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Reaction mechanism and kinetics for CO₂ reduction on nickel single atom catalysts from quantum mechanics

Hossain, Md Delowar and Huang, Yufeng and Yu, Ted H. and Goddard, William A., III and Luo, Zhengtang (2020) Reaction mechanism and kinetics for CO₂ reduction on nickel single atom catalysts from quantum mechanics. Nature Communications, 11 . Art. No. 2256. ISSN 2041-1723. PMCID PMC7205999. doi:10.1038/s41467-020-16119-6.

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Experiments have shown that graphene-supported Ni-single atom catalysts (Ni-SACs) provide a promising strategy for the electrochemical reduction of CO₂ to CO, but the nature of the Ni sites (Ni-N₂C₂, Ni-N₃C₁, Ni-N₄) in Ni-SACs has not been determined experimentally. Here, we apply the recently developed grand canonical potential kinetics (GCP-K) formulation of quantum mechanics to predict the kinetics as a function of applied potential (U) to determine faradic efficiency, turn over frequency, and Tafel slope for CO and H₂ production for all three sites. We predict an onset potential (at 10 mA cm⁻²) U_(onset) = −0.84 V (vs. RHE) for Ni-N₂C₂ site and U_(onset) = −0.92 V for Ni-N₃C₁ site in agreement with experiments, and U_(onset) = −1.03 V for Ni-N₄. We predict that the highest current is for Ni-N₄, leading to 700 mA cm⁻² at U = −1.12 V. To help determine the actual sites in the experiments, we predict the XPS binding energy shift and CO vibrational frequency for each site.

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URLURL TypeDescription CentralArticle
Hossain, Md Delowar0000-0003-3440-8306
Huang, Yufeng0000-0002-0373-2210
Yu, Ted H.0000-0003-3202-0981
Goddard, William A., III0000-0003-0097-5716
Luo, Zhengtang0000-0002-5134-9240
Additional Information:© The Author(s) 2020. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit Received 30 September 2019; Accepted 07 April 2020; Published 07 May 2020. This project was supported by the Research Grant Council of Hong Kong SAR (Project numbers 16204818), NSFC-RGC Joint Research Scheme (N_HKUST607/17), the Innovation and Technology Commission (ITC-CNERC14SC01), the Guangzhou Science & Technology (Project 201704030134). This work was also supported by the Joint Center for Artificial Photosynthesis (JCAP), a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993. The calculations were performed on computer clusters at the materials and process simulation center (MSC) at Caltech, the high-performance computing (HPC) facility at Caltech, and the HKUST (funded by the School of Engineering). Data availability: The data that support the findings of this study are available from the corresponding author upon request. Author Contributions: M.D.H., W.A.G., and Z.T.L. conceived the idea and designed the research. M.D.H. performed all the calculations. M.D.H., Y.H., and T.H.Y. participated in discussions analyzing the data obtained from the calculations. M.D.H., W.A.G., and Z.T.L. wrote the paper with helpful comments from Y.H. and T.H.Y. The authors declare no competing interests.
Funding AgencyGrant Number
Research Grant Council of Hong Kong16204818
National Natural Science Foundation of ChinaN_HKUST607/17
Innovation and Technology Commission (Hong Kong)ITC-CNERC14SC01
Guangzhou Science and Technology Plan201704030134
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
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PubMed Central ID:PMC7205999
Record Number:CaltechAUTHORS:20200511-085432577
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Official Citation:Hossain, M.D., Huang, Y., Yu, T.H. et al. Reaction mechanism and kinetics for CO2 reduction on nickel single atom catalysts from quantum mechanics. Nat Commun 11, 2256 (2020).
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103091
Deposited By: Tony Diaz
Deposited On:11 May 2020 18:25
Last Modified:15 Feb 2022 22:48

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