DOCSLIB.ORG

Synthesis, Characterization and Physical/Chemical Properties Of

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis, Characterization and Physical/Chemical Properties Of Synthesis, characterization and physical/chemical properties of polyoxometalate-based materials Zur Erlangung des akademischen Grades eines DOKTORS DER NATURWISSENSCHAFTEN (Dr. rer. nat.) von der KIT-Fakultät für Chemie und Biowissenschaften des Karlsruher Instituts für Technologie (KIT) genehmigte Dissertation von M.Sc. Marcel Patrick Merkel aus Mannheim-Neckarau, Deutschland Karlsruhe, 2019 KIT-Dekan: Prof. Dr. Reinhard Fischer Referent: Prof. Dr. Annie Powell Korreferent: Prof. Dr. Peter Roesky Tag der mündlichen Prüfung: 26. Juli 2019 Für meine Familie und meine Freundin Dr. Krisana Peewasan Acknowledgements This thesis was carried out from October 2015 to June 2019 at the Institute for Inorganic Chemistry at the Karlsruhe Institute of Technology (KIT) under supervision of Prof. Dr. Annie K. Powell. First of all I would like to thank Prof. Dr. Annie K. Powell for giving me the opportunity to do my PhD study in a comfortable and very welcoming atmosphere in her working group. Additionally, I would like to thank her for a very kindness, excellent support and interesting topic. In addition, I would like to thank deeply from my heart to all: - Dr. Masooma Ibrahim: for the many tips and suggestions and the wonderful support that I was allowed to enjoy during the time of this study. - Gertraud Amschlinger: for her kindness and cozy atmosphere and for every help I got. - Dr. Christopher Anson: for solving and refining my single crystal X-ray structures and nice conversations. - Dr. Olaf Fuhr and Prof. Dr. Dieter Fenske: for measuring single crystals and nice conversations. - Dr. Andreas Eichhöfer: for the introductions to single crystal X-ray diffractometers, powder X-ray diffractometer and for every help I received from him. - Sven Stahl: for introduction in NMR-spectrometer, for ordering all chemicals, measuring all the elemental analyses and for every help. - My colleagues: Dr. Nicolas Leblanc, Dr. Sebastian Schmidt, Dr. Yan Peng, Dr. Markus Schroth, Lena Friedrich, Anthony Carter, Hagen Kämmerer, Thomas Ruppert, Rouven Pfleger and Umaira Shuaib: for every kind conversation, help with reactions and cozy atmosphere. - Cooperation Partners: Dr. George E. Kostakis, Dr. Mbomekalle Israël, Prof. Dr. Pedro De Oliveira and Dr. Ying-Chu Chen.. - My lovely family and friends: Especially to my parents Christoph and Gabrielle Merkel, my brother Dr. Marcus Merkel, my aunt Renate Ott, my uncle Thomas Ott and my grandparents Anna and Joachim Prudlik and Josef and Elfriede Cebulla: for supporting me and being always there for me. My dear girlfriend: Dr. Krisana Peewasan: for every support and every help I got from her. Annotation : The ions shown in the figures are not to scale. Organic hydrogen atoms, as well as solvent molecules are often not shown for clarity. The numerical values such as bond lengths and angles are given in standard deviation. This is in parentheses after each value and refers to the last digit. The lengths are given in Angstroms, where 1 Å = 1.10-10 m. The abbreviation TM stands for transition metals in low oxidation state. SUMMARY Polyoxometalate based metal organic frameworks (POMOFs) can be regarded in general terms as frameworks containing Polyoxometalates (POMs). Here, we can identify three distinct categories: (a) POMs occupying the cavities of a metal organic framework (MOF) structure (POM@MOF), (b) POMs used as secondary building units (SBUs) in the network and (c) POMs as part of the linker of the framework. For this research presented in this thesis, it was decided to concentrate on the barely explored area (c). Furthermore, it seemed a useful strategy to compare combining metals from the d series (TM = Cu, Zn, Cd, Mn, Mo) with rare earth metal ions (RE = Y, La – Lu). The first stage of the exploration was to develop suitable L – POM – L linkers, where L is a Tris-functionalized ((OHCH 2)3CNH 2) unit and POM is the Anderson- Evans POM. This Polyanion was chosen because it provides three octahedrally arranged coordination sites above and below the central plane, which can be occupied by three hydroxyl groups of a Tris ligand. This Tris-ligand can be functionalized at the amine group using suitable N-R forming reagents, such as R’HC=O, R’HC-X (X = Cl, Br) and R’COCl. R was chosen such the terminus T func provides a coordinating group for a TM or RE nodes. T func can be for example N py , OCOO , N C≡N, etc. In this way L – POM – L linkers were formed. Two of these L – POM – Ls proved to be particularly successful for producing transition metal based POMOFs, where the functional group is pyridyl and RE based POMOFs, where the functional group is carboxylate. These could be characterized using single crystal X-ray diffraction, which is important in this field since we ultimately should be able to relate the functionality to topology. In this context optical properties such as bandgap, UV-vis and Fourier Transform Infrared (FT-IR) Spectroscopy were investigated. The highlight within the TM-based series was the activity of [N(n-C4H9)4]5[CuCl(DMF){MnMo 6O18 ((OCH 2)3CN=CH 3 (4-C5H4N)) 2}2]⋅3DMF (13) for the A -Coupling without the need for inert conditions. For the RE-series the Dy based compound [Dy(DMF) 4(H 2O)] 2[Dy 3 I (DMF) 6][((MnMo 6O18 )((OCH 2)3CNHCH 2(C6H4)COO)2]3·5DMF (12) -Dy proved to be the most versatile. Finally, a completely new topology was discovered for compound [Zn(DMF) 4][Zn(DMF) 2MnMo 6O18 {(OCH 2)3CN=CH(4-C5H4N)} 2]2 ⋅10DMF (14A) and interestingly the synthesis for this compound has a bifurcation in terms of topology since the equally abundant component [(Zn(DMF) 3)2(Zn(DMF) 4MnMo 6O18 {(OCH 2)3CN=CH(4-C5H4N)} 2)2]⋅9DMF (14B) of the reaction has a completely different topologically structure. II Zusammenfassung Polyoxometallat-basierte Metall organische Netzwerke (POMOFs) können allgemein als Netzwerke angesehen werden, welche Polyoxometallate (POMs) beinhalten. Hier lassen sich drei Kategorien unterscheiden: (a) POMs, welche die Hohlräume einer Metal organic framework (MOF)-Struktur belegen (POM@MOF), (b) POMs, die als Sekundary Building Units (SBUs) im Netzwerk verwendet werden und (c) POMs, die als Teil des Linkers des Frameworks genutzt werden. In der vorgestellten Arbeit wurden die POMOFs der Kategorie (c) untersucht. Darüber hinaus wurde die Kombination aus Metallen der d - Reihe (TM = Cu, Zn, Cd, Mn, Mo) mit Seltenerdmetallionen (RE = Y, La - Lu) verglichen. Im ersten Teil der Forschungsarbeit wurden L-POM-L-Linker entwickelt, wobei L eine Tris-funktionalisierte ((OHCH 2)3CNH 2) Einheit und POM das Anderson- Evans-Polyanion ist. Dieses Polyanion weist drei oktaedrisch angeordnete Koordinationsstellen oberhalb und unterhalb der zentralen Ebene auf, die von drei Hydroxylgruppen eines Tris - Liganden besetzt werden können. Dieser Tris-Ligand kann an der Aminogruppe unter Verwendung geeigneter N-R-bildender Reagenzien wie R’HC = O, R’HC-X (X = Cl, Br) und R’COCl funktionalisiert werden. R wurde so gewählt, dass der Terminus T func eine koordinierende Gruppe für einen TM- oder RE-Knotenpunkt bereitstellt. T func kann beispielsweise N py , OCOO , N C≡N usw. sein. Auf diese Weise wurden L-POM-L-Linker gebildet. Zwei dieser L-POM-Ls erwiesen sich als besonders erfolgreich für die Herstellung von übergangsmetallbasierten POMOFs, mit Pyridylgruppen als funktionelle Gruppen und RE-basierte POMOFs, bei denen die funktionelle Gruppen Carboxylate sind. Diese konnten mittels Einkristall-Röntgenstrukturanalyse charakterisiert werden, womit die Funktionalität mit der Topologie in Beziehung gesetzt werden konnte. In diesem Zusammenhang wurden optische Eigenschaften wie Bandlücken, UV-Vis- und Fourier-Transformierte-Infrarot- (FT-IR-) Spektroskopie untersucht. Das Highlight innerhalb der TM-basierten Reihe war die Aktivität von III [N( n-C4H9)4]5[CuCl(DMF){MnMo 6O18 ((OCH 2)3CN=CH (4-C5H4N)) 2}2]⋅3DMF (13) für A 3-Kupplungsreaktionen ohne Luftausschluss. Für die RE-Reihe erwies sich die auf Dy basierende Verbindung [Dy(DMF) 4(H 2O)] 2[Dy 3 (DMF) 6][((MnMo 6O18 )((OCH 2)3CNHCH 2(C 6H4)COO) 2]3·5DMF (12) -Dy als die vielseitigste. Schließlich wurde für eine weitere Verbindung [Zn(DMF) 4] [Zn(DMF) 2MnMo 6O18 {(OCH 2)3CN=CH(4-C5H4N)} 2]2 ⋅10DMF (14A) eine völlig neue Topologie entdeckt. Interessanterweise weist die Synthese für diese Verbindung eine Bifurkation in Bezug auf die Topologie auf, da die ebenso häufig vorkommende Komponente [(Zn(DMF) 3)2(Zn(DMF) 4MnMo 6O18 {(OCH 2)3 CN=CH(4-C5H4N)} 2)2]⋅9DMF (14B) der Reaktion eine völlig andere topologische Struktur aufweist. IV Table of Contents 1 Historical Background 7 2 Motivation and Objective 9 3 Introduction 11 3.1 Polyoxometalates ................................................................................. 11 3.1.1 Classification of POMs ......................................................................... 13 3.1.2 Isomers of polyoxometalates ................................................................. 23 3.1.3 Lacunary derivatives of polyanions ...................................................... 25 3.2 Metal-Organic Frameworks (MOFs) ................................................ 27 3.2.1 Primary Buildings Units (PBUs) ........................................................... 28 3.2.2 Linkers for MOFs .................................................................................. 28 3.2.3 Secondary Building Units (SBUs) ........................................................ 30 3.2.4 Topological consideration of MOFs ..................................................... 31 3.2.5 Crystal-to-crystal (CTC) (topotactic) transformation
Load more

Recommended publications
  • Vanadium(V)-Substitution Reactions of Wells–Dawson-Type 6− Polyoxometalates: from [X2M18O62] (X = P, As; M = Mo, W) 7− to [X2VM17O62]
    Inorganics 2015, 3, 355-369; doi:10.3390/inorganics3030355 OPEN ACCESS inorganics ISSN 2304-6740 www.mdpi.com/journal/inorganics Article Vanadium(V)-Substitution Reactions of Wells–Dawson-Type 6− Polyoxometalates: From [X2M18O62] (X = P, As; M = Mo, W) 7− to [X2VM17O62] Tadaharu Ueda *, Yuriko Nishimoto, Rie Saito, Miho Ohnishi and Jun-ichi Nambu Department of Applied Science, Faculty of Science, Kochi University, Kochi 780-8520, Japan * Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +81-88-844-8299; Fax: +81-88-844-8359. Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car Received: 14 April 2015 / Accepted: 25 June 2015 / Published: 14 July 2015 Abstract: The formation processes of V(V)-substituted polyoxometalates with the Wells–Dawson-type structure were studied by cyclic voltammetry and by 31P NMR and Raman spectroscopy. Generally, the vanadium-substituted heteropolytungstates, 7− 7− [P2VW17O62] and [As2VW17O62] , were prepared by mixing equimolar amounts of the 10− 10− corresponding lacunary species—[P2W17O61] and [As2W17O61] —and vanadate. According to the results of various measurements in the present study, the tungsten site in 6− 6− the framework of [P2W18O62] and [As2W18O62] without defect sites could be substituted 7− 7− with V(V) to form the [P2VW17O62] and [As2VW17O62] , respectively. The order in which the reagents were mixed was observed to be the key factor for the formation of Dawson-type V(V)-substituted polyoxometalates. Even when the concentration of each reagent was identical, the final products differed depending on the order of their addition to the reaction mixture. Unlike Wells–Dawson-type heteropolytungstates, the molybdenum sites in the 6− 6− framework of [P2Mo18O62] and [As2Mo18O62] were substituted with V(V), but formed 4− 4− 7− Keggin-type [PVMo11O40] and [AsVMo11O40] instead of [P2VMo17O62] and 7− [As2VMo17O62] , respectively, even though a variety of reaction conditions were used.
    [Show full text]
  • Polyoxometalate Bleaching of Kraft Pulp
    In: Proceedings of the 1995 TAPPI Pulping conference; 1995 October 1-5; Chicago, IL. Atlanta, GA: TAPPI PRESS: 153-156.Book 1. POLYOXOMETALATE BLEACHING OF KRAFT used in kraft pulping is envisioned. In bleaching. fully oxidized PULP: A HIGHLY SELECTIVE CLOSED MILL POM complexes are reacted with unbleached pulp under anaerobic TECHNOLOGY. conditions. During oxidative bleaching. the POM complexes are reduced and oxidized residual lignin fragments are dissolved by the I. A. Weinstock, R. H. Atalla. R. S. Reiner, M. A. Moen bleaching liquor. Afterwards, the reduced POM liquor is reoxidized and K. E. Hammel by oxygen under conditions that convert dissolved lignin fragments USDA Forest Service. to carbon dioxide and water. Thus, the POM liquor can be Forest Products Laboratory1 continually reused with mill closure achieved by use of a recovery Madison, Wisconsin U.S.A. system, in which. analogously to the kraft recovery system. active POM liquors are reactivated and organic materials consumed. C. L. Hill C. J. Houtman Emory University University of Wisconsin-Madison Closed Mill Polyoxometalate Blenching Process Department of Chemistry DepartmentofChemical Engineering Atlanta, Georgia U.S.A. Madison, Wisconsin. U.S.A. ABSTRACT A process for using polyoxometalate (POM) salts and oxygen in the commercial bleaching of chemical pulps is herein described. A clear advantage of polyoxometalates over oxygen alone. hydrogen peroxide or ozone is their inherently high oxidative selectivity for the residual lignin in softwood kraft pulps. Softwood kraft pulps delignified to low kappa numbers using POM salts possess Figure 1. Schematic diagram of an effluent-free papermaking properties comparable to those obtained using polyoxometalate bleaching process.
    [Show full text]
  • (Hetero)Polyoxometalates for Simultaneously
    (19) TZZ¥__T (11) EP 3 175 867 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 07.06.2017 Bulletin 2017/23 A61L 2/232 (2006.01) A47J 31/44 (2006.01) A01N 25/10 (2006.01) A01N 59/16 (2006.01) (2006.01) (2006.01) (21) Application number: 15197882.2 A61L 2/238 C02F 1/72 C09D 5/16 (2006.01) D06F 35/00 (2006.01) (2006.01) (2006.01) (22) Date of filing: 03.12.2015 F24C 15/00 F24C 15/20 H05B 6/64 (2006.01) A47L 15/42 (2006.01) A61L 2/235 (2006.01) A61L 9/18 (2006.01) C08K 5/00 (2006.01) C08K 5/56 (2006.01) C02F 103/00 (2006.01) (84) Designated Contracting States: (72) Inventors: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • SCHEPERS, Klaus GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO 35619 Braunfels (DE) PL PT RO RS SE SI SK SM TR • MISCHO, Horst Designated Extension States: 54295 Trier (DE) BA ME • BIRKEL, Alexander Designated Validation States: 64287 Darmstadt (DE) MA MD (74) Representative: Teipel, Stephan et al (71) Applicant: POM Patentverwaltungs GbR Lederer & Keller 35619 Braunfels (DE) Patentanwälte Partnerschaft mbB Unsöldstrasse 2 80538 München (DE) (54) USE OF (HETERO)POLYOXOMETALATES FOR SIMULTANEOUSLY IMPARTING ANTIMICROBIAL PROPERTIES TO A SURFACE OF A SUBSTRATE AND REDUCING THE GROWTH OF A BIOFILM ON THE SURFACE OF THE SUBSTRATE (57) The present invention relates to the use of at a substrate comprising a (hetero)polyoxometalate or a leastone (hetero)polyoxometalate for simultaneously im- mixture of (hetero)polyoxometalates, wherein the sub- partingantimicrobial propertiesto a surface ofa substrate strate is selected from a polymer body, paint, varnish and and reducing the growth of a biofilm on the surface of the coating.
    [Show full text]
  • Hybrid Organic-Inorganic Materials Based on Polyoxometalates and Ionic Liquids and Their Application in Catalysis
    Hindawi Publishing Corporation ISRN Chemical Engineering Volume 2014, Article ID 963792, 13 pages http://dx.doi.org/10.1155/2014/963792 Review Article Hybrid Organic-Inorganic Materials Based on Polyoxometalates and Ionic Liquids and Their Application in Catalysis Svetlana Ivanova Departamento de Qu´ımica Inorganica´ e Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla-CSIC, Avenida AmericoVespucio49,41092Sevilla,Spain´ Correspondence should be addressed to Svetlana Ivanova; [email protected] Received 2 October 2013; Accepted 7 November 2013; Published 28 January 2014 Academic Editors: P. Maki-Arvela,¨ A. Ragauskas, and A. M. Seayad Copyright © 2014 Svetlana Ivanova. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. An overview of the recent advances in the field of polyoxometalate, ionic liquid hybrids, is proposed with a special attention paid to their application in catalysis, more precisely biphasic and heterogeneous catalysis. Both components of the hybrids are separately outlined pointing to their useful properties and potential for catalysis, followed by the description of the hybrids preparation and synergy between components in a large range of organic transformations. And finally a vision on the future developments is proposed. 1. Polyoxometalates: General Aspects [6–9]. There are literally thousands of compounds in the polyoxometalate category which defers on their size, shape, Polyoxometalates (POMs) are a class of anionic metal-oxygen and composition. Recently, Long et al. [10]proposedavery clusters built by the connection of [MO] polyhedra of elegant way to classify the POM’s compounds in-as-called the early transition metals in their highest oxidation states “polyoxometalate periodic table.” Th e y prop o s e d t h re e bro a d [1, 2].
    [Show full text]
  • The Reactivity and Stability of Polyoxometalate Water Oxidation Electrocatalysts
    molecules Review The Reactivity and Stability of Polyoxometalate Water Oxidation Electrocatalysts Dandan Gao 1, Ivan Trentin 1, Ludwig Schwiedrzik 2 , Leticia González 2,* and Carsten Streb 1,3,* 1 Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany; [email protected] (D.G.); [email protected] (I.T.) 2 Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währinger Str. 17, 1090 Vienna, Austria; [email protected] 3 Helmholtz-Institute Ulm (HIU), Helmholtzstr. 11, 89081 Ulm, Germany * Correspondence: [email protected] (L.G.); [email protected] (C.S.) Academic Editor: Mark Symes Received: 4 December 2019; Accepted: 27 December 2019; Published: 31 December 2019 Abstract: This review describes major advances in the use of functionalized molecular metal oxides (polyoxometalates, POMs) as water oxidation catalysts under electrochemical conditions. The fundamentals of POM-based water oxidation are described, together with a brief overview of general approaches to designing POM water oxidation catalysts. Next, the use of POMs for homogeneous, solution-phase water oxidation is described together with a summary of theoretical studies shedding light on the POM-WOC mechanism. This is followed by a discussion of heterogenization of POMs on electrically conductive substrates for technologically more relevant application studies. The stability of POM water oxidation catalysts is discussed, using select examples where detailed data is already available. The review finishes with an outlook on future perspectives and emerging themes in electrocatalytic polyoxometalate-based water oxidation research. Keywords: polyoxometalate; water oxidation catalysis; oxygen evolution reaction; self-assembly; electrocatalysis 1.
    [Show full text]
  • Applications of Polyoxometalates in Heterogenous Catalysis Piotr Putaj
    Applications of polyoxometalates in heterogenous catalysis Piotr Putaj To cite this version: Piotr Putaj. Applications of polyoxometalates in heterogenous catalysis. Other. Université Claude Bernard - Lyon I, 2012. English. NNT : 2012LYO10038. tel-00869429 HAL Id: tel-00869429 https://tel.archives-ouvertes.fr/tel-00869429 Submitted on 3 Oct 2013 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. N° d’ordre 38-2012 Année 2012 THESE DE L‘UNIVERSITE DE LYON délivrée par L’UNIVERSITE CLAUDE BERNARD LYON 1 ECOLE DOCTORALE DE CHIMIE DIPLOME DE DOCTORAT (arrêté du 7 août 2006) soutenue publiquement le 21/03/2012 par M. Piotr Putaj Applications des polyoxométalates en catalyse hétérogène Directeur de thèse : M. Frédéric Lefebvre Jury : M. Stéphane Daniele (Président) Mme Catherine Marchal-Roch M. Régis Gauvin M. Richard Villanneau M. José M. Fraile M. Frédéric Lefebvre N° d’ordre 38-2012 Année 2012 THESE DE L‘UNIVERSITE DE LYON délivrée par L’UNIVERSITE CLAUDE BERNARD LYON 1 ECOLE DOCTORALE DE CHIMIE DIPLOME DE DOCTORAT (arrêté du 7 août 2006) soutenue publiquement le 21/03/2012 par M. Piotr Putaj Applications of polyoxometalates in heterogenous catalysis Directeur de thèse : M.
    [Show full text]
  • Research Progress on Catalytic Water Splitting Based on Polyoxometalate/Semiconductor Composites
    catalysts Review Research Progress on Catalytic Water Splitting Based on Polyoxometalate/Semiconductor Composites Yue Wu * and Lihua Bi * College of Chemistry, Jilin University, Changchun 130012, China * Correspondence: [email protected] (Y.W.); [email protected] (L.B.) Abstract: In recent years, due to the impact of global warming, environmental pollution, and the energy crisis, international attention and demand for clean energy are increasing. Hydrogen energy is recognized as one of the clean energy sources. Water is considered as the largest potential supplier of hydrogen energy. However, artificial catalytic water splitting for hydrogen and oxygen evolution has not been widely used due to its high energy consumption and high cost during catalytic cracking. Therefore, the exploitation of photocatalysts, electrocatalysts, and photo-electrocatalysts for rapid, cost effective, and reliable water splitting is essentially needed. Polyoxometalates (POMs) are regarded as the potential candidates for water splitting catalysis. In addition to their excellent catalytic properties and reversibly redox activities, POMs can also modify semiconductors to overcome their shortcomings, and improve photoelectric conversion efficiency and photocatalytic activity, which has attracted more and more attention in the field of photoelectric water splitting catalysis. In this review, we summarize the latest applications of POMs and semiconductor composites in the field of photo-electrocatalysis (PEC) for hydrogen and oxygen evolution by catalytic water splitting in recent years and take the latest applications of POMs and semiconductor composites in photocatalysis for water splitting. In the conclusion section, the challenges and strategies of photocatalytic and PEC water-splitting by POMs and semiconductor composites are discussed. Citation: Wu, Y.; Bi, L.
    [Show full text]
  • Ion-Pairing in Polyoxometalate Chemistry: Impact of Fully Hydrated Alkali Metal Cations on Properties of the Keggin 3- [PW12O40] Anion
    Dalton Transactions Ion-Pairing in Polyoxometalate Chemistry: Impact of Fully Hydrated Alkali Metal Cations on Properties of the Keggin 3- [PW12O40] Anion Journal: Dalton Transactions Manuscript ID DT-ART-06-2020-002239.R1 Article Type: Paper Date Submitted by the 14-Jul-2020 Author: Complete List of Authors: Kaledin, Alexey; Emory University, Cherry L. Emerson Center for Scientific Computation Yin, Qiushi; Emory University Hill, Craig; Emory University Lian, Tianquan; Emory University Musaev, D.; Emory University Page 1 of 15 Dalton Transactions Ion-Pairing in Polyoxometalate Chemistry: Impact of Fully Hydrated Alkali 3- Metal Cations on Properties of the Keggin [PW12O40] Anion Alexey L. Kaledin,1 Qiushi Yin,2 Craig L. Hill,1,2 Tianquan Lian,1,2 and Djamaladdin G. Musaev1,2,* 1 Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322 USA 2 Department of Chemistry, Emory University, Atlanta, Georgia 3032 USA Abstract The counterions of polyoxometalates (POMs) impact properties and applications of this growing class of inorganic clusters. Here, we used density functional theory (DFT) to elucidate the impact of fully hydrated alkali metal cations on the geometry, electronic structure, and chemical properties 3- of the polyoxotungstate anion [PW12O40] . The calculations show that the HOMO of the free anion 3- [PW12O40] is a linear combination of the 2p AOs of the bridging oxygens, and the first few LUMOs are the 5d orbitals of the tungsten atoms. The S0 S1 electron excitation, near 3 eV, is associated with the O(2p) W(5d) transition. Anion/cation complexation leads to formation of 3- + [PW12O40] [M (H2O)16]3 ion-pair complexes, where with the increase of atomic number of M, the + M (H2O)16 cluster releases several water molecules and interacts strongly with the 3- + polyoxometalate anion.
    [Show full text]
  • Building Nanostructured Polystyrene Latex Beads Covered
    BUILDING NANOSTRUCTURED POLYSTYRENE LATEX BEADS COVERED WITH POLYOXOMETALATE CLUSTERS A Thesis Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Xinyue Chen May, 2015 BUILDING NANOSTRUCTURED POLYSTYRENE LATEX BEADS COVERED WITH POLYOXOMETALATE CLUSTERS Xinyue Chen Thesis Approved: Accepted: ________________________________ ________________________________ Advisor Dean of the College Dr. Tianbo Liu Dr. Eric J. Amis ________________________________ ________________________________ Faculty Reader Interim Dean of the Graduate School Dr. Mesfin Tsige Dr. Rex Ramsier ________________________________ ________________________________ Department Chair Date Dr. Coleen Pugh ii ABSTRACT Polyoxometalates (POMs) are a class of metal oxide frameworks, whose structures, morphologies, and elecrionic properties can be designed and tuned to meet with different demands.1 POM-organic hybrids are usually made by linking organic part onto the active site of POMs. They have been widely applied in the field of catalysis, electronics, medicine and biology because they have some extraordinary properties.2 As far as making POMs into catalysts, there are some problems: 1) poor processability and recyclability for homogenous catalyst; 2) low efficiency for the heterogeneous catalyst.3 In this work, we developed a new way to fabricate POM based latex particles via emulsion polymerization. These nanoparticles are formed with core-shell structure with polystyrene as core and POMs covered the surface and can be used as quasi-homogenous catalyst, which are easy to recycle and also can maximize the catalytic efficiency. This work explored a new idea to make POM-base catalysts. iii ACKNOWLEDGEMENTS I would like to thank my adviser, Dr. Tianbo Liu, for providing me the opportunity to conduct this project, and thanks to Dr.
    [Show full text]
  • Synthesis and Characterization of 8-Yttrium(III)-Containing 81-Tungsto-8-Arsenate(III), 43− [Y8(CH3COO)(H2O)18(As2w19o68)4(W2O6)2(WO4)]
    Inorganics 2015, 3, 267-278; doi:10.3390/inorganics3020267 OPEN ACCESS inorganics ISSN 2304-6740 www.mdpi.com/journal/inorganics Article Synthesis and Characterization of 8-Yttrium(III)-Containing 81-Tungsto-8-Arsenate(III), 43− [Y8(CH3COO)(H2O)18(As2W19O68)4(W2O6)2(WO4)] 1,† 1,2 1, Masooma Ibrahim , Bassem S. Bassil and Ulrich Kortz * 1 Department of Life Sciences and Chemistry, Jacobs University, P.O. Box 750 561, 28725 Bremen, Germany; E-Mails: [email protected] (B.S.B.); [email protected] (M.I.) 2 Department of Chemistry, Faculty of Sciences, University of Balamand, P.O. Box 100, Tripoli, Lebanon † Present address: Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. * Author to whom correspondence should be addressed; E-Mail: [email protected]; Fax: +49-421-200 3102; Tel: +49-421-200 3235 (U.K.). Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car Received: 10 April 2015 / Accepted: 20 May 2015 / Published: 11 June 2015 Abstract: The 8-yttrium(III)-containing 81-tungsto-8-arsenate(III) 43− [Y8(CH3COO)(H2O)18(As2W19O68)4(W2O6)2(WO4)] (1) has been synthesized in a one-pot 9− reaction of yttrium(III) ions with [B-α-AsW9O33] in 1 M NaOAc/HOAc buffer at pH 4.8. Polyanion 1 is composed of four {As2W19O68} units, two {W2O10} fragments, one {WO6} group, and eight YIII ions. The hydrated cesium-sodium salt of 1 (CsNa-1) was characterized in the solid-state by single-crystal XRD, FT-IR spectroscopy, thermogravimetric and elemental analyses.
    [Show full text]
  • Polyoxometalate (POM)-Layered Double Hydroxides (LDH) Composite Materials: Design and Catalytic Applications
    catalysts Review Polyoxometalate (POM)-Layered Double Hydroxides (LDH) Composite Materials: Design and Catalytic Applications Tengfei Li 1, Haralampos N. Miras 2,* ID and Yu-Fei Song 1,3,* ID 1 State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; [email protected] 2 WestCHEM, School of Chemistry, the University of Glasgow, Glasgow G12 8QQ, UK 3 Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China * Correspondence: [email protected] (H.N.M.); [email protected] or [email protected] (Y.-F.S.); Tel.: +44-(0)-141-330-4375 (H.N.M.); +86-10-6443-1832 (Y.-F.S.); Fax: +86-10-6443-1832 (Y.-F.S.) Academic Editor: Ivan V. Kozhevnikov Received: 9 August 2017; Accepted: 24 August 2017; Published: 1 September 2017 Abstract: Layered double hydroxides (LDHs) are an important large class of two-dimensional (2D) anionic lamellar materials that possess flexible modular structure, facile exchangeability of inter-lamellar guest anions and uniform distribution of metal cations in the layer. Owing to the modular accessible gallery and unique inter-lamellar chemical environment, polyoxometalates (POMs) intercalated with LDHs has shown a vast array of physical properties with applications in environment, energy, catalysis, etc. Here we describe how polyoxometalate clusters can be used as building components for the construction of systems with important catalytic properties. This review article mainly focuses on the discussion of new synthetic approaches developed recently that allow the incorporation of the element of design in the construction of a fundamentally new class of materials with pre-defined functionalities in catalytic applications.
    [Show full text]
  • A Survey of Applications of Polyoxometalates
    Chem. Rev. 1998, 98, 359−387 359 A Survey of Applications of Polyoxometalates Dimitris E. Katsoulis Dow Corning Corporation, Central Research and Development, Midland, Michigan 48686 Received June 2, 1997 (Revised Manuscript Received November 8, 1997) Contents I. Introduction 359 II. Corrosion Resistant Coatings 362 III. POMs as Additives in Sol−Gel Inorganic Matrixes 364 IV. POMs as Additives in Organic Nonconductive 366 Matrixes V. Dyes/Pigments/Inks 366 VI. Recording Materials 367 VII. Electrophotography. Toners 367 VIII. Precursors of Oxide Films (Optoelectronics; 368 Optical Components) IX. Membranes. Sensors 370 A. Selective Electrodes 370 B. Gas Sensors 371 C. Solid-State Electrochromic Devices 372 Dimitris E. Katsoulis was born in Athens, Greece in 1955. He received D. Electrochemical (Fuel) Cells 372 a B.S. degree in Chemistry from University of Athens in 1977. He subsequently joined the research group of Prof. Michael T. Pope at X. Electrode Modification by POMs 374 Georgetown University and obtained a Ph.D. degree in 1985. He XI. Capacitors 375 continued with a postdoctoral assignment at Georgetown University, and XII. POMs as Dopants in Electrically Conductive 375 in 1988 he joined the Science and Technology function of Dow Corporation Polymers in Midland Michigan. He is currently an Associate Research Scientist in the Rigid Materials Science Expertise Center (Central R&D) in Dow XIII. Wood Pulp Bleaching (Oxidative Delignification) 376 Corning. His research interests include hybrid materials, with focus on XIV. Analysis 377 siloxane-polyoxometalate compositions, sol−gel chemistry, silsesquioxanes, XV. Protein Precipitation Agents 380 gel systems, polymer matrix composites, and nanocomposites. XVI. Staining Agents 380 XVII.
    [Show full text]