Granted Patent
B2
US 12,269,020 · App. 18/402,535 · Granted Apr 8, 2025
Nanofiber electrocatalyst
Assignee:
UChicago Argonne, LLC
B01J31/1691B01J21/185B01J23/10B01J23/20B01J23/28B01J23/34B01J23/745B01J23/75B01J23/83B01J23/8871B01J27/24B01J35/30B01J35/33B01J35/58B01J35/613B01J35/615B01J35/617B01J35/643B01J35/647B01J37/04B01J37/084B01J37/348C08L23/0853C08L33/12C08L33/20C08L39/06C08L75/04C08L77/00B01J31/181B01J2531/11B01J2531/36B01J2531/37B01J2531/38B01J2531/48B01J2531/57B01J2531/58B01J2531/64B01J2531/66B01J2531/72B01J2531/842B01J2531/845B01J2531/847B82Y30/00B82Y40/00C08L77/06
View Patent ↗
Loading inventors, assignments & file history…
Abstract
A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.
Claims (12)
1. A nanofiber catalyst comprising:
a transition metal oxide fibrous material comprising a plurality of pores, wherein:
the transition metal oxide fibrous material has metal oxide framework (MOF) morphology filled by transition metal oxide particles, the transition metal oxide fibrous material being a bimetallic or trimetallic transition metal oxide; and
the transition metal oxide particles are connected by interconnected metal oxide structure to form nanofibrous network;
wherein the catalyst has a specific surface area of 100-1000 m 2 /gram.
2. The nanofiber catalyst of claim 1 , wherein at least 80% of the plurality of pores have an average pore diameter of less than 2 nm.
3. The nanofiber catalyst of claim 1 , wherein the plurality of pores have a porous nano-network catalyst network morphology.
4. The nanofiber catalyst of claim 1 , wherein the catalyst has a specific surface area of 750-1000 m 2 /gram.
5. The nanofiber catalyst of claim 1 , wherein the transition metal oxides particles are fused together via electrospinning.
6. The nanofiber catalyst of claim 5 , wherein the transition metal oxide particles are subject to high temperature pyrolysis following electrospinning.
7. The nanofiber catalyst of claim 1 , wherein the interconnected metal oxide structure includes atomically dispersed carbon.
8. The nanofiber catalyst of claim 1 , wherein a portion of the transition metal oxide particles have been converted through thermolysis to carbonitride.
Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Jan 2, 2024
From: CHONG, LINA; LIU, DI-JIA
To: UCHICAGO ARGONNE, LLC
Reel/Frame 065998/0224 →
Continuity (4)
Provisional Application
62552340
· Aug 30, 2017
References Cited (145)
US 550223A
· Griscom
· 1895
[cited by applicant]
US 3572993A
· Rogers
· 1971
[cited by applicant]
US 5795384A
· Coyle et al.
· 1998
[cited by applicant]
US 5851285A
· Johnsson et al.
· 1998
[cited by applicant]
US 7507690B2
· Krumpelt et al.
· 2009
[cited by applicant]
US 7550223B2
· Zelenay et al.
· 2009
[cited by applicant]
US 8709964B2
· Ewald et al.
· 2014
[cited by applicant]
US 8821776B2
· Lopez et al.
· 2014
[cited by applicant]
US 8835343B2
· Liu et al.
· 2014
[cited by applicant]
US 9012344B2
· Liu et al.
· 2015
[cited by applicant]
US 9180443B1
· Serov et al.
· 2015
[cited by applicant]
US 9350026B2
· Liu et al.
· 2016
[cited by applicant]
US 9825308B1
· Liu et al.
· 2017
[cited by applicant]
US 20030145681A1
· El-Shall et al.
· 2003
[cited by applicant]
US 20030228972A1
· Birss et al.
· 2003
[cited by applicant]
US 20080286490A1
· Bogdanoff et al.
· 2008
[cited by applicant]
US 20090183996A1
· Richter et al.
· 2009
[cited by applicant]
US 20100323272A1
· Ozaki
· 2010
[cited by applicant]
US 20140099571A1
· Proietti et al.
· 2014
[cited by applicant]
US 20140120454A1
· Takahashi
· 2014
[cited by applicant]
US 20150231622A1
· Kitagawa et al.
· 2015
[cited by applicant]
US 20170012277A1
· Wang
· 2017
[cited by applicant]
US 20170145599A1
· Mu et al.
· 2017
[cited by applicant]
US 20180294485A1
· Armel et al.
· 2018
[cited by applicant]
CN 102962036B
· 2013
[cited by applicant]
CN 104370820B
· 2015
[cited by applicant]
CN 105854853A
· 2016
[cited by applicant]
CN 106835362A
· 2017
[cited by applicant]
CN 106865362B
· 2017
[cited by applicant]
CN 107442125B
· 2017
[cited by applicant]
CN 108722486A
· 2018
[cited by applicant]
CN 109126885A
· 2019
[cited by applicant]
CN 111477886A
· 2020
[cited by applicant]
DE 102005053430A1
· 2007
[cited by applicant]
EP 0754783A1
· 1997
[cited by applicant]
JP 2007277105A
· 2007
[cited by applicant]
JP 2012200674A
· 2012
[cited by applicant]
JP 2016204701A
· 2016
[cited by applicant]
WO WO2007007113A2
· 2007
[cited by applicant]
WO WO2010051619A1
· 2010
[cited by applicant]
WO WO2012028989A1
· 2012
[cited by applicant]
WO WO2015077039A1
· 2015
[cited by applicant]
WO WO2015173553A1
· 2015
[cited by applicant]
WO WO2016000032A1
· 2016
[cited by applicant]
Alia, et al., “Activity and Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction”, Journal of the Electrochemical Society, 163(11), pp. F3105-F3112 (2016).
[cited by applicant]
Ayers, et al., “Perspectives on Low-Temperature Electrolysis and Potential for Renewable Hydrogen at Scale,” Annual Review of Chemical and Biomolecular Engineering 10, pp. 219-239 (2019).
[cited by applicant]
Back, et al., “Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements,” Chemical Science 8(2), pp. 1090-1096 (2017).
[cited by applicant]
Bai, et al., “Synthesis and field-emission behavior of highly oriented boron carbonitride nanofibers,” Applied Physics Letters 76(18), pp. 2624-2626 (2000).
[cited by applicant]
Bard & Faulkner, “Electromechanical Methods: Fundamentals and Applications,” John Wiley & Sons, Inc. (2011).
[cited by applicant]
Barkholtz, et al., “Enhanced performance of non-PGM catalysts in air operated PEM-fuel cells,” International Journal of Hydrogen Energy 41(47), pp. 22598-22604 (2016).
[cited by applicant]
Bernt & Gasteiger, “Influence of lonomer Content in IrO2/TiO2 Electrodes on PEM Water Electrolyzer Performance,” Journal of the Electrochemical Society 163(11), pp. F3179-F3189 (2016).
[cited by applicant]
Carmo, et al., “A comprehensive review on PEM water electrolysis,” International Journal of Hydrogen Energy 38(12), pp. 4901-4934 (2013).
[cited by applicant]
Chatti, et al., “Intrinsically stable in situ generated electrocatalyst for long-term oxidation of acidic water at up to 80 C,” Nature Catalysis 2, pp. 457-465 (2019).
[cited by applicant]
Chen, et al., “Bimetallic metal—organic framework-derived carbon nanocubes as efficient electrocatalysts for oxygen evolution reaction,” Journal of Solid State Chemistry 291, 121679, 6 pages (2020).
[cited by applicant]
Chong, et al., “Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl-Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells,” ChemElectroChem 3(10), pp. 1541-1545 (2016).
[cited by applicant]
Danilovic, et al., “(Plenary) Challenges in Going from Laboratory to Megawatt Scale PEM Electrolysis,” ECS Transactions 75(14), pp. 395-402 (2016).
[cited by applicant]
Danilovic, et al., “Using Surface Segregation To Design Stable Ru—Ir Oxides for the Oxygen Evolution Reaction in Acidic Environments,” Angewandte Chemie 126(51), pp. 14240-14245 (2014).
[cited by applicant]
Dresselhaus & Thomas, “Alternative energy technologies,” Nature 414, pp. 332-337 (2001).
[cited by applicant]
Faubert, et al., “Activation and Characterization of Fe-based Catalysts for the Reduction of Oxygen in Polymer Electrolyte Fuel Cells,” Electrochimica Acta 43(14-15), pp. 1969-1984 (1998).
[cited by applicant]
Gao, et al., “Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction,” Nature Communications 8, 14503, 9 pages (2017).
[cited by applicant]
Gray, “Powering the planet with solar fuel,” Nature Chemistry 1, p. 7 (2009).
[cited by applicant]
Hahn, et al., “Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons,” Proceedings of the National Academy of Sciences 114(23), pp. 5918-5923 (201…
[cited by applicant]
Hu, et al., “IrO2/Nb—TiO2 electrocatalyst for oxygen evolution reaction in acidic medium,” International Journal of Hydrogen Energy 39(13), pp. 6967-69796 (2014).
[cited by applicant]
Huan, et al., “Electrochemical Reduction of CO2 Catalyzed by Fe—N—C Materials: a Structure-Selectivity Study,” ACS Catalysis, 7, pp. 1520-1525 (2017).
[cited by applicant]
Huo, et al., “A versatile, industrially relevant, aqueous room temperature synthesis of HKUST-1 with high space-time yield,” Journal of Materials Chemistry A, 1, pp. 15220-15223 (2013).
[cited by applicant]
Huynh, et al., “A Functionally Stable Manganese Oxide Oxygen Evolution Catalyst in Acid,” Journal of the American Chemical Society 136(16), pp. 6002-6010 (2014).
[cited by applicant]
Hwang, et al., “Perovskites in catalysis and electrocatalysis,” Science 358(6364), pp. 751-756 (2017).
[cited by applicant]
Indra, et al., “Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides,” Journal of the American Chemical Society 136(50), pp. 17530-17536 (2014).
[cited by applicant]
Janiak, et al., “MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)”, New Journal of Chemistry 34(11), pp. 2337-2388 (2010).
[cited by applicant]
Jaouen, et al., “Cross-Laboratory Experimental Study of Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction,” ACS Applied Materials & Interfaces 1(8), pp. 1623-1639 (2009).
[cited by applicant]
Jasinski, “A New Fuel Cell Cathode Catalyst”, Nature 201, pp. 1212-1213 (1986).
[cited by applicant]
Kanan & Nocera, “In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2,” Science 321(5892), pp. 1072-1075 (2008).
[cited by applicant]
Katsounaros, et al., “Oxygen Electrochemistry as a Cornerstone for Sustainable Energy Conversion,” Angewandte Chemie 53(1), pp. 102-121 (2014).
[cited by applicant]
Keskin, et al., “Atomically detailed models of gas mixture diffusion through CuBTC membranes,” Microporous and Mesoporous Materials 125(1-2), pp. 101-106 (2009).
[cited by applicant]
Kornienko, et al., “Metal-Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide,” Journal of the American Chemical Society 137, pp. 14129-14135 (2015).
[cited by applicant]
Kumar, et al., “Highly selective electrochemical reduction of carbon dioxide using Cu based metal organic framework as an electrocatalyst,” Electrochemistry Communications, 25, pp. 70-73 (2012).
[cited by applicant]
Kumar, et al., “New trends in the development of heterogeneous catalysts for electrochemical CO2 reduction,” Catalysis Today 270, pp. 19-30 (2016).
[cited by applicant]
Kwon, et al., “Cobalt Assisted Synthesis of IrCu Hollow Octahedral Nanocages as Highly Active Electrocatalysts toward Oxygen Evolution Reaction,” Advanced Functional Materials 27(7), 1604688, 8 pages (2017).
[cited by applicant]
Lee, et al., “Sustainable production of formic acid by electrolytic reduction of gaseous carbon dioxide,” Journal of Materials Chemistry A 3(6), pp. 3029-3034 (2015).
[cited by applicant]
Lefevre, et al., “Fe-based Catalysts for the Reduction of Oxygen in Polymer Electrolyte Membrane Fuel Cell Conditions: Determination of the Amount of Peroxide Released During Electroreduction and its Influence on the St…
[cited by applicant]
Lefevre, et al., “Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells,” Science 324, pp. 71-74 (2009).
[cited by applicant]
Liang, et al., “Non-noble trimetallic Cu—Ni—Co nanoparticles supported on metal-organic frameworks as highly efficient catalysts for hydrolysis of ammonia borane,” Journal of Alloys and Compounds 741, pp. 501-508 (2018).
[cited by applicant]
Lux, et al., “Heat-treatment of metal—organic frameworks for green energy applications,” CrystEngComm 17, pp. 10-22 (2015).
[cited by applicant]
Ma, et al., “Cobalt Imidazolate Framework as Precursor for Oxygen Reduction Reaction Electrocatalysts,” Chemistry: A European Journal 17(7), pp. 2063-2067 (2011).
[cited by applicant]
Ma, et al., “Framework-Catenation Isomerism in Metal-Organic Frameworks and Its Impact on Hydrogen Uptake,” Journal of the American Chemistry Society 129, pp. 1858-1859 (2007).
[cited by applicant]
McCrory, et al., “Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices,” Journal of the American Chemical Society 137(13), pp. 4347-4357 (2015).
[cited by applicant]
Meng, et al., “Strain Regulation to Optimize the Acidic Water Oxidation Performance of Atomic-Layer IrOx,” Advanced Materials 31(37), 1903616, 8 pages (2019).
[cited by applicant]
Mondschein, et al., “Crystalline Cobalt Oxide Films for Sustained Electrocatalytic Oxygen Evolution under Strongly Acidic Conditions,” Chemistry of Materials 29(3), pp. 950-957 (2017).
[cited by applicant]
Moreno-Hernandez, et al., “Crystalline nickel manganese antimonate as a stable water-oxidation catalyst in aqueous 1.0 M H2SO4,” Energy & Environmental Science 10(10), pp. 2103-2108 (2017).
[cited by applicant]
Nie, et al., “Selectivity of CO2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps,” Angewandte Chemie 52(9), pp. 2459-2462 (2013).
[cited by applicant]
Nong, et al., “A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core-shell electrocatalysts,” Nature Catalysis 1, pp. 841-851 (2018).
[cited by applicant]
Oh, et al., “Electrochemical Catalyst—Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction,” Journal of the American Chemical Society 138(38), pp. 12552-12563 (…
[cited by applicant]
Oh, et al., “Oxide-supported Ir nanodendrites with high activity and durability for the oxygen evolution reaction in acid PEM water electrolyzers,” Chemical Science 6(6), pp. 3321-3328 (2015).
[cited by applicant]
Oh, et al., “Preparation of Mesoporous Sb- , F- , and In-Doped SnO2 Bulk Powder with High Surface Area for Use as Catalyst Supports in Electrolytic Cells,” Advanced Functional Materials 25(7), pp. 1074-1081 (2015).
[cited by applicant]
Park, et al., “Iridium-Based Multimetallic Nanoframe@Nanoframe Structure: An Efficient and Robust Electrocatalyst toward Oxygen Evolution Reaction,” ACS Nano 11(6), pp. 5500-5509 (2017).
[cited by applicant]
Pei, et al., “Synthesis and catalysis of chemically reduced metal—metalloid amorphous alloys,” Chemical Society Reviews 41(24), pp. 8140-8162 (2012).
[cited by applicant]
Proietti et al., “Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells”, Nature Communications 2, 416, 9 pages (2011).
[cited by applicant]
Reier, et al., “Electrocatalytic Oxygen Evolution Reaction in Acidic Environments—Reaction Mechanisms and Catalysts,” Advanced Energy Materials 7(1), 1601275, 18 pages (2017).
[cited by applicant]
Rungtaweevoranit, et al., “Copper Nanocrystals Encapsulated in Zr-based Metal—Organic Frameworks for Highly Selective CO2 Hydrogenation to Methanol,” Nano Letters 16(12), pp. 7645-7649 (2016).
[cited by applicant]
Sardar, et al., “Water-Splitting Electrocatalysis in Acid Conditions Using Ruthenate-Iridate Pyrochlore,” Angewandte Chemie 126(41), pp. 11140-11144 (2014).
[cited by applicant]
Seitz, et al., “A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction,” Science 353(6303), pp. 1011-1014 (2016).
[cited by applicant]
Senthil Raja, et al., “Composition-balanced trimetallic MOFs as ultra-efficient electrocatalysts for oxygen evolution reaction at high current densities,” Applied Catalysis B: Environmental 279, 119375, 14 pages (2020).
[cited by applicant]
Serov, et al., “Templated bi-metallic non-PGM catalysts for oxygen reduction,” Electrochimica Acta 80, pp. 213-218 (2012).
[cited by applicant]
Serov, et al., “Tri-metallic transition metal-nitrogen-carbon catalysts derived by sacrificial support method synthesis,” Electrochimica Acta 109, pp. 433-439 (2013).
[cited by applicant]
Shan, et al., “Charge-Redistribution-Enhanced Nanocrystalline Ru@IrOx Electrocatalysts for Oxygen Evolution in Acidic Media,” Chem 5(2), pp. 445-459 (2019).
[cited by applicant]
Smith, et al., “Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis,” Science 340(6128), pp. 60-63 (2013).
[cited by applicant]
Studt, et al., “Discovery of a Ni—Ga catalyst for carbon dioxide reduction to methanol,” Nature Chemistry 6, pp. 320-324 (2014).
[cited by applicant]
Suen, et al., “Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives,” Chemical Society Reviews 46(2), pp. 337-365 (2017).
[cited by applicant]
Sun, et al., “Catalytic Hydrolysis of Ammonia Borane via Cobalt Palladium Nanoparticles,” ACS Nano 5(8), pp. 6458-6464 (2011).
[cited by applicant]
Tan, et al., “Construction of hierarchical trimetallic organic framework leaf-like nanostructures derived from carbon nanotubes for gas-sensing applications,” Journal of Hazardous Materials 400, 123155, 9 pages (2020).
[cited by applicant]
US Notice of Allowance on U.S. Appl. No. 15/203,083 Dtd Jul. 19, 2017.
[cited by applicant]
Van Veen, “Oxygen Reduction on Monomeric Transition Metal Phthalocyanines in Acid Electrolyte,” Electrochimica Acta 21, pp. 921-928 (1979).
[cited by applicant]
Wang, et al., “Improving the activity and stability of Ir catalysts for PEM electrolyzer anodes by SnO2:Sb aerogel supports: does V addition play an active role in electrocatalysis?,” Journal of Materials Chemistry A 5(…
[cited by applicant]
Wu, et al., “Polyaniline-Derived Non-Precious Catalyst for the Polymer Electrolyte Fuel Cell Cathode,” ECS Transactions 16(2), pp. 159-170 (2008).
[cited by applicant]
Yi, et al., “Hollow Metallic Microspheres: Fabrication and Characterization,” The Journal of Physical Chemistry C 113(4), pp. 1222-1226 (2009).
[cited by applicant]
Yue, et al., “Template-Free Synthesis of Hierarchical Porous Metal-Organic Frameworks,” Journal of the American Chemical Society 135(26), pp. 9572-9575 (2013).
[cited by applicant]
Zhang, et al., “Honeycomb-like mesoporous nitrogen-doped carbon supported Pt catalyst for methanol electrooxidation,” Carbon 93, pp. 1050-1058 (2015).
[cited by applicant]
Zhao, et al., “Highly Efficient Non-Precious Metal Electrocatalysts Prepared from One-Pot Synthesized Zeolitic Imidazolate Frameworks,” Advanced Materials 26(7), pp. 1093-1097 (2014).
[cited by applicant]
Zhao, et al., “Iron imidazolate framework as precursor for electrocatalysts in polymer electrolyte membrane fuel cells,” Chemical Science 3(11), pp. 3200-3205 (2012).
[cited by applicant]