Granted Patent
B2
US 12,378,685 · App. 18/328,524 · Granted Aug 5, 2025
Surface modification of metal catalysts with hydrophobic ligands or ionomers
Inventors:
Yueshen Wu (Irvine, CA); Chengtian Shen (Irvine, CA); Benjamin Kash (Berkeley, CA); Shreeya Negi (Aptos, CA); Coline Boulanger (Saint-Vincent-de-Pertignas, FR)
Assignee:
Twelve Benefit Corporation
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Abstract
Provided herein are hydrophobically-modified metal nanoparticle cathode catalysts for electrochemical reactions. The hydrophobic modifications may be incorporated onto the nanoparticles by either directly binding ligands or ionomers to the nanoparticles, or by indirectly binding an ionomer to the nanoparticle through a linker. The hydrophobically-modified metal nanoparticles may be hydrophobic ally-modified gold nanoparticles.
Claims (37)
1. A CO x reduction reactor comprising:
a membrane electrode assembly comprising:
a cathode catalyst layer, the cathode catalyst layer comprising metal nanoparticles having surfaces, the metal nanoparticles immobilized on a carbon-containing support material;
an anode catalyst layer; and
a membrane disposed between the cathode catalyst layer and the anode catalyst layer;
wherein the metal nanoparticles in the presence of a bifunctional linker form a modified metal nanoparticle catalyst on the carbon-containing support material,
wherein the bifunctional linker comprises at least one sulfur-containing group,
wherein the modified metal nanoparticle catalyst in the presence of at least one hydrophobic moiety and an amine affixes the at least one hydrophobic moiety to the modified metal nanoparticle catalyst, and
wherein the at least one hydrophobic moiety comprises an ionomer.
2. The CO x reduction reactor of claim 1 , wherein the membrane comprises a bipolar membrane or an anion exchange membrane.
3. The CO x reduction reactor of claim 1 , wherein the metal nanoparticles comprise gold, silver, palladium, copper or a combination thereof.
4. The CO x reduction reactor of claim 3 , wherein the metal nanoparticles comprise gold.
5. The CO x reduction reactor of claim 1 , wherein the at least one sulfur-containing group is bonded to the surfaces of the metal nanoparticles.
6. The CO x reduction reactor of claim 5 , wherein the at least one sulfur-containing group comprises a thiol or a dithiol.
7. The CO x reduction reactor of claim 1 , wherein the ionomer comprises a homopolymer or a copolymer, and wherein the homopolymer or copolymer has an aromatic backbone.
8. The CO x reduction reactor of claim 1 , wherein the ionomer is bonded to the surfaces of the metal nanoparticles through the bifunctional linker.
9. The CO x reduction reactor of claim 8 , wherein the bifunctional linker comprises 2-(dimethylamino)ethanethiol or a salt thereof.
10. The CO x reduction reactor of claim 1 , wherein the metal nanoparticles on the carbon-containing support material comprise from about 10 percent to 50 percent by weight of metal.
11. The CO x reduction reactor of claim 1 , wherein the metal nanoparticles have a particle size of from about 1 nm to 50 nm.
12. The CO x reduction reactor of claim 1 , wherein the metal nanoparticles have a particle size of from about 5 nm to 10 nm.
13. The CO x reduction reactor of claim 1 , wherein a ratio of the at least one hydrophobic moiety to the metal nanoparticles on the carbon-containing support material is from about 0.1:1 to about 8:1.
14. The CO x reduction reactor of claim 1 , wherein a mass ratio of the bifunctional linker to the metal nanoparticles on the carbon-containing support material is from about 1:10 to about 10:1.
15. A method of electrochemically reducing CO x comprising:
(a) providing a carbon oxide to a CO x reduction reactor, and
(b) electrochemically reducing the carbon oxide at a cathode of a CO x electrolyzer to produce a carbon containing product,
wherein the CO x reduction reactor comprises a membrane electrode assembly comprising:
a cathode catalyst layer, the cathode catalyst layer comprising metal nanoparticles having surfaces, the metal nanoparticles immobilized on a carbon-containing support material;
an anode catalyst layer; and
a membrane disposed between the cathode catalyst layer and the anode catalyst layer;
wherein the metal nanoparticles in the presence of a bifunctional linker form a modified metal nanoparticle catalyst on the carbon-containing support material,
wherein the bifunctional linker comprises at least one sulfur-containing group,
wherein the modified metal nanoparticle catalyst in the presence of at least one hydrophobic moiety and an amine affixes the at least one hydrophobic moiety to the modified metal nanoparticle catalyst, and
wherein the at least one hydrophobic moiety comprises an ionomer.
16. The method of claim 15 , wherein the membrane comprises a bipolar membrane or an anion exchange membrane.
17. The method of claim 15 , wherein the carbon containing product comprises carbon monoxide, a hydrocarbon, formic acid, an alcohol or a combination thereof.
18. The method of claim 15 , wherein the metal nanoparticles comprise gold, silver, palladium, copper or a combination thereof.
19. The method of claim 15 , wherein a mass ratio of the bifunctional linker to the metal nanoparticles on the carbon-containing support material is from about 1:10 to about 10:1.
Assignments (2)
SECURITY INTEREST
Recorded Jan 19, 2026
From: TWELVE BENEFIT CORPORATION
To: SUMITOMO MITSUI BANKING CORPORATION
Reel/Frame 074435/0926 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Aug 2, 2023
From: WU, YUESHEN; SHEN, CHENGTIAN; KASH, BENJAMIN; NEGI, SHREEYA; BOULANGER, COLINE
To: TWELVE BENEFIT CORPORATION
Reel/Frame 064468/0874 →
Continuity (2)
Provisional Application
63476722
· Dec 22, 2022
References Cited (364)
US 4042496A
· Tsushima et al.
· 1977
[cited by applicant]
US 4089758A
· McAloon
· 1978
[cited by applicant]
US 4116889A
· Chlanda et al.
· 1978
[cited by applicant]
US 4176215A
· Molnar et al.
· 1979
[cited by applicant]
US 4253900A
· Dege et al.
· 1981
[cited by applicant]
US 4355116A
· Lee et al.
· 1982
[cited by applicant]
US 4655886A
· Oda et al.
· 1987
[cited by applicant]
US 4766161A
· Chlanda et al.
· 1988
[cited by applicant]
US 4828941A
· Sterzel
· 1989
[cited by applicant]
US 5039389A
· McMichael
· 1991
[cited by applicant]
US 6358651B1
· Chen et al.
· 2002
[cited by applicant]
US 7704369B2
· Olah et al.
· 2010
[cited by applicant]
US 7883817B2
· Hori et al.
· 2011
[cited by applicant]
US 8137859B2
· Shin et al.
· 2012
[cited by applicant]
US 8268026B2
· Norbeck et al.
· 2012
[cited by applicant]
US 8277631B2
· Eastman et al.
· 2012
[cited by applicant]
US 8652104B2
· Goral et al.
· 2014
[cited by applicant]
US 8652704B2
· Sano et al.
· 2014
[cited by applicant]
US 8697129B2
· Qian et al.
· 2014
[cited by applicant]
US 9012345B2
· Masel et al.
· 2015
[cited by applicant]
US 9486480B2
· Ayoub et al.
· 2016
[cited by applicant]
US 9587071B2
· Sun et al.
· 2017
[cited by applicant]
US 20030059658A1
· Kohler et al.
· 2003
[cited by applicant]
US 20050147859A1
· Kiefer et al.
· 2005
[cited by applicant]
US 20100028736A1
· Unlu et al.
· 2010
[cited by applicant]
US 20110237830A1
· Masel
· 2011
[cited by applicant]
US 20120171583A1
· Bocarsly et al.
· 2012
[cited by applicant]
US 20120328942A1
· Thomas-Alyea et al.
· 2012
[cited by applicant]
US 20130105304A1
· Kaczur et al.
· 2013
[cited by applicant]
US 20130345325A1
· Lecomte et al.
· 2013
[cited by applicant]
US 20140202875A1
· Mofakhami
· 2014
[cited by applicant]
US 20140206894A1
· Cole et al.
· 2014
[cited by applicant]
US 20140287347A1
· Vincent et al.
· 2014
[cited by applicant]
US 20150030888A1
· Popat et al.
· 2015
[cited by applicant]
US 20150136613A1
· Li et al.
· 2015
[cited by applicant]
US 20160151739A1
· Jakobsson et al.
· 2016
[cited by applicant]
US 20160194766A1
· Eastman et al.
· 2016
[cited by applicant]
US 20180151890A1
· Ishida et al.
· 2018
[cited by applicant]
US 20180265440A1
· Kudo et al.
· 2018
[cited by applicant]
US 20190062931A1
· Stark et al.
· 2019
[cited by applicant]
US 20190127865A1
· Li et al.
· 2019
[cited by applicant]
US 20200318247A1
· Fernandez Sanchis et al.
· 2020
[cited by applicant]
US 20200376479A1
· Masel
· 2020
[cited by applicant]
US 20210381116A1
· Kashi et al.
· 2021
[cited by applicant]
US 20210387139A1
· Voskian et al.
· 2021
[cited by applicant]
US 20230155153A1
· Huo et al.
· 2023
[cited by applicant]
US 20230264148A1
· Boettcher et al.
· 2023
[cited by applicant]
US 20230265568A1
· Kuhl et al.
· 2023
[cited by applicant]
US 20240327999A1
· Cave et al.
· 2024
[cited by applicant]
CA 1071143A
· 1980
[cited by applicant]
CA 2960595A1
· 2016
[cited by applicant]
CN 1471740A
· 2004
[cited by applicant]
CN 102576902A
· 2012
[cited by applicant]
CN 102912374A
· 2013
[cited by applicant]
CN 104247118A
· 2014
[cited by applicant]
CN 104619886A
· 2015
[cited by applicant]
CN 104919088A
· 2015
[cited by applicant]
CN 106715760A
· 2017
[cited by applicant]
CN 107735512A
· 2018
[cited by applicant]
DE 102018210303A1
· 2020
[cited by applicant]
EP 1261058A2
· 2002
[cited by applicant]
EP 3378968A1
· 2018
[cited by applicant]
JP H01502673A
· 1989
[cited by applicant]
JP H02166128A
· 1990
[cited by applicant]
JP H04228591A
· 1992
[cited by applicant]
JP H0625444A
· 1994
[cited by applicant]
JP H06145379A
· 1994
[cited by applicant]
JP H10507305A
· 1998
[cited by applicant]
JP 2000251906A
· 2000
[cited by applicant]
JP 2002306975A
· 2002
[cited by applicant]
JP 2002352810A
· 2002
[cited by applicant]
JP 2013520779A
· 2013
[cited by applicant]
JP 2014022249A
· 2014
[cited by applicant]
JP 2014504424A
· 2014
[cited by applicant]
JP 2014525115A
· 2014
[cited by applicant]
JP 2014194079A
· 2014
[cited by applicant]
JP 2015533944A
· 2015
[cited by applicant]
JP 2017527701A
· 2017
[cited by applicant]
JP 2018003059A
· 2018
[cited by applicant]
JP 2019515142A
· 2019
[cited by applicant]
JP 2021059788A
· 2021
[cited by applicant]
KR 100962903B1
· 2010
[cited by applicant]
KR 20140142185A
· 2014
[cited by applicant]
KR 20150073651A
· 2015
[cited by applicant]
WO WO9611507A1
· 1996
[cited by applicant]
WO WO2011104542A1
· 2011
[cited by applicant]
WO WO2011136296A1
· 2011
[cited by applicant]
WO WO2012174463A1
· 2012
[cited by applicant]
WO WO2016039999A1
· 2016
[cited by applicant]
WO WO2016108603A1
· 2016
[cited by applicant]
WO WO2017144395A1
· 2017
[cited by applicant]
WO WO2017169682A1
· 2017
[cited by applicant]
WO WO2017176306A1
· 2017
[cited by applicant]
WO WO2017192787A1
· 2017
[cited by applicant]
WO WO2018195045A1
· 2018
[cited by applicant]
WO WO2019020239A1
· 2019
[cited by applicant]
WO WO2019120812A1
· 2019
[cited by applicant]
WO WO2019136018A2
· 2019
[cited by applicant]
WO WO2019206882A1
· 2019
[cited by applicant]
WO WO2020020691A1
· 2020
[cited by applicant]
WO 2020112919A1
· 2020
[cited by applicant]
WO WO2020212139A1
· 2020
[cited by applicant]
WO WO2021007508A1
· 2021
[cited by applicant]
WO WO2021252535A2
· 2021
[cited by applicant]
Gao et al. Chem. Commun., 2020, 56, 7021 (Year: 2020).
[cited by examiner]
Rucareanu et al. Chem. Mater. 2006, 18, 4674-4680 (Year: 2006).
[cited by examiner]
Nakashima et al. (Polymer Journal ‘2015’ 47, 171-176) (Year: 2015).
[cited by examiner]
Aeshala, L.M. et al., “Effect of Cationic and Anionic Solid Polymer Electrolyte on Direct Electrochemical Reduction of Gaseous CO
[cited by applicant]
Aeshala, L.M. et al., “Effect of solid polymer electrolyte on electrochemical reduction of CO2, Separation and Purification Technology,” 94, (2012), pp. 131-137.
[cited by applicant]
Ahlfield J., et al., “PEM/AEM Junction Design for Bipolar Membrane Fuel Cells,” Journal of the Electrochemical Society, 2017, vol. 164 (12), pp. F1165-F1171.
[cited by applicant]
Badami, M. “Leakage effects on the performance characteristics of a regenerative blower for the hydrogen recirculation of a PEM fuel cell,” Energy Conversion and Management, vol. 55, Mar. 2012, pp. 20-25.
[cited by applicant]
Badami, M., “Theoretical model with experimental validation of a regenerative blower for hydrogen recirculation in a PEM fuel cell system,” Energy Conversion and Management, vol. 51, Issue 3, Mar. 2010, pp. 553-560.
[cited by applicant]
Bakshi M., et al., “How Surfactants Control Crystal Growth of Nanomaterials,” ACS Crystal Growth & Design, 2016, vol. 16, pp. 1104-1133.
[cited by applicant]
Balster, J. et al., “Tailoring the Interface Layer of the Bipolar Membrane”, Journal of Membrane Science, vol. 365, No. 1-2, Dec. 2010, pp. 389-398.
[cited by applicant]
Blaszczyk, J., “In-Situ Anode Recirculation Rate Measurement Method (Draft),” Ogura Industrial Corporation, Ballard Power Systems, Full Cell Seminar & Exposition 2011, Oct. 31-Nov. 3, 2011, 22 pages.
[cited by applicant]
CA First Office Action issued on Oct. 15, 2019, in Application No. 3,022,807.
[cited by applicant]
CA First Office Action issued on Sep. 30, 2019, in Application No. 3,022,812.
[cited by applicant]
CA Office Action dated Jan. 9, 2023 in Application No. CA20173022812.
[cited by applicant]
CA Office Action dated Jun. 21, 2023, in Application No. CA20173124239.
[cited by applicant]
CA Office Action dated May 3, 2022 in Application No. CA20173124239.
[cited by applicant]
CA Second Office Action issued on Aug. 28, 2020, in Application No. 3,022,812.
[cited by applicant]
CA Second Office Action issued on Oct. 14, 2020, in Application No. 3,022,807.
[cited by applicant]
Choo et al. Modulated Ionomer Distribution in the Catalyst Layer of Polymer Electrolyte Membrane Fuel Cells for High Temperature Operation, Chemsuschem, vol. 7, Issue 8, Aug. 2014, pp. 2335-2341.
[cited by applicant]
CN First Office Action issued on Jul. 28, 2021, in Application No. 201780036099.2.
[cited by applicant]
CN First Office Action issued on Jul. 7, 2021, in Application No. 201780035746.8.
[cited by applicant]
CN Office Action dated Feb. 7, 2022, in Application No. CN2017800357468.
[cited by applicant]
CN Office Action dated Jul. 5, 2022 in Application No. CN20178035746 With English translation.
[cited by applicant]
Delacourt, C., “Electrochemical reduction of carbon dioxide and water to syngas (CO+H2) at room temperature,” Manuscript, Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory and Department …
[cited by applicant]
Delacourt et al., “Design of an Electrochemical Cell Making Syngas (CO+H2) from CO2 and H2O Reduction at Room Temperature,” Journal of the Electrochemical Society, 155 (1), (2008), pp. B42-B49.
[cited by applicant]
Endrodi, B., “Multilayer Electrolyzer Stack Converts Carbon Dioxide to Gas Products at High Pressure with Multilayer Electrolyzer Stack Converts Carbon,” acs Energy Lett. 2019, 4, 1770-1777.
[cited by applicant]
EP office action dated May 23, 2023, in application No. EP21152137.2.
[cited by applicant]
EP Office Action issued on Sep. 4, 2020, in Application No. 17793299.3.
[cited by applicant]
EP Search Report issued on Apr. 20, 2021, in Application No. 21152137.2.
[cited by applicant]
EP Search Report issued on Dec. 2, 2019, in Application No. 17793299.3.
[cited by applicant]
EP Search Report issued on Dec. 4, 2019, in Application No. 17793300.9.
[cited by applicant]
Extended European search report dated May 27, 2022, in Application No. EP21181985.9.
[cited by applicant]
Final Office Action issued in issued on Apr. 2, 2019, in U.S. Appl. No. 15/586,182.
[cited by applicant]
Final Office Action issued in issued on Jan. 8, 2020, in U.S. Appl. No. 15/586,173.
[cited by applicant]
Gangeri, M et al., “Fe and Pt Carbon Nanotubes for the Electrocatalytic Conversion of Carbon Dioxide to Oxygenates”, Catalysis Today, May 2009, vol. 143, pp. 57-63.
[cited by applicant]
Haesuwannakij, S., et al., “The Impact of the Polymer Chain Length on the Catalytic Activity of Poly(N-vinyl-2-pyrrolidone)-supported Gold Nanoclusters,” Scientific Reports, 2017, vol. 7(1), pp. 1-8.
[cited by applicant]
Hao, J.H. et al., “Preparation of Solvent-resistant Anion-exchange Membranes”, Desalination, Jun. 2000, vol. 129, No. 1, pp. 15-22.
[cited by applicant]
Hori, Y., “Chapter 48: Co2-reduction, catalyzed by metal electrodes,” Handbook of Fuel Cells—Fundamentals, Technology and Applications, vol. 2, Electrocatalysis, 2003. pp. 720-733.
[cited by applicant]
Hori, Y., et al., “Electroreduction of CO to CH4 and C2H4 at a Copper Electrode in Aqueous Solutions at Ambient Temperature and Pressure”, Journal of the American Chemical Society, Aug. 5, 1987, vol. 109, pp. 5022-5023.
[cited by applicant]
Hori, Y et al., “Silver-coated Ion Exchange Membrane Electrode Applied to Electrochemical Reduction of Carbon Dioxide”, Electrochimica Acta, Aug. 2003, vol. 48, pp. 2651-2657.
[cited by applicant]
IN Office Action dated Feb. 2, 2022 in Application No. IN202118009885.
[cited by applicant]
IN Office Action dated Feb. 7, 2022 in Application No. IN202118007175.
[cited by applicant]
IN Office Action issued on Aug. 10, 2020, in Application No. 201817041221.
[cited by applicant]
IN Office Action issued on Aug. 19, 2020, in Application No. 201817041222.
[cited by applicant]
International Preliminary Report on Patentability and Written opinion dated Jun. 9, 2022 in Application No. PCT/US2020/062080.
[cited by applicant]
International Preliminary Report on Patentability dated Dec. 22, 2022, in PCT Application No. PCT/US2021/036475.
[cited by applicant]
International Search Report and Written Opinion dated Feb. 23, 2022, in Application No. PCT/US2021/55902.
[cited by applicant]
International Preliminary Report on Patentability issued on Jun. 10, 2021, in PCT Application No. PCT/US2019/063471.
[cited by applicant]
International Preliminary Report on Patentability issued on Nov. 15, 2018, in PCT Application No. PCT/US2017/030935.
[cited by applicant]
International Search Report and Written Opinion dated Feb. 24, 2022, in Application No. PCT/US2021/055900.
[cited by applicant]
International Search Report and Written Opinion dated Jan. 10, 2022, in Application No. PCT/US2021/036475.
[cited by applicant]
International Search Report and Written Opinion dated Mar. 10, 2023 in PCT Application No. PCT/US2022/079570.
[cited by applicant]
International Search Report and Written Opinion issued in PCT Application No. PCT/US2020/062080 on Mar. 16, 2021.
[cited by applicant]
International Search Report and Written Opinion issued on Aug. 7, 2017, in PCT Application No. PCT/US2017/030935.
[cited by applicant]
International Search Report and Written Opinion issued on Sep. 13, 2017, in PCT Application No. PCT/US2017/030936.
[cited by applicant]
James, B.D., et al. 2017 DOE Hydrogen and Fuel Cells Program Review, Fuel Cell Systems Analysis, Strategic Analysis, Project IDI FC163, Jun. 8, 2017, 34 pages.
[cited by applicant]
JP Office Action dated Dec. 7, 2021, in Application No. JP2020-213422 with English translation.
[cited by applicant]
JP Office Action issued on Jan. 28, 2020, in Application No. 2018-558130.
[cited by applicant]
JP Office Action issued on Jan. 28, 2020, in Application No. 2018-558138.
[cited by applicant]
Kortlever R., et al., “Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide ,” The Journal of Physical Chemistry Letters, 2015, vol. 6(20), pp. 4073-4082.
[cited by applicant]
Li, D., et al., “Fabrication of pH-Responsive Nanocomposites of Gold Nanoparticles/Poly(4-vinylpyridine),” Chem. Mater, 2007, vol. 19, pp. 412-417.
[cited by applicant]
Li, et al., “Electrolysis of Co2 to Syngas in Bipolar Membrane-Based Electrochemical Cells,” ACS Publications, ACS Energy Letters, 2016, 1, pp. 1149-1153.
[cited by applicant]
Li, et al., “Electrolytic Conversion of Bicarbonate into CO in a Flow Cell,” Cell Press, Joule 3, Jun. 19, 2019, pp. 1487-1497.
[cited by applicant]
Li, W., “Electrocatalytic Reduction of CO
[cited by applicant]
Li, Y., et al., “Electronic Structure of Thiolate-Covered Gold Nanoparticles: Au
[cited by applicant]
Lin, B. et al., “Alkaline Stable C2-Substituted Imidazolium-Based Anion-Exchange Membranes,” Chemistry of Material, 2013, vol. 25, pp. 1858-1867.
[cited by applicant]
Liu C., et al., “Constructing a Multifunctional Interface Between Membrane and Porous Transport Layer for Water Electrolyzers,” ACS Applied Materials & Interfaces, 2021, vol. 13, pp. 16182-16196.
[cited by applicant]
Lobato, J. et al., “Study of the influence of the amount of PBI-H3PO4 in the catalytic layer of a high temperature PEMFC”, International Journal of Hydrogen Energy, 2010, vol. 35, pp. 1347-1355.
[cited by applicant]
Lu et al. “A selective and efficient electrocatalyst for carbon dioxide reduction,” Nature communication, Jan. 30, 2014.
[cited by applicant]
Ma, L., et al., “Polyvinyl Alcohol-modified Gold Nanoparticles with Record-high Activity for Electrochemical Reduction of Co
[cited by applicant]
Ma, M., et al., “Insights into the Carbon Balance for C02 Electroreduction on Cu using Gas Diffusion Electrode Reactor Designs”, Energy & Environmental Science, Feb. 12, 2020, vol. 13, pp. 977-985.
[cited by applicant]
Machine translation of Kang et al KR20150073651A, 2015.
[cited by applicant]
Machine translation of Shin et al WO2016108603A1, 2016.
[cited by applicant]
Maheswari, S. et al., “Oxygen Reduction Catalysts for Alkaline Polymer Electrolyte Fuel Cells”, ECS Transactions, 2010, vol. 33, No. 1, pp. 1795-1807.
[cited by applicant]
Mandal M., et al., “Improved Polymer Electrolyte Membrane Water Electrolyzer Performance by Using Carbon Black as a Pore Former in the Anode Catalyst Layer,” Journal of Power Sources, 2022, vol. 541, pp. 1-13.
[cited by applicant]
Mayerhofer B., et al., “Bipolar Membrane Electrode Assemblies for Water Electrolysis,” ACS Applied Energy Materials, 2020, vol. 3, pp. 9635-9644.
[cited by applicant]
McDonald M., et al., “Graphene Oxide as a Water Dissociation Catalyst in the Bipolar Membrane Interfacial Layer,” ACS Applied Materials & Interfaces, 2014, vol. 6, pp. 13790-13797.
[cited by applicant]
Morsy S., et al., “Role of Surfactants in Nanotechnology and Their Applications,” International Journal of current Microbiology and Applied Sciences, 2014, vol. 3(5), pp. 237-260.
[cited by applicant]
Mourdikoudis, S., et al., “Oleylamine in Nanoparticle Synthesis,” American Chemical Society, Chemistry of Materials, 2013, vol. 25, pp. 1465-1476.
[cited by applicant]
Narayanan, S.R., et al., “Electrochemical Conversion of Carbon Dioxide to Formate in Alkaline Polymer Electrolyte Membrane Cells,” Journal of the Electrochemical Society, 2011, vol. 158, No. 2, pp. A167-A173.
[cited by applicant]
Notice of Allowance dated Aug. 16, 2021, in U.S. Appl. No. 16/842,659.
[cited by applicant]
Notice of Allowance issued in issued on Apr. 13, 2021, in U.S. Appl. No. 16/842,659.
[cited by applicant]
Notice of Allowance issued in issued on Jan. 29, 2020, in U.S. Appl. No. 15/586,173.
[cited by applicant]
Notice of Allowance issued on Sep. 16, 2020, in U.S. Appl. No. 15/586,182.
[cited by applicant]
O'Brien, C.P. et al., Single Pass CO2 Conversion exceeding 85% in the Electrosynthesis of Multicarbon Products via Local CO2 Regeneration, ACS Energy Let., 2021, vol. 6, 21 pages.
[cited by applicant]
Office Action issued in issued on Apr. 2, 2019, in U.S. Appl. No. 15/586,173.
[cited by applicant]
Office Action issued in issued on Nov. 1, 2018, in U.S. Appl. No. 15/586,173.
[cited by applicant]
Office Action issued in issued on Nov. 1, 2018, in U.S. Appl. No. 15/586,182.
[cited by applicant]
Office Action issued in issued on Sep. 16, 2020, in U.S. Appl. No. 16/842,659.
[cited by applicant]
Office Action issued on Dec. 30, 2019, in U.S. Appl. No. 15/586,182.
[cited by applicant]
Office Action issued on Jul. 2, 2020, in U.S. Appl. No. 15/586,182.
[cited by applicant]
Parrondo, J. et al., “Degradation of Anion Exchange Membranes Used for Hydrogen Production by Ultrapure Water Electrolysis,” Including Supplemental Material, RSC Advances, 2014, vol. 4, 17 Pages.
[cited by applicant]
Patru, A., et al., “Design Principles of Bipolar Electrochemical Co-Electrolysis Cells for Efficient Reduction of Carbon Dioxide from Gas Phase at Low Temperature,” Journal of the Electrochemical Society, 166 (2), (2019…
[cited by applicant]
Phan C., et al., “Role of Capping Agent in Wet Synthesis of Nanoparticles,” The Journal of Physical Chemistry A, 2017, vol. 121, pp. 3213-3219.
[cited by applicant]
Pickup, P. et al., “Electronically Conducting Cation-exchange Polymer Powders: Synthesis, Characterization and Applications in PEM Fuel Cells and Supercapacitors”, Journal of New Materials for Electrochemical Systems, 2…
[cited by applicant]
Preliminary Report on Patentability issued on Nov. 6, 2018, in PCT Application No. PCT/US2017/030936.
[cited by applicant]
SA Office Action dated Sep. 26, 2023, in application No. SA522441684 with English Translation.
[cited by applicant]
Shang, H., et al., “Effect of Surface Ligands on Gold Nanocatalysts for CO2 Reduction,” The Royal Society of Chemistry, 2020, vol. 11, pp. 12298-12306.
[cited by applicant]
Sharma, et al., “Electrocatalytic conversion of carbon dioxide to fuels: a review on the interaction between CO2 and the liquid electrolyte,” Wires Energy Environ 2017, 6:e239. doi: 10.1002/wene.239, pp. 1-21.
[cited by applicant]
Shi, L. et al., “A shorted membrane electrochemical cell powered by hydrogen to remove CO
[cited by applicant]
Shironita S., et al., “Methanol Generation by Co2 Reduction at a Pt-ru/c Electrocatalyst Using a Membrane Electrode Assembly,” Journal of Power Sources, Oct. 2013, vol. 240(15), pp. 404-410.
[cited by applicant]
U.S. Final Office Action dated Aug. 30, 2023, in U.S. Appl. No. 17/342,406.
[cited by applicant]
U.S. Final office Action dated Nov. 21, 2022 in U.S. Appl. No. 17/247,036.
[cited by applicant]
U.S. Non-Final office Action dated Jan. 20, 2023 in U.S. Appl. No. 16/949,538.
[cited by applicant]
U.S. Non-Final Office Action dated Mar. 14, 2023 in U.S. Appl. No. 17/342,406.
[cited by applicant]
U.S. Non-Final Office Action dated May 24, 2022, in U.S. Appl. No. 17/247,036.
[cited by applicant]
U.S. Non-Final Office Action dated Sep. 22, 2023, in U.S. Appl. No. 18/327,835.
[cited by applicant]
U.S. Notice of Allowance dated Feb. 10, 2023 in U.S. Appl. No. 17/247,036.
[cited by applicant]
U.S. Notice of Allowance dated Mar. 2, 2023 in U.S. Appl. No. 17/247,036.
[cited by applicant]
U.S. Notice of Allowance dated Mar. 8, 2023 in U.S. Appl. No. 16/949,538.
[cited by applicant]
U.S. Notice of Allowance dated May 22, 2023 in U.S. Appl. No. 16/949,538.
[cited by applicant]
U.S. Appl. No. 17/030,172, inventors Kuhl et al., filed Sep. 23, 2020.
[cited by applicant]
U.S. Appl. No. 18/053,945, inventors Huo et al., filed Nov. 9, 2022.
[cited by applicant]
U.S. Appl. No. 18/299,672, inventors Kuhl et al., filed Apr. 12, 2023.
[cited by applicant]
U.S. Appl. No. 18/300,380, inventors Ziyang Huo et al., filed Apr. 13, 2023.
[cited by applicant]
U.S. Appl. No. 18/306,928, inventors Kendra P. Kuhl et al., filed Apr. 25, 2023.
[cited by applicant]
U.S. Appl. No. 18/327,835, inventors Zhao S, et al., filed Jun. 1, 2023.
[cited by applicant]
Varcoe, J.R., “Anion-exchange Membranes in Electrochemical Energy Systems,” Energy & Environmental Science, 2014, vol. 7, pp. 3135-3191.
[cited by applicant]
Verma, et al., “The effect of electrolyte composition on the electroreduction of CO2 to CO on Ag based gas diffusion electrodes,” Phys. Chem. Chem. Phys., 2016, 18, pp. 7075-7084.
[cited by applicant]
Voskian, S. et al., “Faradaic electro-swing reactive adsorption for CO
[cited by applicant]
Wang, et al., “Approaches for the preparation of non-linear amphiphilic polymers and their applications to drug delivery”, Advanced Drug Delivery Reviews, 2012, vol. 64, pp. 852-865.
[cited by applicant]
Xia, Chuan, et al., “Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid electrolyte devices,” Nature Energy, http://www.nature.com/natureenergy; https://doi.org/10.1038/s4…
[cited by applicant]
Xu, C. et al., Preparation of PVA-GA-CS/PVA-Fe-SA Bipolar Membrane and Its Application in Electro-generation of 2,2-dimethyl-3-hydroxypropionic Acid, Journal of Membrane Science, vol. 307, No. 2, Jan. 2008, pp. 218-224.
[cited by applicant]
Yang, B. et al., “Preparation of a Bipolar Membrane by Photografting Polymerization”, Frontiers of Chemistry in China, vol. 3, No. 1, Jan. 2008, pp. 10-13.
[cited by applicant]
Zhan, et al., “Multiarm Star Poly(epsilon-caprolactone) with Hyperbranched Polyamidoamine as Core Capable of Selective Accommodating Cationic or Anionic Guests”, Chinese Journal of Polymer Science, 2015. vol. 33, No. 6,…
[cited by applicant]
Zhang, L., et al., “A Polymer Solution to Prevent Nanoclustering and Improve the Selectivity of Metal Nanoparticles for Electrocatalytic CO
[cited by applicant]
Zhao, Y., et al., “Engineering Surface Amine Modifiers of Ultrasmall Gold Nanoparticles Supported on Reduced Graphene Oxide for Improved Electrochemical CO2 Reduction,” Advanced Energy Materials, 2018, pp. 1-9.
[cited by applicant]
Zheng, et al., “Hyperbranched polymers: advances from synthesis to applications”, Chemical Society Reviews, 2015, vol. 44, pp. 4091-4130.
[cited by applicant]
Zhu, Q., et al., “Opportunities for Electrocatalytic CO
[cited by applicant]
Zhu, Wenlei et al., “Active and Selective Conversion of CO2 to CO on Ultrathin Au Nanowires,” Journal of American Chemical Society, 2014, 136, pp. 16132-16135.
[cited by applicant]
CN Office Action dated Feb. 13, 2025 in CN Application No. 201980086718.8, with English Translation.
[cited by applicant]
JP Office Action dated Jan. 28, 2025 in JP Application No. 2022-530995, with English Translation.
[cited by applicant]
U.S. Corrected Notice of Allowance dated Dec. 16, 2024 in U.S. Appl. No. 17/303,329.
[cited by applicant]
U.S. Final Office Action dated Mar. 17, 2025 in U.S. Appl. No. 17/369,952.
[cited by applicant]
U.S. Notice of Allowance dated Jan. 15, 2025 in U.S. Appl. No. 18/299,672.
[cited by applicant]
U.S. Notice of Allowance dated Jan. 23, 2025 in U.S. Appl. No. 18/327,835.
[cited by applicant]
U.S. Notice of Allowance dated Mar. 13, 2025 in U.S. Appl. No. 17/303,329.
[cited by applicant]
U.S. Notice of Allowance dated Mar. 19, 2025 in U.S. Appl. No. 18/300,380.
[cited by applicant]
BR Office Action dated Aug. 15, 2023, in Application No. BR1120210103686 with English translation.
[cited by applicant]
CA Office Action dated Feb. 28, 2024 in CA Application No. 3120748.
[cited by applicant]
Chen L., et al., “Design Principles for Water Dissociation Catalysts in High-performance Bipolar Membranes,” Nature Communications, 2022, vol. 13 Article No. 3846, pp. 1-10.
[cited by applicant]
IN Office Action dated Jan. 31, 2023 in Application No. IN202117028812.
[cited by applicant]
International Preliminary Report on Patentability and Written Opinion dated May 23, 2024 in PCT Application No. PCT/US2022/079570.
[cited by applicant]
International Preliminary Report on Patentability dated Jun. 10, 2021 in Application No. PCT/US2019/063471.
[cited by applicant]
International Search Report and Written Opinion dated Apr. 26, 2024 in PCT Application No. PCT/US2023/075864.
[cited by applicant]
International Search Report and Written Opinion dated May 6, 2024 in PCT Application No. PCT/US2022/081209.
[cited by applicant]
International Search Report and Written Opinion issued on Mar. 19, 2020, in PCT Application No. PCT/US2019/063471.
[cited by applicant]
Invitation to Pay Additional Fees dated May 28, 2024 in PCT Application No. PCT/US2023/085244.
[cited by applicant]
JP Office Action dated Dec. 5, 2023 in JP Application No. 2021-528976 with English translation.
[cited by applicant]
JP Office Action dated Feb. 6, 2024 in JP Application No. 2022-187975, with English Translation.
[cited by applicant]
JP Office Action dated Sep. 5, 2023, in Application No. JP2021-528976 with English translation.
[cited by applicant]
Pappijn, C., et al., “Challenges and Opportunities of Carbon Capture and Utilization: Electrochemical Conversion of CO2 to Ethylene,” Original research, 2020, vol. 8, pp. 1-12.
[cited by applicant]
SA Examination Report dated Aug. 8, 2023, in Application No. 521422124 with English Translation.
[cited by applicant]
SA Examination Report dated Feb. 6, 2024, in SA Application No. 521422124, with English Translation.
[cited by applicant]
Seo M.H., et al., “Synthesis, Characterization, and Electrocatalytic Properties of a Polypyrrole-composited Pd/C Catalyst,” International Journal of Hydrogen Energy, 2011, vol. 36(18), pp. 11545-11553.
[cited by applicant]
Sturman, M., et al., “Process Parameters in the Electrochemical Reduction of Carbon Dioxide to Ethylene,” ChemBioEng, 2021, vol. 8(3), pp. 149-188.
[cited by applicant]
U.S. Corrected Notice of Allowance dated Jan. 9, 2023 in U.S. Appl. No. 16/697,066.
[cited by applicant]
U.S. Corrected Notice of Allowance dated Mar. 19, 2024 in U.S. Appl. No. 18/145,702.
[cited by applicant]
U.S. Final Office Action dated Feb. 8, 2024 in U.S. Appl. No. 18/327,835.
[cited by applicant]
U.S. Final Office Action dated Jul. 2, 2024 in U.S. Appl. No. 18/327,835.
[cited by applicant]
U.S. Final Office Action dated Mar. 21, 2024 in U.S. Appl. No. 18/300,380.
[cited by applicant]
U.S. Non Final Office Action dated Feb. 23, 2022 in U.S. Appl. No. 16/697,066.
[cited by applicant]
U.S. Non-Final Office Action dated Jan. 19, 2024 in U.S. Appl. No. 17/303,329.
[cited by applicant]
U.S. Non-Final Office Action dated Jan. 19, 2024 in U.S. Appl. No. 18/306,928.
[cited by applicant]
U.S. Non-Final Office Action dated Jan. 22, 2024 in U.S. Appl. No. 17/369,952.
[cited by applicant]
U.S. Non-Final Office Action dated Jan. 23, 2024 in U.S. Appl. No. 18/299,672.
[cited by applicant]
U.S. Non-Final Office Action dated Jul. 5, 2024 in U.S. Appl. No. 17/369,952.
[cited by applicant]
U.S. Non-Final Office Action dated Jun. 17, 2024 in U.S. Appl. No. 17/342,406.
[cited by applicant]
U.S. Non-Final Office Action dated Nov. 8, 2023 in U.S. Appl. No. 18/145,702.
[cited by applicant]
U.S. Notice of Allowance dated Mar. 6, 2024 in U.S. Appl. No. 18/145,702.
[cited by applicant]
U.S. Notice of Allowance dated Sep. 29, 2022 in U.S. Appl. No. 16/697,066.
[cited by applicant]
U.S. Restriction Requirement dated Oct. 29, 2021, in U.S. Appl. No. 16/697,066.
[cited by applicant]
Xie K., et al., “Bipolar Membrane Electrolyzers Enable High Single Pass CO
[cited by applicant]
International Preliminary Report on Patentability and Written Opinion dated Jun. 20, 2024 in PCT Application No. PCT/US2022/081209.
[cited by applicant]
International Search Report and Written Opinion dated Jul. 19, 2024 in PCT Application No. PCT/US2023/085244.
[cited by applicant]
AE Search Report and Examination Report dated Jun. 20, 2024 in AE Application No. P6000880 /2021.
[cited by applicant]
Australian Examination Report dated Oct. 22, 2024, in AU Application No. 2019386085.
[cited by applicant]
BR Office Action and Search Report dated Sep. 11, 2024 in BR Application No. 112022010144-9, with English Translation.
[cited by applicant]
CN Office Action dated Jun. 27, 2024 in CN Application No. 201980086718.8 with English translation.
[cited by applicant]
JP Office Action dated Oct. 29, 2024 in JP Application No. 2022-187975 with English translation.
[cited by applicant]
KR Office Action dated Oct. 16, 2024 in KR Application No. 10-2021-7019873 with English Translation.
[cited by applicant]
SA Office Action dated Sep. 16, 2024 in SA Application No. 524452150 with English translation.
[cited by applicant]
U.S. Final Office Action dated Jul. 17, 2024 in U.S. Appl. No. 17/303,329.
[cited by applicant]
U.S. Final Office Action dated Jul. 18, 2024 in U.S. Appl. No. 18/306,928.
[cited by applicant]
U.S. Final Office Action dated Sep. 10, 2024 in U.S. Appl. No. 18/299,672.
[cited by applicant]
U.S. Non-Final Office Action dated Dec. 11, 2024 in U.S. Appl. No. 17/342,406.
[cited by applicant]
U.S. Non-Final Office Action dated Oct. 31, 2024 in U.S. Appl. No. 18/300,380.
[cited by applicant]
U.S. Notice of Allowance dated Nov. 14, 2024 in U.S. Appl. No. 17/303,329.
[cited by applicant]