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(12) United States Patent (10) Patent No.: US 9,623.404 B2 Hupp Et Al

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(12) United States Patent (10) Patent No.: US 9,623.404 B2 Hupp Et Al USOO9623404B2 (12) United States Patent (10) Patent No.: US 9,623.404 B2 Hupp et al. (45) Date of Patent: Apr. 18, 2017 (54) METAL, ORGANIC FRAMEWORKS FOR 35/1057 (2013.01); B01J 35/1061 (2013.01); THE CATALYTIC DETOXFICATION OF C07F 7/006 (2013.01); A62D 2101/02 CHEMICAL WARFARE NERVE AGENTS (2013.01); B01D 2253/204 (2013.01); B01D 2253/306 (2013.01); B01D 2253/308 (71) Applicant: NORTHWESTERN UNIVERSITY, (2013.01); Evanston, IL (US) (Continued) (58) Field of Classification Search (72) Inventors: Joseph T. Hupp, Northfield, IL (US); CPC .............. B01D 53/04; B01D 2253/204; B01D Omar K. Farha, Morton Grove, IL 2253/306; B01D 2253/308; B01D (US); Michael J. Katz, Evanston, IL 2257/408; B01D 2259/4583; B01J 20/226 (US); Joseph E. Mondloch, Evanston, USPC ........ 95/90; 96/108; 423/210, 236; 502/150, IL (US) 502/152, 153,401; 55/DIG. 33, DIG. 35 See application file for complete search history. (73) Assignee: NORTHWESTERN UNIVERSITY, Evanston, IL (US) (56) References Cited (*) Notice: Subject to any disclaimer, the term of this U.S. PATENT DOCUMENTS patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. 8,883,676 B1 * 1 1/2014 Peterson ................ B01J 20,226 (21) Appl. No.: 14/585,718 9,216.404 B1* 12/2015 Peterson ................ B01J 20,226 (Continued) (22) Filed: Dec. 30, 2014 OTHER PUBLICATIONS (65) Prior Publication Data Mondloch et al. “Vapor-Phase Metalation by Atomic Layer Depos US 2016/O175827 A1 Jun. 23, 2016 tion in a Metal-Organic Framework” Jul. 2013, Journal of the Related U.S. Application Data American Chemical Society, pp. 10294-10297.* (Continued) (60) Provisional application No. 61/922.370, filed on Dec. 31, 2013. Primary Examiner — Frank Lawrence (74) Attorney, Agent, or Firm — The Marbury Law (51) Int. C. Group PLLC BOLD 53/04 (2006.01) BOI 3/16 (2006.01) (57) ABSTRACT (Continued) A method of using a metal organic framework (MOF) (52) U.S. C. comprising a metal ion and an at least bidendate organic CPC ............. B01J 31/1691 (2013.01); A62B 7/10 ligand to catalytically detoxify chemical warfare nerve (2013.01); A62D 3/35 (2013.01); A62D 9/00 agents including exposing the metal-organic-framework (2013.01); B0 ID 53/04 (2013.01); B01.J (MOF) to the chemical warfare nerve agent and catalytically 20/226 (2013.01); B01J 35/023 (2013.01); decomposing the nerve agent with the MOF. B01J 35/1019 (2013.01); B01J 35/1023 (2013.01); B01J 35/1028 (2013.01); B01.J 32 Claims, 7 Drawing Sheets US 9,623.404 B2 Page 2 (51) Int. Cl. Peterson, G.W., et al., “Removal of Chlorine Gases From Streams BOI 35/ (2006.01) of Air Using Reactive Zirconium Hydroxide Based Filtration Media.” Ind. Eng. Chem. Res., vol. 51, pp. 2675-2681, (2012). BOI 35/02 (2006.01) Wagner, G.W., et al., “Effect of Adsorbed Water and Surface C07F 7/00 (2006.01) Hydroxyls on the Hydrolysis of VX, GD, and HD on Titania A62D 3/35 (2007.01) Materials: The Development of Self-Decontaminating Paints.” Ind. A62B 7/10 (2006.01) Eng. Chem. Res., vol. 51, pp. 3598-3603, (2012). Bandosz, T. J. et al., “Reactions of VX, GD, and HD with Zr(OH) BOI 20/22 (2006.01) 4. Near Instantaneous Decontamination of VX.” J. Phys. Chem. A62D 9/00 (2006.01) vol. 116, pp. 11606-11614, (2002). A62D 101/02 (2007.01) Wang, S., et al., “Organophophorous Ester Degradation by Chromium(III) Terephthalate Metal—Organic Framework (MIL (52) U.S. Cl. 101) Chelated to N,N-Dimethylaminopyridine and Related CPC .................. BOID 2257/408 (2013.01); B0ID Aminopyridines.” ACS Appl. Mater. Interfaces, 2013. (5): p. 1269 2259/4583 (2013.01); B01.J 2531/46 (2013.01); 1278. B01J 2531/48 (2013.01); B01J 2531/49 Smith, B. M.. “Catalytic methods for the destruction of chemical (2013.01) warfare agents under ambient conditions.” Chem. Soc. Rev., 2008. (37): p. 470-478. (56) References Cited Bigley, et al., "Catalytic Mechanism for Phosphotriesterases.” Biochim. Biophys. Acta, 2013, 1834(1): p. 443-453. U.S. PATENT DOCUMENTS Katz, M. J. et al., “Simple and Compelling Biomimetic Metal Organic Framework Catalyst for the Degradation of Nerve Agent 2010/0081186 A1* 4, 2010 Lee .......................... A62D 3.36 Simulants.” Angew Chem Int Ed. 2013. (53): p. 497-501. 435/177 Peterson, G.W. et al., “Detoxification of Chemical Warfare Agents 2011/0010826 A1 1/2011 Kaskel ..................... A62D 5700 by CuBTC,” J. Porous Mater, 2013. (21): p. 121-126. 2/457 Peterson, G. W. et al., “Effects of pelletization pressure on the 2011/0126713 A1* 6/2011 Legare ................... A62B 23/02 physical and chemical properties of the metal—organic frameworks 96.135 Cu3(BTC)2 and UiO-66,” Microporous and Mesoporous Materials, vol. 179, pp. 48-53, (2013). OTHER PUBLICATIONS Li, H., et al., “Design and Synthesis of an Exceptionally Stable and Highly Porous Metal-Organic Framework.” Nature, 1999. Ferey, G., “Hybrid Porous Solids: Past, Present.” Future. Chemical 402(6759): p. 276-279. Society Reviews, vol. 37, pp. 191-214 (2008). Wilmer, C.E., et al., "Large-Scale Screening of Hypothetical Metal Farha, O.K., et al., “DeNovo Synthesis of a Metal-Organic Frame Organic Frameworks,” Nature Chemistry, 2012. 4(2): p. 83-89. work Material Featuring Ultrahigh Surface Area and Gas Storage Furukawa, H., et al., Ultrahigh Porosity in Metal-Organic Frame Capacities.” Nature Chemistry, vol. 2, pp. 944-948 (2010). works, Science, 2010. 329(5990): p. 424-428. Wilmer, C.E., et al., “Structure-Property Relationships of Porous Chae, H.K., et al., “A Route to High Surface Area, Porosity and Materials for Carbon Dioxide Separation and Capture.” Energy & Inclusion of Large Molecules in Crystals,” Nature, 2004. Environmental Science, vol. 5, pp. 9849-9856, (2012). 427(6974): p. 523-527. Raushel, F. M.. “Catalytic Detoxification.” Nature, vol. 469, pp. 310-311 (2011). * cited by examiner U.S. Patent Apr. 18, 2017 Sheet 1 of 7 US 9,623.404 B2 F.G. C. FG. d U.S. Patent Apr. 18, 2017 Sheet 2 of 7 US 9,623.404 B2 COs:- FG, 2a FG, 2b U.S. Patent Apr. 18, 2017 Sheet 3 of 7 US 9,623.404 B2 iii * Ti, Zr, Hf,(us-OH),(u-O),(O.), (where x + y + Z = 6) * 12 linkers coordinate Zr * Four proximal i-OH groups per Zre FG, 3a . Zr, Hf,Ti,(us-O),(us-OH),(HO),(OH),(O.) (where x + y + z c 6) * 8 linkers coordinate Zr * Four proximal -OH groups, four termina water molecules and four terminal hydroxyl groups per Zr FG, 3. U.S. Patent Apr. 18, 2017 Sheet 4 of 7 US 9,623.404 B2 100 O-68 333K UiO-66298 K no catalyst 50 100 U.S. Patent Apr. 18, 2017 Sheet S of 7 US 9,623.404 B2 ^ X-1 NU-1000-dehyd 60 y - 298 K Y NU-3000-dehyd, 2 week exposure t-- - - - - Time (min) FG. 4b. U.S. Patent Apr. 18, 2017 Sheet 6 of 7 US 9,623.404 B2 SO4. 500a SO2 FG, 5a FG. Sb SA OOC FG. Sc U.S. Patent Apr. 18, 2017 Sheet 7 Of 7 US 9,623.404 B2 83 F.G. 6b US 9,623.404 B2 1. 2 METAL, ORGANIC FRAMEWORKS FOR metal-organic-framework (MOF) to the chemical warfare THE CATALYTIC DETOXIFICATION OF nerve agent and catalytically decomposing the nerve agent CHEMICAL WARFARE NERVE AGENTS with the MOF. A further embodiment includes a method of manufactur RELATED APPLICATIONS ing a MOF-based gas respirator for filtering and detoxifying nerve agents. This application claims the benefit of U.S. Provisional Additionally, another embodiment relates to a method of Application No. 61/922,370, filed Dec. 31, 2013, hereby making MOFs for catalytically detoxifying chemical war incorporated by reference in its entirety. fare nerve agents with a half-life rate of no greater than 45 10 minutes. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT BRIEF DESCRIPTION OF THE DRAWINGS This invention was made with government Support under FIGS. 1a-1d are ball and stick illustrations of metal 15 organic frameworks including (a) CoMOF74, (b) NU100, HDTRA1-10-1-0023 awarded by the Defense Threat Reduc (c) AlMIL53, and (d) NU125. tion Agency and DE-AC05-06OR23100 (SubK No. FIGS. 2a-2b are synthesis schemes to produce metal 10-20903 DOE Oak Ridge Tenn.) awarded by the Depart organic frameworks (shown as ball and stick illustrations) ment of Energy. The government has certain rights in the including (a) UiO-66 and (b) NU-1000. invention. FIG. 3a-3b are ball and stick illustrations of the metal node/cluster of (a) UiO-66 illustrating hydroxyl groups FIELD bridged between two Zirconium atoms in a twelve-connected Zre cluster, and (b) NU-1000 illustrating the bridging The present invention is directed to metal-organic frame hydroxyl groups, terminal hydroxyl groups, and terminal works as catalysts and Sorbents for the capture and detoxi 25 water molecules in an eight-connected Zre cluster (metal fication of chemical warfare nerve agents. node). FIG. 4a are conversion profiles (percentage detoxified BACKGROUND versus time in minutes) of the detoxification of a chemical warfare nerve agent simulant, methyl paraoxon, using UiO Extensive research over the past few years has focused on 30 66. This plot shows a detoxification half-life of 45 minutes the synthesis and characterization of highly tunable, at 298 K. microporous materials with high internal surface areas. FIG. 4b are conversion profiles (percentage detoxified Metal-Organic Frameworks (MOFs) are a crystalline subset versus time in minutes) of the detoxification of a chemical of these materials that have shown promise for a wide array warfare nerve agent simulant, methyl paraoxon, using of gas, Vapor, and liquid applications ranging from Storage, 35 NU-1000 and dehydrated NU-1000.
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