Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544-5263
Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA 90095-1592
Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544-5263, Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA 90095-1592, Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ 08544-5263
The electrochemical CO 2 reduction reaction (CO 2 RR) powered by excess zero-carbon-emission electricity to produce especially multicarbon (C 2+ ) products could contribute to a carbon-neutral to carbon-negative economy. Foundational to the rational design of efficient, selective CO 2 RR electrocatalysts is mechanistic analysis of the best metal catalyst thus far identified, namely, copper (Cu), via quantum mechanical computations to complement experiments. Here, we apply embedded correlated wavefunction (ECW) theory, which regionally corrects the electron exchange-correlation error in density functional theory (DFT) approximations, to examine multiple C–C coupling steps involving adsorbed CO (*CO) and its hydrogenated derivatives on the most ubiquitous facet, Cu(111). We predict that two adsorbed hydrogenated CO species, either *COH or *CHO, are necessary precursors for C–C bond formation. The three kinetically feasible pathways involving these species yield all three possible products: *COH–CHO, *COH–*COH, and *OCH–*OCH. The most kinetically favorable path forms *COH–CHO. In contrast, standard DFT approximations arrive at qualitatively different conclusions, namely, that only *CO and *COH will prevail on the surface and their C–C coupling paths produce only *COH–*COH and *CO–*CO, with a preference for the first product. This work demonstrates the importance of applying qualitatively and quantitatively accurate quantum mechanical method to simulate electrochemistry in order ultimately to shed light on ways to enhance selectivity toward C 2+ product formation via CO 2 RR electrocatalysts.
Zhao, Qing, et al. "Charting C–C coupling pathways in electrochemical CO <sub>2</sub> reduction on Cu(111) using embedded correlated wavefunction theory." Proceedings of the National Academy of Sciences of the United States of America, vol. 119, no. 44, Oct. 2022. https://doi.org/10.1073/pnas.2202931119
Zhao, Qing, Martirez, John Mark P., & Carter, Emily A. (2022). Charting C–C coupling pathways in electrochemical CO <sub>2</sub> reduction on Cu(111) using embedded correlated wavefunction theory. Proceedings of the National Academy of Sciences of the United States of America, 119(44). https://doi.org/10.1073/pnas.2202931119
Zhao, Qing, Martirez, John Mark P., and Carter, Emily A., "Charting C–C coupling pathways in electrochemical CO <sub>2</sub> reduction on Cu(111) using embedded correlated wavefunction theory," Proceedings of the National Academy of Sciences of the United States of America 119, no. 44 (2022), https://doi.org/10.1073/pnas.2202931119
@article{osti_1895198,
author = {Zhao, Qing and Martirez, John Mark P. and Carter, Emily A.},
title = {Charting C–C coupling pathways in electrochemical CO <sub>2</sub> reduction on Cu(111) using embedded correlated wavefunction theory},
annote = { The electrochemical CO 2 reduction reaction (CO 2 RR) powered by excess zero-carbon-emission electricity to produce especially multicarbon (C 2+ ) products could contribute to a carbon-neutral to carbon-negative economy. Foundational to the rational design of efficient, selective CO 2 RR electrocatalysts is mechanistic analysis of the best metal catalyst thus far identified, namely, copper (Cu), via quantum mechanical computations to complement experiments. Here, we apply embedded correlated wavefunction (ECW) theory, which regionally corrects the electron exchange-correlation error in density functional theory (DFT) approximations, to examine multiple C–C coupling steps involving adsorbed CO (*CO) and its hydrogenated derivatives on the most ubiquitous facet, Cu(111). We predict that two adsorbed hydrogenated CO species, either *COH or *CHO, are necessary precursors for C–C bond formation. The three kinetically feasible pathways involving these species yield all three possible products: *COH–CHO, *COH–*COH, and *OCH–*OCH. The most kinetically favorable path forms *COH–CHO. In contrast, standard DFT approximations arrive at qualitatively different conclusions, namely, that only *CO and *COH will prevail on the surface and their C–C coupling paths produce only *COH–*COH and *CO–*CO, with a preference for the first product. This work demonstrates the importance of applying qualitatively and quantitatively accurate quantum mechanical method to simulate electrochemistry in order ultimately to shed light on ways to enhance selectivity toward C 2+ product formation via CO 2 RR electrocatalysts. },
doi = {10.1073/pnas.2202931119},
url = {https://www.osti.gov/biblio/1895198},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {ISSN 0027-8424},
number = {44},
volume = {119},
place = {United States},
publisher = {Proceedings of the National Academy of Sciences},
year = {2022},
month = {10}}
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1895198
Alternate ID(s):
OSTI ID: 1962800 OSTI ID: 1963053
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 44 Vol. 119; ISSN 0027-8424