Competition Between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media

Overview

Journal Langmuir

Publisher American Chemical Society

Specialty Chemistry

Date 2017 Apr 29

PMID 28453940

Citations 46

Authors

Hideshi Ooka

Marta C Figueiredo

Marc T M Koper

Affiliations

Soon will be listed here.

Abstract

Understanding the competition between hydrogen evolution and CO reduction is of fundamental importance to increase the faradaic efficiency for electrocatalytic CO reduction in aqueous electrolytes. Here, by using a copper rotating disc electrode, we find that the major hydrogen evolution pathway competing with CO reduction is water reduction, even in a relatively acidic electrolyte (pH 2.5). The mass-transport-limited reduction of protons takes place at potentials for which there is no significant competition with CO reduction. This selective inhibitory effect of CO on water reduction, as well as the difference in onset potential even after correction for local pH changes, highlights the importance of differentiating between water reduction and proton reduction pathways for hydrogen evolution. In-situ FTIR spectroscopy indicates that the adsorbed CO formed during CO reduction is the primary intermediate responsible for inhibiting the water reduction process, which may be one of the main mechanisms by which copper maintains a high faradaic efficiency for CO reduction in neutral media.

Citing Articles

Decoupling CO effects from electrochemistry: A mechanistic study of copper catalyst degradation.

Serra-Maia R, Varley J, Weitzner S, Yu H, Shi R, Biener J iScience. 2025; 28(3):111851.

PMID: 40040807 PMC: 11879610. DOI: 10.1016/j.isci.2025.111851.

Proton-Transfer Dynamics Regulates CO Electroreduction Products via Hydrogen Coverage.

Fan Q, Xiao T, Liu H, Yan T, Lin J, Kuang S ACS Cent Sci. 2024; 10(12):2331-2337.

PMID: 39735305 PMC: 11672531. DOI: 10.1021/acscentsci.4c01534.

Electrolyte Anions Suppress Hydrogen Generation in Electrochemical CO Reduction on Cu.

Fuller L, Zhang G, Noh S, Van Lehn R, Schreier M Angew Chem Int Ed Engl. 2024; 64(10):e202421196.

PMID: 39724507 PMC: 11878348. DOI: 10.1002/anie.202421196.

Parameter Dependency of Electrochemical Reduction of CO in Acetonitrile - A Data Driven Approach.

Deacon-Price C, Mijatovic A, Hoefsloot H, Rothenberg G, Garcia A Chemphyschem. 2024; 26(4):e202400794.

PMID: 39523599 PMC: 11832059. DOI: 10.1002/cphc.202400794.

Time-Resolved Infrared Spectroscopic Evidence for Interfacial pH-Dependent Kinetics of Formate Evolution on Cu Electrodes.

Katsoukis G, Heida H, Gutgesell M, Mul G ACS Catal. 2024; 14(18):13867-13876.

PMID: 39324054 PMC: 11420947. DOI: 10.1021/acscatal.4c03521.

References

Kortlever R, Shen J, Schouten K, Calle-Vallejo F, Koper M . Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide. J Phys Chem Lett. 2016; 6(20):4073-82. DOI: 10.1021/acs.jpclett.5b01559. View

Kuhl K, Hatsukade T, Cave E, Abram D, Kibsgaard J, Jaramillo T . Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J Am Chem Soc. 2014; 136(40):14107-13. DOI: 10.1021/ja505791r. View

Strmcnik D, Uchimura M, Wang C, Subbaraman R, Danilovic N, Van der Vliet D . Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption. Nat Chem. 2013; 5(4):300-6. DOI: 10.1038/nchem.1574. View

Auinger M, Katsounaros I, Meier J, Klemm S, Biedermann P, Topalov A . Near-surface ion distribution and buffer effects during electrochemical reactions. Phys Chem Chem Phys. 2011; 13(36):16384-94. DOI: 10.1039/c1cp21717h. View

Wuttig A, Liu C, Peng Q, Yaguchi M, Hendon C, Motobayashi K . Tracking a Common Surface-Bound Intermediate during CO2-to-Fuels Catalysis. ACS Cent Sci. 2016; 2(8):522-8. PMC: 4999975. DOI: 10.1021/acscentsci.6b00155. View

Trummal A, Lipping L, Kaljurand I, Koppel I, Leito I . Acidity of Strong Acids in Water and Dimethyl Sulfoxide. J Phys Chem A. 2016; 120(20):3663-9. DOI: 10.1021/acs.jpca.6b02253. View

Tang W, Peterson A, Varela A, Jovanov Z, Bech L, Durand W . The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction. Phys Chem Chem Phys. 2011; 14(1):76-81. DOI: 10.1039/c1cp22700a. View

Ma M, Djanashvili K, Smith W . Controllable Hydrocarbon Formation from the Electrochemical Reduction of CO2 over Cu Nanowire Arrays. Angew Chem Int Ed Engl. 2016; 55(23):6680-4. DOI: 10.1002/anie.201601282. View

Loiudice A, Lobaccaro P, Kamali E, Thao T, Huang B, Ager J . Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction. Angew Chem Int Ed Engl. 2016; 55(19):5789-92. DOI: 10.1002/anie.201601582. View

10.

Jackson M, Surendranath Y . Donor-Dependent Kinetics of Interfacial Proton-Coupled Electron Transfer. J Am Chem Soc. 2016; 138(9):3228-34. DOI: 10.1021/jacs.6b00167. View

11.

Qiao J, Liu Y, Hong F, Zhang J . A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem Soc Rev. 2013; 43(2):631-75. DOI: 10.1039/c3cs60323g. View

12.

Kas R, Kortlever R, Milbrat A, Koper M, Mul G, Baltrusaitis J . Electrochemical CO2 reduction on Cu2O-derived copper nanoparticles: controlling the catalytic selectivity of hydrocarbons. Phys Chem Chem Phys. 2014; 16(24):12194-201. DOI: 10.1039/c4cp01520g. View

13.

Tu C, Tripp B, Ferry J, Silverman D . Bicarbonate as a proton donor in catalysis by Zn(II)- and Co(II)-containing carbonic anhydrases. J Am Chem Soc. 2001; 123(25):5861-6. DOI: 10.1021/ja010301o. View