacting may be derived from inorganic acids including, but not limited to , performed at a temperature of 25 - 140° C . , preferably hydrochloric , hydrobromic , sulfuric , sulfamic , phosphoric , 40 - 120° C . , preferably 45 - 110° C . , preferably 50 - 100° C . , and nitric ; and those derived from organic acids including, preferably 60 - 95° C ., preferably 70 - 90° C ., or about 85° C . but not limited to , acetic , propionic , succinic, glycolic , In a preferred embodiment, the reacting may be performed stearic , lactic , malic , tartaric , citric , ascorbic , pamoic , for a time period of 2 - 36 hours , preferably 4 -30 hours , maleic , hydroxymaleic , phenylacetic , glutamic , benzoic , preferably 6 - 24 hours , preferably 8 - 20 hours, preferably salicyclic , sulfanilic , 2 - acetoxybenzoic , fumaric , toluenesul 10 - 18 hours , preferably 12 - 16 hours . The zinc modified fonic , methanesulfonic , ethane disulfonic , oxalic , isethionic , metal organic framework may be isolated and purified by and mixtures thereof and the like . methods known to those of ordinary skill in the art , such a [0104 ] As used herein , a solvate refers to a physical filtration , decantation , aqueous work - up , extraction with association of a compound with one or more solvent mol organic solvents , distillation , crystallization , column chro ecules, whether organic or inorganic , preferably water in a matography , and high pressure liquid chromatography hydrate . This physical association may include hydrogen (HPLC ) on normal phase or reversed phase . bonding . In certain instances the solvent molecules may be [0109 ] In a preferred embodiment, the obtained zincmodi incorporated in the crystal lattice of the crystalline solid . The fied metal organic framework crystals are washed or rinsed solvent molecules may be present in a regular arrangement with a polar aprotic solvent, preferably dimethylformamide and / or a non - ordered arrangement. The solvate may com 1 - 10 times, preferably 2 - 5 times , or about 3 times to obtain prise either a stoichiometric or nonstoichiometric amount of preferably colorless cubic crystals . In certain embodiments , the solvent molecules. Solvate encompasses both solution the reacting may further comprise activating the zinc modi phase and isolable solvates . As used herein , a hydrate is a fied metal organic framework . As used herein , activation substance that contains water or its constituent elements . refers to removal of axial aqua ligands from a metal organic The chemical state of the water varies widely between framework , the activation giving unsaturated metal sites different classes of hydrates . In organic chemistry , a hydrate without affecting the rigid framework of the metal organic is a compound formed by the addition of water or its framework . In a preferred embodiment, the zinc modified elements to another molecule . Many organic molecules , as metal organic framework is activated by soaking in a polar US 2017 /0326536 A1 Nov . 16 , 2017 protic solvent or non - polar solvent, preferably dichlo ment the immersion is performed for a time period of 1 - 120 romethane or methanol, most preferably methanol for 1 - 10 hours, preferably 12 - 96 hours, preferably 24 -84 hours , pref days, preferably 2 - 5 days, or about 3 days optionally with erably 36 - 78 hours , preferably 48 - 72 hours . In a preferred decanting and replenishment of fresh solvent. The obtained embodiment, the solution of a salt or hydrate of the second zinc modified metal organic framework may further be dried metal ions comprises a polar protic solvent or non -polar under preferably reduced pressure ( i . e . vacuum ) at a tem solvent, preferably dichloromethane or methanol, most pref perature of 50 -300° C . , preferably 100 - 250° C ., preferably erably methanol as a solvent . The thereby obtained metal 125 - 200° C ., preferably 150 - 180° C . organic framework catalyst may be isolated and purified by [ 0110 ] In another step of the process , at least a portion of methods known to those of ordinary skill in the art , such a the zinc modified metal organic framework is transmetal filtration , decantation , aqueous work - up , extraction with lated by being immersed in a solution of a salt or hydrate of organic solvents , distillation , crystallization , column chro the second metal ions. matography, and high pressure liquid chromatography [ 0111] As used herein transmetallating or transmettalation (HPLC ) on normal phase or reversed phase . refers to a type of organometallic reaction that involves the 0114 ] In a preferred embodiment, the obtained metal transfer of ligands from one metal to another . Generally the organic framework catalyst crystals are washed or rinsed reaction is an irreversible process due to thermodynamic and with a polar protic solvent, preferably methanol. In certain kinetic reasons. Thermodynamics will favor the reaction embodiments , the transmetallating may further comprise based on the electronegativities of the metals and kinetics activating the metal organic framework catalyst . In a pre will favor the reaction if there are empty orbitals on both ferred embodiment, the metal organic framework catalyst is metals . In terms of the present disclosure , the transmetalla activated or washed for remove any residual metal ions by tion may be redox - transmetallation and / or redox - transmet soaking in a polar protic solvent or non -polar solvent, allation / ligand exchange , preferably redox - transmetallation / preferably dichloromethane or methanol, most preferably ligand exchange . methanol. The obtained cation - exchanged metal organic [ 0112] In a preferred embodiment, the second metal ions framework may further be dried under preferably reduced are at least one selected from the group consisting of iron ( II ) pressure ( i. e . vacuum ) at a temperature of 10 - 100° C . , ions, cobalt ( II ) ions , and copper ( II) ions. Exemplary preferably 15 - 80° C ., preferably 20 -60° C ., preferably suitable salts or hydrates of the second metal ions include, 25 - 40° C . but are not limited to , copper ( II ) bromide, copper ( II) [0115 ] According to a third aspect , the present disclosure chloride, copper ( II ) chloride dihydrate , copper ( II ) cyclo relates to a method for an oxidation of a cyclic hydrocarbon hexanbutyrate , copper ( II ) fluoride, copper ( II ) fluoride comprising contacting the cyclic hydrocarbon with the metal hydrate, copper ( II ) hydroxide , copper ( II ) hydroxide phos organic framework catalyst of the present disclosure in any phate , copper ( II ) molybdate, copper ( II ) nitrate , copper ( II ) of its embodiments in the presence of a solvent and an nitrate hemi( pentahydrate ), copper ( II ) nitrate hydrate , cop oxidizing agent to form an oxidized cyclic hydrocarbon . per ( II ) perchlorate , copper ( II ) pyrophosphate hydrate , [0116 ] As used herein , oxidation refers to the loss of copper ( II ) selenite dehydrate , copper ( II ) sulfate , copper ( II ) electrons or the increase in oxidation state by a molecule , sulfate pentahydrate , copper ( II ) tartrate hydrate , copper ( II ) atom , or ion ( i . e . the cyclic hydrocarbon ) . Redox (short for tetrafluoroborate hydrate , tetraamminecopper (II ) sulfate reduction - oxidation reaction ) is a chemical reaction in which monohydrate , ammonium cobalt ( II ) sulfate hexahydrate , the oxidation states of atoms are changed . Any such reaction cobalt ( II ) bromide, cobalt ( II ) carbonate hydrate , cobalt ( II ) involves both a reduction process and a complimentary chloride , cobalt ( II ) chloride hydrated , cobalt ( II ) cyanide oxidation process, two key concepts involved with electron dehydrate , cobalt ( II) fluoride , cobalt ( II ) fluoride tetrahy transfer processes. Redox reactions include all chemical drate , cobalt ( II ) hydroxide , cobalt ( II) iodide , cobalt ( II ) reactions in which atoms have their oxidation state changed ; nitrate hexahydrate , cobalt ( II ) oxalate dehydrate , cobalt ( II ) in general, redox reactions involve the transfer of electrons perchlorate hexahydrate , cobalt ( II) phosphate hydrate , between chemical species . The chemical species from which cobalt ( II) sulfate heptahydrate , cobalt ( II) sulfate hydrate , the electron is stripped is said to have been oxidized , while cobalt ( II ) tetrafluoroborate hexahydrate , cobalt ( II ) thiocya the chemical species to which the electron is added is said nate, ammonium iron ( II ) sulfate hexahydrate , iron ( II ) to have been reduced . The processes of oxidation and bromide , iron ( II ) chloride, iron ( II ) chloride tetrahydrate , reduction occur simultaneously and cannot happen indepen iron ( II ) fluoride , iron (II ) iodide , iron (II ) molybdate , iron dently of one another. Although oxidation and reduction ( II ) oxalate dehydrate , iron ( II ) perchlorate hydrate , iron ( II ) properly refer to change in oxidation state , the actual transfer sulfate hydrate , iron ( II ) tetrafluoroborate hexahydrate , of electronsmay not actually occur. The oxidation state of an potassium hexacyanoferrate (II ) trihydrate , and the like . In a atom refers to the fictitious change that an atom would have preferred embodiment, the salt or hydrate of the second if all bonds between atoms of different elements were 100 % metal ions is at least one selected from the group consisting ionic . Thus , oxidation can best be defined as an increase in of Cu ( NO3) 2 . 3H2O , CO (NO3 ) 2 . 6H2O , and FeCl2 . 6H20 . oxidation , and reduction as a decrease in oxidation state . In [0113 ] In a preferred embodiment , the zinc modified metal practice , the transfer of electrons will always cause a change organic framework is the limiting reagent and is immersed in oxidation state ; however, many reactions may be classi in a 0 .01 - 10 M solution of a salt or hydrate of the second fied as redox even though no electron transfer occurs ( i. e . metal ions , preferably 0 .05 - 5 . 0 M , preferably 0 . 1 - 1 . 0 M , those involving covalent bonds ) . As used herein , catalytic preferably 0 . 25 - 0 .75 M solution of a salt or hydrate of the oxidations are processes that oxidize compounds using second metal ions . In a preferred embodiment the immersion catalysts . is performed at a temperature of 10 - 100° C . , preferably [0117 ] In terms of the present disclosure, the oxidations 20 -80° C ., preferably 25 -70° C . , preferably 30 -60° C ., may be classified into groups depending on the type of bond preferably 35 - 50° C ., or about 40° C . In a preferred embodi change involved . These groups may include, but are not US 2017 /0326536 A1 Nov . 16 , 2017 limited to , eliminations of hydrogen , reactions involving [0120 ] In certain embodiments , the cyclic hydrocarbon is cleavage of carbon - carbon bonds , reaction involving an alicyclic compound or carbocycle . As used herein an replacement of hydrogen by oxygen , reactions in which alicyclic compound is an organic compound that is both oxygen is added to the substrate , and oxidative coupling, aliphatic and cyclic . They may contain one or more all preferably reactions involving replacement of hydrogen by carbon rings which may be either saturated or unsaturated , oxygen . In inorganic chemistry, where ionic bonds are but do not have aromatic character. Alicyclic compounds common , an oxidation may be defined as the loss of one or may have one or more aliphatic side chains attached , such as more electrons by an atom . In organic chemistry , however , for example , methylcyclohexane . In certain embodiments , where polar covalent bonds are common , an oxidation is a the cyclic hydrocarbon may be a simple alicyclic compound reaction that results in a loss of electron density by carbon . such as a monocyclic cycloalkane. Exemplary suitable This loss is usually caused either by bond formation between monocyclic cycloalkanes include , but are not limited to , carbon and a more electronegative atom ( usually oxygen , cyclopropane, cyclobutane , cyclopentane, cyclohexane , nitrogen , or a halogen ) or by bond breaking between carbon cycloheptane, cyclooctane , cyclotridecane, and the like, and a less electronegative atom (usually hydrogen ). Thus, preferably cyclohexane. In certain embodiments , the cyclic oxidation refers to a decrease of electron density of carbon hydrocarbon may be a bicyclic or polycyclic alkane . Exem by forming for example C — 0 , C - N , and / or C — X bonds plary bicyclic or polycyclic alkanes include, but are not or breaking C - H bonds . limited to , bicycloundecane , norbornane , decalin , cubane , [0118 ] The practice in organic chemistry is to designate a basketane , housane , and the like . In certain embodiments , series of functional groups, in a qualitative way , arranged in the cyclic hydrocarbon may be a spiro compound . As used order of increasing oxidation state , and then to define an herein , spiro compounds have two or more rings that are oxidation as a conversion of a functional group in a molecule connected through only one carbon atom . In certain embodi from one category to another. Alkanes are at the lowest ments , the cyclic hydrocarbon may be a monocyclic oxidation level in that they have the maximum possible cycloalkene ( cycloolefin ) or bicyclic cycloalkene . Exem number of C - H bonds, and Co , is at the highest level plary monocyclic or bicyclic cycloalkenes include, but are because it has the maximum possible number of C - O not limited to , cyclopropene, cyclobutene , cyclopentene , bonds. As used herein , any reaction that converts a com cyclohexene , cycloheptene , cyclooctene, 1 , 3 -cyclohexadi pound from a lower level to a higher level is an oxidation . ene , 1 , 4 - cyclohexadiene , 1 , 5 -cyclooctadiene , norbornene , It is noted that this classification applies generally to only a norbornadiene, methylenecyclohexane, 1 -methylcyclohex single carbon atom or two adjacent carbon atoms. For ene, and the like. In certain embodiments , the cyclic hydro example , CH CHz or RH can be thought to have a low carbon may comprise one or more exocyclic double bonds, oxidation state ( ~ - 4 ) , H2C = CH , or — C — C — , CH2OH or such as for example , the isotoluenes . ROH , CH2Cl or RC1, and CH NH , or RNH , can be thought [0121 ] In certain embodiments , the cyclic hydrocarbon is to have an increased oxidation state ( ~ - 2 ) , HC = CH or an aromatic hydrocarbon or arene . As used herein , an - C = C — , H2C = O or R R C = O , CH2Cl2 or R R2CCl2 , aromatic hydrocarbon or arene is a hydrocarbon with sigma H2C = NH , and HO C — C — OH can be thought to have a bonds and delocalized pi electrons between carbon atoms further increased oxidation state ( ~ 0 ) , HCO H or RCOOH , forming a circle. In contrast , aliphatic hydrocarbons lack this CHC1z or CRC1z , HC = N or RC = N and RCONH , can be delocalization . The configuration of six carbon atoms in thought to have an even further increased oxidation state aromatic compounds is known as a benzene ring , after the ( ~ + 2 ) , and CO2 and CCl4 can be though to have a highest simplest possible such hydrocarbon , benzene . In termsof the oxidation state ( ~ + 4 ) . As used herein , oxidation refers to loss present disclosure , the aromatic hydrocarbon may be mono of bonds to a hydrogen atom and / or gain of bonds to a more cyclic (MAH ) or polycyclic (PAH ) . In certain embodiments , electronegative element such as oxygen , nitrogen , and / or the the cyclic hydrocarbon is benzene or a benzene derivative . halogens, preferably oxygen . In a preferred embodiment, the As used herein , benzene derivatives refer to from one to six oxidation is a transition of a CH3 group to a HC = O or substituents attached to a central benzene core . Exemplary COOH group , or a CH , group to a HC - OH or C = O group , suitable benzene derivatives include , but are not limited to , or a CH group to a C – OH group . toluene , ethylbenzene, o -xylene , m -xylene , p -xylene , mixed [0119 ] As used herein , a hydrocarbon is an organic com xylenes , mesitylene , durene , 2 - phenylhexane, biphenyl, and pound consisting entirely of hydrogen and carbon and which the like, preferably toluene . are thus group 14 hydrides . Hydrocarbons from which one [0122 ] In certain embodiments , the cyclic hydrocarbon is hydrogen atom has been removed are functional groups a polycyclic aromatic hydrocarbon (PAH ) . As used herein a referred to as hydrocarbyls. Aromatic hydrocarbons polycyclic aromatic hydrocarbon is an aromatic hydrocar ( arenes ), alkanes, alkenes , cycloalkanes and alkyne -based bon that consists of fused aromatic rings and does not compounds are different types of hydrocarbons. As used contain heteroatoms or carry substituents . Exemplary suit herein a cyclic compound ( ring compound ) is a term for a able polycyclic hydrocarbons include , but are not limited to , compound in the field of chemistry in which one or more naphthalene , naphthenes , anthracene , phenathrene , tet series of atoms in the compound is connected to form a ring . racene, chrysene , triphenylene , pyrene , pentacene , benzo [ a ] Rings may vary in size from three to many atoms, and pyrene , corannulene , benzo [ g , h , i ] perylene , coronene, ova preferably refer to examples where all the ring atoms are lene , benzo [ c ] fluorene , acenaphthene, acenaphthylene , carbon (i . e . are carbocycles) . Depending on the ring size , the benzo [ a ]anthracene , benzo [ b ] fluoranthene, benzo [ j ] fluo bond order of the individual links between ring atoms, and ranthene , benzo [ k ] fluoranthene , benzo [ e ]pyrene , cyclopenta their arrangement within the rings the cyclic hydrocarbon [ c , d ]pyrene , dibenz [ a , h ] anthracene, dibenzo [a , e )pyrene , may be aromatic or aliphatic ( non -aromatic ) . In terms of the dibenzo [ a , h )pyrene , dibenzo [ a , i ]pyrene , dibenzo [ a , l] pyrene , present disclosure, the cyclic hydrocarbon may be aromatic fluoroanthene , fluorene , indeno [ 1, 2 , 3 - c , d )pyrene , 5 -methyl or aliphatic . chrysene and the like. US 2017 /0326536 A1 Nov . 16 , 2017 14

[0123 ] It is equally envisaged that the method of the be substituted may be selected from the group including, but present disclosure may be adapted to additional optionally not limited to , hydroxyl, amino , alkylamino , arylamino , substituted alkyl, cycloalkyl, aryl, or heterocyclic substrates alkoxy, aryloxy, nitro , cyano , sulfonic acid , sulfate , phos or similar moieties of larger and /or more complex com phonic acid , phosphate or phosphonate or mixtures thereof. pounds. The substituted moiety may be either protected or unpro 101241 As used herein , the term “ substituted ” refers to at tected as necessary , and as known to those skilled in the art . least one hydrogen atom that is replaced with a non [ 0128 ] As used herein , the term “ heterocyclyl ” unless hydrogen group , provided that normal valencies are main otherwise specified refers to a 3 - 8 , preferably 4 - 8 , more tained and that the substitution results in a stable compound . preferably 4 - 7 membered monocyclic ring or a fused 8 - 12 When a compound or substituent ( R group denoted as R1, membered bicyclic ring which may be saturated or partially R , R , and so forth ) is noted as " optionally substituted ” , the unsaturated , which monocyclic or bicyclic ring contains 1 to substituents are selected from the exemplary group includ 4 heteroatoms selected from oxygen , nitrogen , silicon or ing, but not limited to , halo , hydroxyl, alkoxy , oxo , alkanoyl, sulfur. Examples of such monocyclic rings include aryloxy , alkanoyloxy , amino , alkylamino , arylamino , aryl oxaziridinyl, homopiperazinyl, oxiranyl , dioxiranyl, aziridi alkylamino , disubstituted amines ( e . g . in which the two nyl , pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, amino substituents are selected from the exemplary group piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thi including , but not limited to , alkyl, aryl or arylalkyl) , azolidinyl, hydantoinyl, valerolactamyl, oxiranyl, oxetanyl, alkanylamino , aroylamino , aralkanoylamino , substituted dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, alkanoylamino , substituted arylamino , substituted aral dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl , tetrahy kanoyl amino , thiol , alkylthio , arylthio , arylalkylthio , alky dropyranyl, tetrahydropyridyl, tetrahydropyrimidinyl, tetra Ithiono , arylthiono , aryalkylthiono , alkylsulfonyl, arylsulfo hydrothiophenyl, tetrahydrothiopyranyl, diazepanyl and nyl, arylalkylsulfonyl, sulfonamide ( e . g . — SO NH2) , azepanyl. Examples of such bicyclic rings include indolinyl, substituted sulfonamide , nitro , cyano , carboxy, carbamyl isoindolinyl, benzopyranyl, quinuclidinyl , 2 ,3 ,4 , 5 - tetra ( e. g . CONH2) , substituted carbamyl (e . g. – CONHalkyl, hydro - 1 , 3 ,benzazepine , 4 - (benzo - 1 , 3 ,dioxol - 5 -methyl ) pip - CONHaryl, CONHarylalkyl or cases where there are erazine, and tetrahydroisoquinolinyl. Further , " substituted two substituents on one nitrogen from alkyl, aryl, or alky heterocyclyl” may refer to a heterocyclyl ring which has one lalkyl) , alkoxycarbonyl, aryl, substituted aryl, guanidine , or more oxygen atoms bonded to the ring ( i. e . as ring atoms) . heterocyclyl ( e . g . indolyl, imidazoyl, furyl, thienyl, thiaz Preferably , said atom which is bonded to the ring selected olyl, pyrrolidyl, pyridyl, pyrimidiyl, pyrrolidinyl, piperidi from nitrogen or sulphur. An example of a heterocyclyl nyl, morpholinyl, piperazinyl, homopiperazinyl and the substituted with one or more oxygen atoms is 1 , 1 - dioxido like ) , substituted heterocyclyl and mixtures thereof and the 1 , 3 -thiazolidinyl . like . The substituted moiety may be either protected or [0129 ] The general nature of the cyclic hydrocarbon sub unprotected as necessary , and as known to those skilled in strate is not viewed as particularly limiting to the oxidation the art . process described herein in any of its embodiments . In a [0125 ] As used herein , the term “ alkyl” unless otherwise preferred embodiment, the cyclic hydrocarbon is at least one specified refers to both branched and straight chain saturated selected from the group consisting of toluene , cyclohexane , aliphatic primary , secondary , and / or tertiary hydrocarbons or and methylcyclohexane . hydrocarbon fragments of typically C , to Co, and specifi [0130 ] As used herein , an oxidizing agent ( oxidant , oxi cally includes, but is not limited to , methyl, trifluoromethyl, dizer ) refers to a substance that has the ability to oxidize ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, t -bu other substances ( i . e . cause them to lose electrons ) . Sub tyl, pentyl , cyclopentyl, isopentyl, neopentyl, hexyl , iso stances that have the ability to oxidize other substances hexyl, cyclohexyl, cyclohexylmethyl, 3 -methylpentyl , 2, 2 ( cause them to lose electrons) are said to be oxidative or dimethylbutyl, and 2 , 3 -dimethylbutyl . As used herein , the oxidizing and are known as oxidizing agents , oxidants , or term optionally includes substituted alkyl groups . Exem oxidizers . That is , the oxidant ( oxidizing agent ) removes plary moieties with which the alkyl group can be substituted electrons from another substance , and is thus itself reduced . may be selected from the group including , but not limited to , Because it " accepts ” electrons , the oxidizing agent may also hydroxyl, amino , alkylamino , arylamino , alkoxy, aryloxy, be called an electron acceptor . Oxygen is a quintessential nitro , cyano , sulfonic acid , sulfate , phosphonic acid , phos oxidizer . Common oxidizing agents include , but are not phate , or phosphonate or mixtures thereof. The substituted limited to , oxygen , hydrogen peroxide , and the halogens. moiety may be either protected or unprotected as necessary , Oxidants are usually chemical substances with elements in and as known to those skilled in the art . high oxidation states (e . g. H2O2, MnO4 , CrO3, Cr20 , 2 -, [0126 ] As used herein , the term " cycloalkyl” refers to OsO2 ) or else highly electronegative elements (02 , F2, Cl2 , cyclized alkyl groups. Exemplary cycloalkyl groups include , Br ) that can gain extra electrons by oxidizing another but are not limited to , cyclopropyl, cyclobutyl, cyclopentyl, substance. In one sense , an oxidizing agent is a chemical cyclohexyl, norbornyl, and adamantyl. Branched cycloalkyl species that undergoes a chemical reaction that removes one groups such as exemplary 1 -methylcyclopropyl and 2- meth or more electrons from another atom . In that sense , it is one ylcyclopropyl groups are included in the definition of component in an oxidation - reduction ( redox ) reaction . In cycloalkyl as used in the present disclosure . another sense , an oxidizing agent is a chemical species that [0127 ] As used herein , the term “ aryl” unless otherwise transfers electronegative atoms, usually oxygen , to a sub specified refers to functional groups or substituents derived strate . Combustion , many explosives , and organic redox from an aromatic ring including , but not limited to , phenyl, reactions typically involve atom - transfer reactions . biphenyl, napthyl, thienyl, and indolyl. As used herein , the [0131 ] In certain embodiments , the oxidizing agent may term optionally includes both substituted and unsubstituted be an electron acceptor. Electron acceptors participate in moieties . Exemplary moieties with which the aryl group can electron - transfer reactions. In this context, the oxidizing US 2017 /0326536 A1 Nov . 16 , 2017 15 agent is called an electron acceptor and the reducing agent solvent of the reaction mixture . In a preferred embodiment , is called an electron donor. Extensive tabulations and rank the oxidizing agent may be present in an excess of 1 . 1 - 50 ings of the electron accepting properties of various reagents molar equivalents of the cyclic hydrocarbon , preferably 2 - 40 (redox potentials ) are available . The mechanism and details molar equivalents , preferably 4 - 30 molar equivalents , pref of the electron transfer event can be described as inner erably 5 - 20 molar equivalents of the cyclic hydrocarbon . sphere or outer sphere . Exemplary electron acceptor oxidiz (0135 ] In a preferred embodiment, an amount of the metal ing agents include , but are not limited to , tetracyanoquinodi organic framework catalyst may range from 1 - 200 grams of methane , the ferrocenium ion Fe (CH3 ) 4 + , which accepts an catalyst per mole of the cyclic hydrocarbon , preferably electron to form Fe ( C Hz) , the radical cation derived from 5 - 150 g /mol , preferably 10 - 100 g /mol , preferably 15 - 80 N (C6H4 - 4 - Br )z (“ Magic blue ” ), and the like . g /mol , preferably 20 - 75 grams of catalyst per mole of the [0132 ] In a preferred embodiment, the oxidizing agent is cyclic hydrocarbon . In certain embodiments , the amount of an atom - transfer reagent. Commonly, an oxidizing agent as the metal organic framework catalyst may range from 0 . 001 an atom - transfer reagent transfers oxygen atoms to a sub 10 mol % of a number of moles of the cyclic hydrocarbon , strate . In this context, the oxidizing agent can be termed an preferably 0 .05 - 5 mol % , preferably 0 .01 - 2 mol % , prefer oxygenation reagent or an oxygen - atom transfer (OAT ) ably 0 . 1 - 1 . 0 mol % of a number of moles of the cyclic agent. Exemplary oxygen - atom transfer agents include , but hydrocarbon , although higher catalyst loadings ( e . g . up to 20 are not limited to , MnO4- (permanganate ) , CrO42 - ( chro mol % , 30 mol % , 40 mol % , 80 mol % ) may be used and mate ), OsO4 (osmium tetroxide) , and C10 * - (perchlorate ) . In the method will still proceed as intended . In certain embodi some instances , these oxide species can also serve as elec ments , the molar ratio of the cyclic hydrocarbon to the metal tron acceptors , as illustrated by the conversion of MnO4 to organic framework catalyst is greater than 100 , preferably MnO42 - ,manganite . In a preferred embodiment, the oxidiz greater than 200 , preferably greater than 400 , preferably ing agent is an oxygen - atom transfer agent. Exemplary greater than 500 . suitable oxygen - atom transfer agent oxidizing agents [0136 ] In a preferred embodiment, the contacting may be include, but are not limited to , oxygen (O2 ) , ozone (O3 ) , performed at a temperature in the range of 40 - 100° C ., hydrogen peroxide (H2O2 ) , tert- butyl hydroperoxide preferably 45 - 95° C . , preferably 50 - 90° C ., preferably ( TBHP ) and other inorganic peroxides , Fenton ' s reagent, 55 - 85° C . , preferably 60 -80° C . , preferably 65 -75° C ., or fluorine ( F ) , chlorine ( C1, ) , bromine (Br ) , iodine (12 ) and about 70° C . An external heat source , such as a water bath other halogens, nitric acid (HNO3 ) and nitrate compounds, or an oil bath , an oven , microwave , or a heating mantle , may sulfuric acid ( H ,SO2 ) , peroxydisulfuric acid ( H , S ,02 ) , per be employed to heat the reaction mixture. In a preferred oxymonosulfuric acid (H2SO3 ) , chlorite , chlorate (C103 ) , embodiment, the external heat source is a thermostatted perchlorate and other analogous halogen compounds, thermocirculator. In one embodiment, the aqueous solution hypochlorite (C10 - ) and other hypohalite compounds, is not heated with microwave irradiation . Preferably, the sodium hypochlorite (NaClO ) hexavalent chromium com reacting is performed under air , preferably in a sealed pounds ( i . e . chromic and dichromic acids and chromium container. In another embodiment, the reacting and contact trioxide ( CrOz ) , pyridinium chlorochromate (PCC ) and ing is performed in an inert atmosphere provided by an inert chromate / dichromate (CrO42 - /Cr20 , 2 -) compounds ), per gas ( i. e . nitrogen and / or argon ). manganate compounds ( i . e . potassium permanganate ) , [0137 ] In a preferred embodiment, the contacting and sodium perborate , nitrous oxide (N2O ) , potassium nitrate reacting may be performed for a time period of 2 - 36 hours , (KNO2 ) , sodium bismuthate , sulfur dioxide (SO , ) , and the preferably 4 -30 hours, preferably 6 - 24 hours, preferably like . In a most preferred embodiment, the oxidizing agent is 8 - 20 hours, preferably 10 - 18 hours, preferably 12 - 16 hours . hydrogen peroxide. The reaction may be shaken / stirred throughout the duration [0133 ] In a preferred embodiment, the contacting and of the contacting and reacting by employing a rotary shaker , reacting is performed in a polar aprotic solvent. Exemplary a magnetic stirrer, or an overhead stirrer. In another embodi suitable polar aprotic solvents include , but are not limited to , ment, the reaction mixture is left to stand ( i . e . not stirred ) . In tetrahydrofuran , ethyl acetate , acetone , dimethylformamide , one embodiment, the reaction mixture is preferably mixed in acetonitrile , dimethyl sulfoxide , nitromethane, propylene a centrifugal mixer with a rotational speed of at least 200 carbonate and mixtures thereof, preferably the solvent is rpm , preferably at least 500 rpm , preferably at least 800 rpm , acetonitrile or dimethylformamide, most preferably the sol preferably at least 1000 rpm , even though it may also be vent is acetonitrile . It is equally envisaged that the present mixed with a spatula . In one embodiment, the reaction method may be adapted to incorporate polar protic solvents mixture is sonicated during the mixing . including , but not limited to , formic acid , n -butanol , isopro [0138 ] The reaction mixture is preferably heterogeneous panol, n -propanol , ethanol, methanol , acetic acid , and water , and comprises suspended metal organic framework catalyst as well as non - polar solvents including , but not limited to , particles in the liquid reaction mixture . In certain embodi pentane, cyclopentane, hexane , cyclohexane, benzene , tolu ments , the metal organic framework catalyst particles may ene , 1 , 4 - dioxane, chloroform , diethyl ether , dichlorometh be dispersed within the reaction mixture , and may further be ane , and mixtures thereof. filtered , washed , reactivated , and / or recycled at the end of a [0134 ] In a preferred embodiment, the cyclic hydrocarbon reaction iteration . In one embodiment, the metal organic is the limiting reagent in the oxidation method . In certain framework catalyst may be placed in a bag or semi- perme embodiments , an amount of the cyclic hydrocarbon may be able membrane and the bag may be immersed in the reaction in a range of 0 .1 - 100 mmol, preferably 0 . 5 - 25 mmol, mixture. Accordingly, the metal organic framework catalyst preferably 1. 0 - 10 mmol, preferably 1. 0 -5 mmol. In a pre remains in the bag or semi-permeable membrane through the ferred embodiment, the cyclic hydrocarbon is present at a contacting and reaction until the oxidation is completed . concentration of 0 .01 - 20 M in the solvent of the reaction Preferably, the membrane that is required for this technique mixture , preferably 0 . 1 - 10 M , preferably 1. 0 -5 .0 M in the shall allow easy transportation of both reactants and prod US 2017 /0326536 A1 Nov . 16 , 2017 16 ucts yet have a pore size that ensures retention of the metal preferably greater than 70 % . In a preferred embodiment, the organic framework catalyst . In certain embodiments , the method has a percent selectivity for a single desired oxidized progress of each reaction iteration may be monitored by cyclic hydrocarbon of greater than 10 % relative to a total methods well known to those of ordinary skill in the art amount of oxidized cyclic hydrocarbon products , preferably including, but not limited to , thin layer chromatography, gas greater 15 % , preferably greater than 20 % , preferably greater chromatography , nuclear magnetic resonance , infrared spec than 25 % , preferably greater than 30 % , preferably greater troscopy, and high pressure liquid chromatography com than 35 % , preferably greater than 40 % , preferably greater bined with ultraviolet detection or mass spectroscopy than 50 % , preferably greater than 60 % , preferably greater [ 0139 ] The general nature of the cyclic hydrocarbon sub than 70 % relative to a total amount of oxidized cyclic strate is not viewed as particularly limiting to the oxidation hydrocarbon products . process described herein in any of its embodiments . In a [0142 ] In a preferred embodiment , the cyclic hydrocarbon preferred embodiment, the cyclic hydrocarbon is at least one is toluene and 15 - 80 % of the toluene is converted to the selected from the group consisting of toluene, cyclohexane , oxidized cyclic hydrocarbon , preferably 20 -70 % , preferably and methylcyclohexane . In certain embodiments, the cyclic 25 -60 % , preferably 30 - 50 % , preferably 35 -45 % of the tolu hydrocarbon is toluene and the formed oxidized cyclic ene is converted to the oxidized cyclic hydrocarbon at a hydrocarbon is at least one selected from the group consist reaction time of greater than 6 hours , preferably greater than ing of benzaldehyde , benzoic acid , benzyl alcohol, and 8 hours, preferably greater than 10 hours , preferably greater cresols (defined as mixed cresols or o , m , p - cresols including than 12 hours , preferably greater than 16 hours , preferably 0 -cresol , m -cresol , and p -cresol ) , preferably benzaldehyde . greater than 20 hours , preferably greater than 24 hours. In certain embodiments , the cyclic hydrocarbon is cyclo [0143 ] In a preferred embodiment , the cyclic hydrocarbon hexane and the formed oxidized cyclic hydrocarbon is at is toluene and the method has a benzaldehyde selectivity least one selected from the group consisting of cyclo relative to a total amount of oxidized cyclic hydrocarbon hexanone , cyclohexanol, 4 - hydroxycyclohexanone , and 1 , 4 products in the range of 15 -70 % relative to a total amount of cyclohexadione , preferably cyclohexanone . In certain oxidation products, preferably 20 -65 % , preferably 30 -60 % , embodiments the cyclic hydrocarbon is methylcyclohexane preferably 35 -55 % relative to a total amount of oxidation and the formed oxidized cyclic hydrocarbon is at least one products . In a preferred embodiment, the cyclic hydrocarbon selected from the group consisting of methylcyclohexanol is toluene and the method has a benzoic acid selectivity ( defined as including 1 -methylcyclohexan - 1 -ol , 2 -methyl relative to a total amount of oxidized cyclic hydrocarbon cyclohexan - 1 - ol, 3 -methylcyclohexan - 1 - ol , and 4 -methyl products of less than 20 % , preferably less than 15 % , pref cyclohexan - 1 -ol ) , methylcyclohexanone (defined as includ erably less than 12 % , preferably less than 10 % , preferably ing 2 -methylcyclohexan - 1 -one , 3 -methylcyclohexan - 1 -one , less than 8 % , preferably less than 6 % , preferably less than and 4 -methyl cyclohexan - 1 -one ) , cyclohexanemethanol, 4 % , preferably less than 2 % . In a preferred embodiment, the cyclohexanal , and 3 -hepten - 2 - one, preferably methyl cyclo cyclic hydrocarbon is toluene and the method has a cresols hexanol or methylcyclohexanone . selectivity relative to a total amount of oxidized cyclic [0140 ] The definitions used in calculating the conversion hydrocarbon products of 30 - 80 % , preferably 33 -70 % , pref and selectivity of the cyclic hydrocarbon to one or more erably 35 -65 % . oxidized cyclic hydrocarbons are represented for the method [0144 ] In a preferred embodiment, the cyclic hydrocarbon of the present disclosure using the metal organic framework is toluene and the second metal ions are copper ( II ) ions and catalyst in any of its embodiments are represented in for the oxidation has the percent conversion from the cyclic mula (I ) and formula (II ) respectively . hydrocarbon to oxidized cyclic hydrocarbon products of greater than 55 % , preferably greater than 60 % , preferably greater than 62 % , preferably greater than 64 % , preferably Conversion of cyclic hydrcoarbon = ( I) greater than 66 % , preferably greater than 68 % , preferably Moles of cyclic hydrocarbon converted , greater than 70 % , preferably greater than 72 % , preferably Moles of cyclic hydrocarbon fed - X100 % greater than 75 % . Selectivity to oxidized product i = (II ) [0145 ] In a preferred embodiment, the cyclic hydrocarbon Moles of oxidized product i is toluene and the second metal ions are iron ( II ) ions and the Moles of cyclic hydrocarbon converted x 100 % oxidation has a benzaldehyde selectivity relative to a total amount of oxidized cyclic hydrocarbon products of greater than 55 % relative to a total amount of oxidation products , The conversion of cyclic hydrocarbon ( i. e . toluene ) ( % ) can preferably greater than 56 % , preferably greater than 57 % , be thought of as moles of cyclic hydrocarbon converted preferably greater than 58 % , preferably greater than 59 % , divided by moles of cyclic hydrocarbon fed multiplied by preferably greater than 60 % , preferably greater than 61 % , 100 % and the selectivity ( i . e . benzaldehyde , benzoic acid , preferably greater than 62 % , preferably greater than 63 % , cresols ) to oxidized cyclic hydrocarbon product can be preferably greater than 64 % , preferably greater than 65 % , thought of as moles of oxidized cyclic hydrocarbon product preferably greater than 70 % , preferably greater than 75 % divided by the moles of cyclic hydrocarbon converted benzaldehyde selectivity relative to a total amount of oxi multiplied by 100 % . dized cyclic hydrocarbon products . In a preferred embodi [0141 ] In a preferred embodiment, the percent conversion ment, the cyclic hydrocarbon is toluene and the second metal from the cyclic hydrocarbon to oxidized cyclic hydrocarbon ions are iron ( II) ions and the oxidation has a cresols products is greater than 15 % , preferably greater than 20 % , selectivity relative to a total amount of oxidized cyclic preferably greater than 25 % , preferably greater than 30 % , hydrocarbon products of less than 40 % , preferably less than preferably greater than 35 % , preferably greater than 40 % , 38 % , preferably less than 36 % , preferably less than 34 % , preferably greater than 50 % , preferably greater than 60100 %% ,. preferably less than 32 % , preferably less than 30 % . US 2017 /0326536 A1 Nov . 16 , 2017 17

[0146 ] In a preferred embodiment, the cyclic hydrocarbon greater than 10 hours, preferably greater than 12 hours , is toluene and the method has a benzaldehyde selectivity preferably greater than 16 hours , preferably greater than 20 relative to a total amount of oxidized cyclic hydrocarbon hours , preferably greater than 24 hours. products greater than or equal to a benzaldehyde selectivity [0150 ] In a preferred embodiment, the cyclic hydrocarbon relative to a total amount of oxidized cyclic hydrocarbon is methylcyclohexane and the method has a methylcyclo products of a substantially similar method performed in a hexanone selectivity relative to a total amount of oxidized substantially similar method performed in a substantially cyclic hydrocarbon products in the range of 15 -60 % relative similar manner with a substantially similar metal organic to a total amount of oxidation products , preferably 20 -50 % , framework catalyst lacking the zinc ( II) ions , the second preferably 30 - 45 % , preferably 35 - 40 % relative to a total metal ions or both . In a preferred embodiment, the cyclic amount of oxidation products . In a preferred embodiment , hydrocarbon is toluene and the method has a benzaldehyde the cyclic hydrocarbon is methylcyclohexanone and the selectivity relative to a total amount of oxidized cyclic method has a methylcyclohexanol selectivity relative to a hydrocarbon products that is at least 5 percentage points total amount of oxidized cyclic hydrocarbon products of greater , preferably at least 10 percentage points , preferably greater than 30 % , preferably greater than 35 % , preferably at least 15 percentage points , preferably at least 20 percent greater than 40 % , preferably greater than 45 % , preferably age points , preferably at least 25 percentage points, prefer greater than 50 % , preferably greater than 55 % , preferably ably at least 30 percentage points , preferably at least 35 percentage points , preferably at least 40 percentage points , greater than 60 % , preferably greater than 5 % , preferably preferably at least 45 percentage points , preferably at least greater than 70 % . In a preferred embodiment, the cyclic 50 percentage points , preferably at least 55 percentage hydrocarbon is methylcyclohexane and the method has a points , preferably at least 60 percentage points , preferably at cyclohexanone methanol selectivity relative to a total least 65 percentage points greater than a benzaldehyde amount of oxidized cyclic hydrocarbon products and a selectivity relative to a total amount of oxidized cyclic cyclohexanal selectivity relative to a total amount of oxi hydrocarbon products of a substantially similar method dized cyclic hydrocarbon products of 1 - 20 % , preferably performed in a substantially similar method performed in a 2 - 15 % , preferably 5 - 10 % . substantially similar manner with a substantially similar [0151 ] In a preferred embodiment, the cyclic hydrocarbon metal organic framework catalyst lacking the zinc (II ) ions , is at least one selected from the group consisting of cyclo the second metal ions or both . hexane and methylcyclohexane and 10 -60 % of the cyclic [0147 ] In a preferred embodiment, the cyclic hydrocarbon hydrocarbon is converted to the oxidized cyclic hydrocar is cyclohexane and 10 -60 % of the cyclohexane is converted bon , preferably 12 -50 % , preferably 15 -48 % , preferably to the oxidized cyclic hydrocarbon , preferably 12 - 50 % , 20 - 45 % , preferably 25 - 40 % of the cyclic hydrocarbon is preferably 15 - 40 % , preferably 18 -35 % , preferably 20 - 33 % converted to the oxidized cyclic hydrocarbon at a reaction of the cyclohexane is converted to the oxidized cyclic time of greater than 12 hours , preferably greater than 16 hydrocarbon at a reaction time of greater than 6 hours, hours , preferably greater than 20 hours , preferably greater preferably greater than 8 hours , preferably greater than 10 than 24 hours . hours , preferably greater than 12 hours , preferably greater [0152 ] In a preferred embodiment, the method further than 16 hours , preferably greater than 20 hours , preferably comprises recovering and reusing the metal organic frame greater than 24 hours . work catalyst of the present disclosure in any of its embodi [ 0148 ] In a preferred embodiment, the cyclic hydrocarbon ments in at least 2 reaction iterations with a less than 20 is cyclohexane and the method has a cyclohexanone selec percentage point decrease in conversion , a less than 20 tivity relative to a total amount of oxidized cyclic hydro percentage point decrease in selectivity or both . In this carbon products in the range of 45 - 80 % relative to a total manner the metal organic framework catalyst can be recov amount of oxidation products, preferably 48 - 75 % , prefer ered and reused in at least 2 reaction iterations , preferably at ably 50 -70 % , preferably 55 -65 % relative to a total amount least 3 , preferably at least 4 , preferably at least 5 , preferably of oxidation products . In a preferred embodiment, the cyclic at least 6 , preferably at least 8 , preferably at least 10 , hydrocarbon is cyclohexanone and the method has a cyclo preferably at least 15 , preferably at least 20 , preferably at hexanol selectivity relative to a total amount of oxidized least 30 , preferably at least 50 reaction iterations. cyclic hydrocarbon products of less than 50 % , preferably [0153 ] In certain embodiments , the metal organic frame less than 45 % , preferably less than 40 % , preferably less than work catalyst may be separated by removing the bag con 35 % , preferably less than 30 % , preferably less than 25 % , taining the metal organic framework catalyst, dialysis in a preferably less than 20 % . In a preferred embodiment, the solvent, or using a micro - filter or a paper filter. The phrase cyclic hydrocarbon is cyclohexane and the method has a recovering , reusing, and / or recycling the metal organic 4 -hydroxy cyclohexanone selectivity relative to a total framework catalyst refers to a process whereby the metal amount of oxidized cyclic hydrocarbon products and a organic framework catalyst is first washed by an organic 1 ,4 - cyclohexadione selectivity relative to a total amount of solvent, reactivated , dried and then added to a new batch of oxidized cyclic hydrocarbon products of 1 - 25 % , preferably reactants ( either the same or a different type of cyclic 2 - 20 % , preferably 5 - 15 % . hydrocarbon substrate ) . Preferred organic solvents for wash [ 0149 ] In a preferred embodiment, the cyclic hydrocarbon ing and/ or reactivating the metal organic framework catalyst is methylcyclohexane and 10 -60 % of the methylcyclo include , without limitation , methanol, acetone, ethanol, tet hexane is converted to the oxidized cyclic hydrocarbon , rahydrofuran , acetonitrile , dichloromethane , ether, glycol preferably 12 - 50 % , preferably 15 - 45 % , preferably 20 - 40 % , ether , acetamide , dimethyl acetamide , dimethyl sulfoxide , or preferably 25 - 35 % of the methylcyclohexane is converted to combinations thereof. Themetal organic framework catalyst the oxidized cyclic hydrocarbon at a reaction time of greater may be dried in vacuum and / or with heating , for example , than 6 hours , preferably greater than 8 hours, preferably the metal organic framework catalyst may be dried in a US 2017 /0326536 A1 Nov . 16 , 2017 vacuum oven . The dried metal organic framework catalyst preferably between the first and fifth reaction iteration , may be optionally stored prior to an additional reaction preferably between the first and fourth reaction iteration , iteration . preferably between , the first and third reaction iteration , [0154 ] In a preferred embodiment , there is a less than 20 preferably between the first and second reaction iteration . percentage point change in percent cyclic hydrocarbon (i . e . [0156 ] It is equally envisaged , that the method of the toluene , cyclohexane , methylcyclohexane ) conversion present disclosure and / or the metal organic framework cata between the first and second reaction iteration , preferably lyst of the present disclosure in any of their embodiments less than 15 percentage points , preferably less than 10 may be adapted to provide catalysis in a wide variety of percentage points , preferably less than 5 percentage points , chemical transformations . Exemplary suitable chemical preferably less than 4 percentage points, preferably less than transformations include , but are not limited to , reduction of 3 percentage points , preferably less than 2 percentage points , carbon - carbon multiple bonds, 1 , 3 - dipolar cycloaddition , preferably a less than 1 percentage point change in percent hydroxymethylation , cyanosilylation of aldehydes , Knoev cyclic hydrocarbon ( i. e . toluene , cyclohexane , methylcyclo enagel condensation , alkylation of aldehydes , oxidation of hexane ) conversion between the first and second reaction olefins , cycloaddition of CO , and epoxides , ring opening of iteration . In certain embodiments , there is a less than 20 epoxides ( oxidation of hydrocarbons) , Heck coupling , oxi percentage point change in percent cyclic hydrocarbon ( i. e . dation of sulfides, aerobic oxidation of olefins, methanolysis toluene, cyclohexane , methylcyclohexane ) conversion , pref of epoxides , epoxidation of olefins, oxidative self - coupling , erably less than 15 percentage points , preferably less than 10 aldol condensttion reactions , Mukaiyama aldol reaction , percentage points , preferably less than 5 percentage points , cyclizations, oxidation of thioethers, transesterification , preferably less than a 2 percentage point change in percent Friedel -Crafts alkylation , Suzuki- Miyaura coupling , hydro cyclic hydrocarbon ( i. e . toluene , cyclohexane , methylcyclo genation of olefins, intermolecular transfer of acyl, isomer hexane ) conversion between the first and twentieth reaction ization , rearrangements , Henry reaction , Click reaction , iteration , preferably between the first and fifteenth reaction cross -dehydrogenative coupling , alcohol oxidation , and the iteration , preferably between the first and tenth reaction like . It is equally envisaged , that the method of the present iteration , preferably between the first and fifth reaction disclosure and / or the metal organic framework catalyst of iteration , preferably between the first and fourth reaction the present disclosure in any of their embodiments may be iteration , preferably between , the first and third reaction adapted to provide a means of gas separation , gas sensing , iteration , preferably between the first and second reaction and gas storage , in particular H , storage . iteration . [0157 ] The examples below are intended to further illus [ 0155 ] In a preferred embodiment, there is a less than 20 trate protocols for preparing and characterizing the metal percentage point change in percent single oxidized cyclic organic frameworks of the present disclosure . Further, they hydrocarbon product ( i . e . benzaldehyde from toluene, cyclo are intended to illustrate assessing the properties and appli hexanone or cyclohexanol from cyclohexane , methylcyclo cations of these metal organic frameworks . They are not hexanol or methyl cyclohexanone from methylcyclohexane ) intended to limit the scope of the claims. selectivity relative to a total amount of oxidized cyclic Example 1 hydrocarbon products between the first and second reaction iteration , preferably less than 15 percentage points , prefer ably less than 10 percentage points , preferably less than 5 Chemicals and Materials percentage points , preferably less than 4 percentage points , [0158 ] All reagents were used as purchased without fur preferably less than 3 percentage points , preferably less than ther purification . 1 , 3 ,5 -benzene tricarboxylic acid ( BTC ) , 2 percentage points, preferably a less than 1 percentage point Cu (NO3 ) 2 3H2O , CO( NO3 ) 2 6H20 , Ni( NO3 ) 2 .6H20 , change in percent single oxidized cyclic hydrocarbon prod Zn (NO3 ) 2 .6H2O , FeCl2 -6H2O , N , N - dimethylformamide uct ( i . e . benzaldehyde from toluene, cyclohexanone or ( DMF) and ethanol were obtained from Sigma - Aldrich . cyclohexanol from cyclohexane , methylcyclohexanol or Acetonitrile was obtained from Sigma - Aldrich . Toluene , methyl cyclohexanone from methylcyclohexane ) selectivity cyclohexane and methylcyclohexane were used as pur relative to a total amount of oxidized cyclic hydrocarbon chased from Sigma- Aldrich . New 10 mL and 20 mL kimble products between the first and second reaction iteration . In scintillation vials were used for the synthesis of various certain embodiments , there is a less than 20 percentage point metal organic frameworks (MOFs ) . change in percent single oxidized cyclic hydrocarbon prod uct ( i . e . benzaldehyde from toluene , cyclohexanone or Example 2 cyclohexanol from cyclohexane, methylcyclohexanol or methyl cyclohexanone from methylcyclohexane ) selectivity Synthesis of Metal Organic Frameworks (HKUST - 1 relative to a total amount of oxidized cyclic hydrocarbon and Zn -HKUST - 1 ) and Transmetallation of products, preferably less than 15 percentage points , prefer ZN -HKUST - 1 ably less than 10 percentage points , preferably less than 5 [0159 ] In a standard procedure , a mixture of Cu (NO3 ) 2. percentage points , preferably less than a 2 percentage point 3H , O ( 0 . 438 g , 1 . 81 mmol) and 1 , 3 , 5 - benzenetricarboxylic change in percent single oxidized cyclic hydrocarbon prod acid (BTC ) ( 0 .236 g , 1 . 12 mmol) were completely dissolved uct ( i . e . benzaldehyde from toluene, cyclohexanone or in a solvent mixture containing N , N -dimethylformamide ( 2 cyclohexanol from cyclohexane, methylcyclohexanol or mL ) , deionized water ( 2 mL ) and ethanol ( 2 mL ) in a tightly methyl cyclohexanone from methylcyclohexane ) selectivity sealed 20 mL vial [ Rowsell, J . L . C . & Yaghi, O . M J . Am . relative to a total amount of oxidized cyclic hydrocarbon Chem . Soc ., 2006 , 128 , 1304 - 1315 . - incorporated herein by products between the first and twentieth reaction iteration , reference in its entirety ] . The tightly covered vial was placed preferably between the first and fifteenth reaction iteration , in an isothermal oven at 85° C . for 20 hours to yield small , preferably between the first and tenth reaction iteration , blue, octahedral crystals . After cooling the vial to room US 2017 /0326536 A1 Nov . 16 , 2017 temperature , the mother liquor was decanted and the tiny peak of BTC at 2933 cm ? was the result of deprotonation crystals were rinsed with DMF three times. The crystals that leads to coordination . The band for the O C - O were then activated by soaking in 5 mL of dichloromethane asymmetric stretching of HKUST- 1 and Zn -HKUST - 1 (DCM ) for 3 days at room temperature during which DCM appeared at 1658 cm and 1640 cm - respectively , due to was decanted and freshly replenished three times . The the binding of the carbonyl oxygen with metal atoms. The crystals were dried under vacuum at 160° C . for 4 hours sharp peaks at 3433 cm - for HKUST- 1 ( FIG . 14 ) and 3434 yielding 0 . 3 g of HKUST- 1 in the form of deep blue crystals . cm - 1 for Zn -HKUST - 1 (FIG . 15 ) are due to the axial H , O FIG . 11 is a typical schematic representation for the syn ligands that are coordinated to the dimeric Cu atoms forming thesis of HKUST- 1 . an octahedral unit . Similarly , FT- IR spectra of Fe - Zn [ 0160 ] Using a modified procedure , a homogeneous mix HKUST- 1 (FIG . 16 ) , Co - Zn - HKUST- 1 (FIG . 17 ) and ture of Zn (NO3 ) 26H , O ( 0 .04 g , 0 . 188 mmol) and 1 , 3 , 5 Cu - Zn -HKUST - 1 (FIG . 18 ) show great similarity to that of benzenetricarboxylic acid (BTC ) ( 0 . 171 g , 1 . 12 mmol) was Zn -HKUST - 1 which indicates that there was substantial dissolved in 10 mL N , N - dimethylformamide in a tightly retention of the MOF framework after transmetallaion . sealed 20 mL scintillation vial [ Bhunia , M . K , Hughes, J . T . Fettinger , J . C . and Navrotsky , A . Langmuir 2013 , 29 , Example 4 8140 -8145 . — incorporated herein by reference in its entirety ) . The tightly covered vial was placed in an isother Field Emission Scanning Electron Microscopy mal oven at 85° C . for 16 hours to form colorless cubic (FESEM ) Analysis of Prepared Metal Organic crystals . After cooling the vial to room temperature, the Frameworks (MOFs ) mother liquor was decanted and the tiny crystals were rinsed [0164 ] Field emission scanning electron microscopy (FE with DMF three times. The crystals were then activated by SEM , Tescan - Lyra- 3 ) was used to provide images of the soaking in methanol for 3 days at room temperature during synthesized catalysts . Scanning electron microscopy (SEM ) which methanol was decanted and freshly replenished three uses a focused beam of high energy electrons to generate a times . The crystals were dried under vacuum at 170° C . for variety of signals at the surface of solid specimens. The 4 hours. FIG . 12 is a typical schematic representation for the signals that are derived from electron - sample interactions synthesis of Zn -HKUST - 1 . reveal information about the sample including external [0161 ] Pure samples of HKUST -1 and Zn -HKUST - 1 morphology ( texture ) , chemical composition , and crystalline metal organic frameworks (MOFs ) were obtained as blue structure as well as the orientation of materials making up and colorless crystals , respectively . The crystals were dried the sample . Accelerated electron in a SEM carry significant under vacuum at 120° C . and stored in air tight vials to amounts of kinetic energy, and this energy is dissipated as a prevent moisture . The dried samples were characterized variety of signals produced by electron -sample interactions using Fourier transform infrared spectrophotometry (FT - IR ) , when the incident electrons are decelerated in the solid scanning electron microscopy (SEM ) and powder X - ray samples. These signals include secondary electrons ( that diffraction (PXRD ). produce SEM images ), backscattered electrons (BSE ) , and [0162 ] Portions of the as- synthesized Zn - HKUST- 1 crys diffracted backscattered electrons (DBSE ) that are used to tals were soaked in 0 . 5 M methanolic solutions of Cu (NO3 ) determine crystal structures and orientations. Secondary 2 -3H2O , CO (NO3 ) 2 -6H2O , and FeCl26H2O for 72 hours at electrons are most valuable for showing morphology and 40° C . At the end of the incubation , the remaining solution topography of samples and backscattered electrons aremost ofmetal ions were decanted , and the transmetallated crystals valuable for illustrating contrasts in the composition of a harvested by filtration . The crystals were washed thoroughly multiphase sample ( i . e . for rapid phase discrimination ) . FIG . with methanol and then soaked in methanol for complete 19 and FIG . 20 show the SEM images of the synthesized removal of residual metal ions . The resulting cation HKUST -1 catalyst at different magnifications. FIG . 21 and exchanged MOFs were dried under reduced pressure at FIG . 22 show the SEM images of the synthesize Zn room temperature . HKUST- 1 catalyst at different magnifications. The SEM images of the synthesized catalysts are shown with the same Example 3 magnification of 2 - 20 um scale bar. The micrograph images show the formation of crystalline materials as expected . Fourier Transform Infrared (FT - IR ) Spectroscopy HKUST- 1 was observed to occur in the form of a polyhedral Analysis of Prepared Metal Organic Frameworks ( octahedral ) crystal ( FIG . 19 and FIG . 20 ) with sizes of a (MOFs ) few microns. The micrograph images of Zn -HKUST - 1 show [0163 ] Fourier transform infrared (FT - IR ) spectra were the formation of polyhedral ( cubic ) crystals ( FIG . 21 and taken on a Nicolet spectrophotometer using KBr within the FIG . 22 ) with sizes of a few microns. standard range of 400 -4000 cm - ? . This method was used to confirm the formation of HKUST- 1 , Zn - HKUST- 1 , as well Example 5 as the transmetallated Zn -HKUST - 1 isostructural metal organic frameworks (MOFs ) . 1 , 3 , 5 - benzenetricarboxylic Powder X - Ray Diffraction ( P - XRD ) Analysis of acid (BTC ) as a ligand shows the C = 0 stretching frequency Prepared Metal Organic Frameworks (MOFs ) of carboxylic acid around 1718 cm - 1 and also a broad O — H [0165 ] Powder X -ray diffraction (P -XRD ) patterns were peak at about 2933 cm which corresponds to the hydrogen collected using a Rigaku Miniflex II instrument with a bonding . FIG . 13 is the FT - IR spectrum of 1 , 3 , 5 - benzentri monochromator of CuKal ( 1 . 5406 Å ) at 30 kV and 15 mA . carboxylic acid (BTC ) . The FT - IR analysis of HKUST- 1 The PXRD patterns were recorded in the static scanning ( FIG . 14 ) and Zn -HKUST - 1 ( FIG . 15 ) indicates that there mode from 50 to 60° ( 28 ) at a detector angular speed of 2° was a significant shift in the C = 0 stretching frequency of min - 1 and step size of 0 . 02°. The wavelength of X - rays is the BTC ligand . The disappearance of the broad acidic O - H approximately the same as the distance between the particles US 2017 /0326536 A1 Nov . 16 , 2017 20 in the lattice. If the beam of X - rays strikes a crystal, the [0168 ] The oxidation of toluene proceeded in the presence X -rays are deflected by the crystal and are detected by a of H2O2 as an oxidizing agent using acetonitrile as solvent photographic plate . This technique was used to examine the to give a mixture of oxygenated products as expected . The morphological structure of the synthesized catalyst. The formation of a mixture of products was the first test of the crystallinity of HKUST- 1 and Zn - HKUST- 1 was probed by catalytic activity of the metal organic frameworks (MOFs ) . The blank experiment, in the absence of an MOF did not PXRD after solvent evacuation under reduced pressure at lead to any significant toluene conversion even after 24 elevated temperatures . The diffraction patterns show that hours . The outcome of the blank experiment was similar to HKUST- 1 (FIG . 23 ) appears isostructural to Zn - HKUST- 1 what had already been previously reported in the literature ( FIG . 24 ) with a slightly larger unit cell (HKUST - 1 , a = 26 . [ Bin Du , Song - il Kim , Lan -Lan , Lou Aizhong, Jia , Gaixia 343 ( 0 . 005 Å ) and Zn -HKUST - 1 , a = 26 . 520 ( 0 .001 Å ) ) . The Liu , Ben Qi, Shuangxi Liu Applied Catalysis A : General, respective patterns were compared to those found in the 2012 425 , 191 - 198 . — incorporated herein by reference in its Cambridge Structural Database (CSD ) . The CSD reference entirety ). HKUST- 1 showed a good activity for title oxida patterns were simulated using Mercury V . 3 . 3 and are shown tion of toluene reaction affording a conversion of 51 % after in FIG . 23 and FIG . 24 . Differences in peak intensities 6 hours . Table 1 summarizes the results of toluene oxidation between simulated and experimental diffractograms can be with HKUST- 1 . attributed to pore occlusion by coordinated guest molecules. The powder patterns of Fe - Zn -HKUST - 1 ( FIG . 25 ) , Co TABLE 1 Zn - HKUST- 1 ( FIG . 26 ) and Cu - Zn -HKUST - 1 ( FIG . 27 ) show that the modified MOFs are isostructural to Zn Results of toluene oxidation with HKUST- 1 HKUST- 1 . This can be confirmed as the XRD pattern of Benzole Beznyl O , M , P each of the modified MOF catalysts shows a reasonable Time % Benzaldehyde Acid Alcohol Cresols level of similarity to the confirmed Zn -HKUST - 1 pattern as (hr ) Conversion (% ) (% ) (% (% ) overlaid in FIG . 25 , FIG . 26 , and FIG . 27 . 51 17 trace 65 60 O trace 5 Example 6 77 auo trace Na 80 16 trace Inductively Coupled Plasma Mass Spectrometry (ICP -MS ) Analysis of Prepared Metal Organic 01691 Cresols were the major products and their amounts in the product mixture decreased from 65 % after 6 hours to Frameworks (MOFs ) 58 % after 24 hours due to the formation of benzoic acids as [0166 ] Inductively coupled plasma mass spectrometry by -product . The formation of cresols in this reaction is not ( ICP -MS ) is an analytical technique which is capable of surprising as this could be as a result of the hydroxylation of detecting metals and several non -metals at concentrations as the aromatic ring in the presence of peroxide. The selectivity low as one part in 1015 (part per quadrillion , ppq) . The in benzaldehyde was also significantly decreasing from 18 % working principle is based on the ionization of the sample in 6 hours to 16 % after 24 hours as the selectivity of benzoic with an inductively coupled plasma followed by the accurate acid has increased with time . This suggests that the rate of separation and quantification of those ions with a mass benzoic acid formation from benzaldehyde is faster than the spectrometer . Compared to atomic absorption spectroscopy , rate of toluene oxidation . Despite the fact that Zn is not a ICP -MS has better sensitivity , precision and speed . Prior to good oxidation metal , Zn -HKUST - 1 pushed the oxidation of ICP -MS analysis , the FeZn -HKUST - 1 , Co - Zn toluene to 22 % after 24 hours with 22 % selectivity . Table 2 HKUST- 1 , and Cu - Zn - HKUST- 1 metal organic frame summarizes the results of toluene oxidation with works were digested using a 30 % HNO3 solution and the Zn -HKUST - 1. This could be attributed to the electronic samples were further diluted to 10 ppm . The ICP -MS structure of the metal organic framework (MOF ) resulting analysis of FeZn -HKUST - 1 revealed that 34 % of the Zn2 + from the coordination of the BTC ligand . The effect of time in Zn -HKUST - 1 was replaced by Fe2+ indicating that the can also be easily observed by considering the significant transmetallation was incomplete . Similarly , 34 % of the Zn2 + differences in conversion and benzaldehyde selectivity with in Zn -HKUST -1 was replaced by Co2 + ions in the Co — Zn the progress of the reaction . It should be noted that the HKUST- 1 catalyst . On the other hand , the analysis ofmetal Zn -HKUST - 1 catalyst did not favor further oxidation of ions in Cu - Zn -HKUST - 1 showed that 90 % of the Zn2 + ions benzaldehyde to benzoic acid . were replaced by Cu2 + . TABLE 2 Example 7 | Results of toluene oxidation with Zn -HKUST - 1 Catalytic Toluene Oxidation Reactions and Analysis Benzole 0 , M , P Time % Benzaldehyde Acid Cresols 10167 ] The catalytic oxidation of toluene in the presence ( hr ) Converision ( % ) ( % ) ( % ) of hydrogen peroxide as an oxidizing agent was performed 1 . 7 at 70° C . using a 10 - point electrothermal reactor . 2 mL of 10 ON toluene and 0 . 03 g of an activated HKUST type MOF 19 catalyst was added into the reaction tube followed by the 28 Paco oooo OOON addition of 4 mL of acetonitrile and 2 mL of H , 0 , . FIG . 28 shows the chemical equation and scheme for the oxidation of toluene. The reaction mixture was stirred and an aliquot [0170 ] The incorporation of Fe into the Zn - HKUST- 1 of the samples was collected after 6 , 12 , 18 , and 24 hours for framework gave a significant improvement to the catalytic gas chromatography mass spectrometer (GC -MS ) and gas activity . Table 3 summarizes the results of toluene oxidation chromatography- flame ionization detector (GC - FID ) analy with FeZn -HKUST - 1 . Apart from the gradual initial sis . increase in the conversion that can be attributed to the US 2017 /0326536 A1 Nov . 16 , 2017 presence of Fe, Fe — Zn — HKUST- 1, clearly exemplified the equation and scheme for the oxidation of cyclohexane . FIG . unique performance of Fe in oxidation reactions , especially 30 shows the chemical equation and scheme for the oxida in terms of selectivity with the catalyst giving the highest tion of methylcyclohexane . benzaldehyde selectivity of 61 % at 6 hours . Unlike Fe - Zn [0172 ] The isostructural HKUST - 1 metal organic frame HKUST- 1 , Co - Zn - HKUST- 1 gave similar performance works (MOFs ) acted as catalysts for the oxidation of cyclo to Zn -HKUST - 1 . Table 4 summarizes the results of toluene hexane with H2O , at 70° C . forming cyclohexanol and oxidation with Co - Zn -HKUST - 1 . Table 5 summarizes the cyclohexanone as major products . Table 6 summarizes the results of toluene oxidation with Cu - Zn - HKUST- 1 . The results of cyclohexane oxidation with HKUST- 1 . HKUST- 1 catalytic activity of Cu modified Zn -HKUST - 1 ( CuZn was observed to be the most active catalyst, achieving the HKUST- 1 ) for toluene oxidation demonstrated that Cu highest conversion of 52 % which is better than those of greatly improves the conversion of toluene relative to Zn well -known catalytic materials previously reported in the HKUST- 1 . After 6 hours Cu - Zn -HKUST - 1 gave a conver literature and comparable to that of modified zeolite [Gob sion of 34 % with 16 % benzaldehyde selectivity , while erna - Ferrón S ., Lillo V . , and Galitn -Mascarós , R . Catal. Zn - HKUST on the other hand gave very low conversion Comm . 2012 , 23 , 30 - 33 . ; and Bagherzadeh , M , Amini, F ., without benzaldehyde over the same time period . Ellern , A . , Woo , L . Inorg . Chem . Comm . 2012 , 15 , 52 -55 . ; and Alavi, S , Hosseini -Monfared , H ., Siczek , M . Journal of TABLE 3 Molecular Catalysis A , 2013 , 377 , 16 - 28 . - each incorpo rated herein by reference in its entirety ) . The catalyst gave Results of toluene oxidation with Fe - Zn - HKUST - 1 an initial low conversion of 9 % but this value increased Benzoic O , M , P steadily as the reaction progresses to 24 hours . The great Time % Benzald Acid Cresols activity of HKUST- 1 could be largely attributed to the heavy ( hr ) ConverisionConverision ( % ) ( % ) ( % ) presence of vacant Cu sites in the framework . In contrast, 33 Zn - HKUST- 1 did not show any significant activity for this reaction even after 24 hours. This inactivity of Zn -HKUST - 1 could be due to the dlo electronic configuration of the Zn 4889 va 35 metal which is unfavorable for alkane oxidation . TABLE 6 TABLE 4 Results of cyclohexane oxidation with HKUST- 1 Results of toluene oxidation with Co - Zn - HKUST- 1 Time % CyclohexanoCyclohexanone C yclohexanol Benzoic O , M , P (hr ) Converision ( % ) Time % Benzaldehyde Acid Cresols 100 (hr ) Converision ( % ) 23 |° AOA 60 40 16 883 40 18 24 WN 6 oooo [0173 ] Drastic improvement in activity was observed when Fe was incorporated into the framework of Zn HKUST- 1 . Table 7 summarizes the results of cyclohexane TABLE 5 oxidation with FeZn -HKUST - 1 . FeZn -HKUST - 1 gave the high conversion of 20 % after 24 hours . Similarly , Results of toluene oxidation with Cu - Zn -HKUST - 1 Co - Zn - HKUST- 1 gave high conversion of 27 % with Benzoic O , M , P reasonable selectivity in cyclohexanol and cyclohexanone . Time 0/0 Benzaldehyde Acid Cresols Table 8 summarizes the results of cyclohexane oxidation ( hr ) Converision ( % ) with Co - Zn -HKUST - 1 . Table 9 summarizes the results of 34 16 cyclohexane oxidation with Cu - Zn - HKUST- 1 . Cu — Zn 12 56 14 HKUST- 1 gave a conversion of 40 % after 24 hours with an 18 65 17 equal ratio of cyclohexanol and cyclohexanone . The activity 24 70 18 of Cu - Zn -HKUST - 1 is similar to what was observed for HKUST- 1 in terms of the conversion and this could be attributed to the Cu atoms which are probably responsible Example 8 for the relatively high conversion . Catalytic Cycloalkane Oxidation Reactions and Analysis TABLE 7 [0171 ] For the oxidation of cycloalkanes, the 10 - point Results of cyclohexane oxidation with FeZn - HKUST - 1 electrothermal reactor and stirrer was charged with a mix 4 -hydroxy ture containing the activated HKUST type MOF catalyst Cyclohex - Cyclohex - cyclohex 1 , 4 ( 0 .03 g ) , acetonitrile ( 4 mL ) , cyclohexane or methylcyclo Time % anone anol anone cyclohexadione hexane ( 0 . 5 mL ) , and 2 mL of 30 % H2O2. Themixture was ( hr ) Converision ( % ) ( % ) vigorously stirred and heated at 70° c . Aliquots of the 6 45 28 2 reaction mixtures were taken after 6 , 12 , 18 , and 24 hours for 12 va 59 12 WN GC -MS and GC - FID analysis . FIG . 29 shows the chemical US 2017 /0326536 A1 Nov . 16 , 2017

TABLE 7 - continued hours with approximately equal amounts of methylcyclo hexanol and methylcyclohexanone produced . There was a Results of cyclohexane oxidation with Fe - Zn - HKUST- 1 gradual increase in the percent conversion to 15 % after 24 4 -hydroxy hours . The effect of Fe incorporation into the Zn -HKUST - 1 Cyclohex - Cyclohex - cyclohex 1 , 4 framework is noteworthy since only Zn -HKUST - 1 was not Time % anone anol a none cyclohexadione active at up to 24 hours under the same reaction conditions . (hr ) Converision ( % ) ( C ) ( % ) ( % ) Similarly , Co - Zn - HKUST showed appreciable activity 18 13 56 21 18 over Zn -HKUST - 1 due to the presence of Co atoms in the 24 20 55 20 21 ??? metal organic framework (MOF ) . Table 12 summarizes the results of methylcyclohexane oxidation with Co - Zn HKUST- 1 . Table 13 summarizes the results of methylcyclo hexane oxidation with Cu - Zn -HKUST - 1 . Table 13 shows TABLE 8 the results obtained for the liquid phase oxidation of meth Results of cyclohexane oxidation with Co - Zn -HKUST - 1 ylcyclohexane where the highest conversion of 45 % was observed after 24 hours forming a higher amount of meth Time Cyclohexanone Cyclohexanol ylcyclohexanol. ( hr ) Converision TABLE 11 ON 60 Ona 65 Results of methylcyclohexane oxidation with Fe - Zn -HKUST - 1 65 Methyl Methyl- Cyclohex cyclohex - cyclohex - ane Time % anol anone methanol Cyclohexanal TABLE 9 (hr ) Converision ( % ) ( % ) Results of cyclohexane oxidation with Cu - Zn - HKUST- 1 3 trace 7 On 10 trace Time % Cyclohexanone Cyclohexanol ?? w (hr ) Converision ( % ) ( % ) 24 25 #

wowu ques TABLE 12 Results ofmethylcyclohexane oxidation with Co - Zn -HKUST - 1 [ 0174 ] Methylcyclohexane was oxidized using the iso Methyl Methyl - Cyclohex structural metal organic frameworks (MOFs ) at 70° C . in the Cyclohex - Cyclohex - ane presence of H , 0 , to afford reasonable yields of oxygenated Time % anol anone methanol Cyclohexanal products . GC -MS analysis revealed the formation of 5 ( hr ) Converision ( % ) ( % ) ( % ) different oxygenated products with methylcyclohexanol and 43 ? trace 61 ??? TO ? methylcyclohexanone being the major products . HKUST- 1 45 ?? +| gave the highest conversion of 48 % for this reaction after 24 44 ? 13 hours with methylcyclohexanol as the major product while 224 1214 it afforded only 18 % conversion after 6 hours . Table 10 summarizes the results of methylcyclohexane oxidation with HKUST- 1. The difference in reaction time largely affects the TABLE 13 conversion but has little effect on the methylcyclohexanol selectivity . Results of methylcyclohexane oxidation with Cu - Zn - HKUST - 1 Methyl Methyl - Cyclohex cyclohex - cyclohex ane TABLE 10 Time % anol anone methanol Cyclohexanal Results of methylcyclohexane oxidation with HKUST- 1 (hr ) Converision ( % ) 55 27 18 Methyl Methyl- Cyclohex 12 65 cyclohex - cyclohex - ane 18 60 Time % anol anone methanol Cyclohexanal 58 ( hr ) Converision ( % ) ( % ) ( % ) 24 ? 66 WA 36 17 trace trace [01761 The reusability of the catalysts was also examined . ?? 05 coa 05 The HKUST- 1 metal organic framework was recovered , AAA washed , and reactivated for two more runs after 6 hours . The dried HKUST- 1 was subjected to powder X - ray diffraction [0175 ] The modification of Zn -HKUST - 1 however gener (PXRD ) to ascertain if the metal organic framework (MOF ) ally improved its activity for methylcyclohexane oxidation . was able to withstand the reaction conditions . The PXRD Table 11 summarizes the results of methylcyclohexane oxi analysis revealed that there was no collapse in the metal dation in the presence of FeZn - HKUST- 1 . With FeZn organic framework (MOF ) after 6 hours . FIG . 31 shows the HKUST - 1 35 conversion of the substrate was observed in 6 great match between the patterns for the unused and used US 2017 /0326536 A1 Nov . 16 , 2017 23

HKUST- 1 catalysts . Since the catalyst was found to be 8 : The metal organic framework catalyst of claim 1, structurally intact, the catalytic activity was tested for tolu wherein the second metal ions are at least one selected from ene oxidation in two repeated runs. There was significant the group consisting of iron ( II ) ions and cobalt ( II ) ions and retention of activity in terms of conversion of toluene and the ratio of zinc ( II ) ions to the second metal ions is in the selectivity for benzaldehyde . FIG . 32 is a graphical illustra range of 0 . 5 to 5 . 0 . tion of the maintained conversion and selectivity of the 9 : A process for producing the metal organic framework catalyst over three runs . catalyst of claim 1 , comprising: (0177 ] In conclusion , pure single crystals of HKUST- 1 reacting 1 , 3 , 5 - benzenetricarboxylic acid with a zinc (II ) and Zn -HKUST - 1 were successfully synthesized using sol salt or hydrate in a solvent at a temperature greater than vothermal methods and the synthesized Zn -HKUST - 1 was 25° C . to form a zinc modified metal organic frame work ; and subjected to modification via transmetallation affording rea transmetallating at least a portion of the zinc modified sonable amounts of transmetallated products . Both the syn metal organic framework by immersing in a solution of thesized and modified metal organic frameworks (MOFs ) a salt or hydrate of the second metal ions . were characterized using FTIR , FESEM , PXRD , and ICP 10 : A method for an oxidation of a cyclic hydrocarbon , MS. Furthermore , the catalytic activity of the MOFs was comprising : tested in the oxidation of toluene , cyclohexane and methyl contacting the cyclic hydrocarbon with the metal organic cyclohexane . FeZn - HKUST - 1 gave the best activity in framework catalyst of claim 1 in the presence of a terms of benzaldehyde selectivity for the oxidation of tolu solvent and an oxidizing agent to form an oxidized ene. cyclic hydrocarbon . [0178 ] Thus, the foregoing discussion discloses and 11: The method of claim 10 , wherein the cyclic hydro describes merely exemplary embodiments of the present carbon is at least one selected from the group consisting of invention . As will be understood by those skilled in the art , toluene , cyclohexane , and methylcyclohexane . the present invention may be embodied in other specific 12 : The method of claim 10 , wherein the solvent is forms without departing from the spirit or essential charac acetonitrile and the oxidizing agent is hydrogen peroxide . teristics thereof . Accordingly , the disclosure of the present 13 : The method of claim 10 , wherein the contacting is invention is intended to be illustrative , but not limiting of the performed at a temperature in the range of 40 - 100° C . for a scope of the invention , as well as other claims. The disclo time period of 2 - 36 hours . sure, including any readily discernible variants of the teach 14 : The method of claim 10 , wherein the cyclic hydro ings herein , defines , in part , the scope of the foregoing claim carbon is toluene and 15 - 80 % of the toluene is converted to terminology such that no inventive subject matter is dedi the oxidized cyclic hydrocarbon at a reaction time of greater cated to the public . than 6 hours. 1 : A metal organic framework catalyst, comprising: 15 : The method of claim 10 , wherein the cyclic hydro zinc ( II ) ions; carbon is toluene and the method has a benzaldehyde second metal ions which are not zinc ( II ) ions ; and selectivity in the range of 15 - 70 % relative to a total amount benzene - 1 , 3 , 5 -tricarboxylic acid ligands ; of oxidized cyclic hydrocarbon products . wherein the benzene - 1 , 3 , 5 - tricarboxylic acid ligands 16 : The method of claim 10 , wherein the cyclic hydro comprise carboxylate groups , each carboxylate group carbon is toluene and the method has a benzaldehyde forming a coordinative bond to the zinc ( II ) ions or the selectivity relative to a total amount of oxidized cyclic second metal ions to form a coordination network in the hydrocarbon products greater than or equal to a benzalde form ofporous polyhedral crystals that are isostructural hyde selectivity relative to a total amount of oxidized cyclic to an HKUST - 1 metal organic framework . hydrocarbon products of a substantially similar method 2 : The metal organic framework catalyst of claim 1, performed in a substantially similar manner with a substan wherein the second metal ions are at least one selected from tially similar metal organic framework catalyst lacking the the group consisting of iron ( II ) ions, cobalt ( II ) ions, and zinc ( II ) ions , the second metal ions, or both . copper (II ) ions. 17: The method of claim 10 , wherein the cyclic hydro 3 : The metal organic framework catalyst of claim 1 , carbon is toluene and the second metal ions are iron ( II ) ions wherein the ratio of zinc ( II ) ions to the additional metal ions and the oxidation has a benzaldehyde selectivity of greater is in the range of 0 .01 to 5 . 0 . than 55 % relative to a total amount of oxidized cyclic 4 : The metal organic framework catalyst of claim 1 , hydrocarbon products . wherein the porous polyhedral crystals have pores with an 18 : The method of claim 10 , wherein the cyclic hydro average diameter of 0 . 2 - 2 . 0 nm and a BET surface area in carbon is at least one selected from the group consisting of the range of 500 - 3000 m²/ g . cyclohexane and methylcyclohexane and 10 -60 % of the 5 : The metal organic framework catalyst of claim 1, cyclic hydrocarbon is converted to the oxidized cyclic wherein the porous polyhedral crystals are octahedral or hydrocarbon at a reaction time of greater than 12 hours . cubic with an average longest linear dimension in the range 19 : The method of claim 10 , wherein the cyclic hydro of 2 - 20 um . carbon is cyclohexane and the method has a cyclohexanone 6 : The metal organic framework catalystof claim 1 , which selectivity in the range of 45 - 80 % relative to a total amount has a larger unit cell dimension a than the HKUST - 1 metal of oxidized cyclic hydrocarbon products . organic framework . 20 : The method of claim 10 , further comprising recover 7 : The metal organic framework catalyst of claim 1 , ing and reusing the metal organic framework catalyst in at wherein the second metal ions are copper ( II ) ions and the least 2 reaction iterations with a less than 20 percentage ratio of zinc ( II ) ions to copper ( II) ions is in the range of point decrease in conversion , selectivity , or both . 0 .01 to 1 . 0 . * * * * *