Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane

Creators: Zhang, Haochen; Chang, Xiaoxia; Chen, Jingguang G.; Goddard, William A., III; Xu, Bingjun; Cheng, Mu-Jeng; Lu, Qi

Abstract

Electroreduction of carbon dioxide to hydrocarbons and oxygenates on copper involves reduction to a carbon monoxide adsorbate followed by further transformation to hydrocarbons and oxygenates. Simultaneous improvement of these processes over a single reactive site is challenging due to the linear scaling relationship of the binding strength of key intermediates. Herein, we report improved electroreduction of carbon dioxide by exploiting a one-pot tandem catalysis mechanism based on computational and electrochemical investigations. By constructing a well-defined copper-modified silver surface, adsorbed carbon monoxide generated on the silver sites is proposed to migrate to surface copper sites for the subsequent reduction to methane, which is consistent with insights gained from operando attenuated total reflectance surface enhanced infrared absorption spectroscopic investigations. Our results provide a promising approach for designing carbon dioxide electroreduction catalysts to enable one-pot reduction of products beyond carbon monoxide and formate.

Additional Information

© 2019 The Author(s). 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 http://creativecommons.org/licenses/by/4.0/. Received 16 December 2018; Accepted 30 June 2019; Published 26 July 2019. Data availability: The data that support the findings of this study are available from the corresponding author upon request. This work is supported by the National Key Research and Development Program of China (grant number 2017YFA0208200) and the National Natural Science Foundation of China (grant numbers 21872079, 21606142). W.A.G. is supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. X.C. and B.X. acknowledge the support of the National Science Foundation CAREER Program (Award No. CBET-1651625). M.-J.C. acknowledges financial support from the Ministry of Science and Technology of the Republic of China under grant no. MOST 107–2113-M-006–008-MY2. Author Contributions: H.Z., M.-J.C., and Q.L. conceived and designed both computational and electrochemical investigations and wrote the manuscript. H.Z. and M.-J.C. performed DFT calculations and analyzed the data. H.Z. and Q.L. carried out the electrocatalytic tests and analyzed the results. H.Z. and Q.L. performed electron microscopy studies, FIB, XPS, and analyzed these data. X.C. and B.X. performed ATR-SEIRAS experiments and analyzed the results. J.G.C., W.A.G., and B.X. contributed to data analysis and writing of this manuscript. The authors declare no competing interests.

Attached Files

Published - s41467-019-11292-9.pdf

Supplemental Material - 41467_2019_11292_MOESM1_ESM.pdf

Files

41467_2019_11292_MOESM1_ESM.pdf

Files (8.1 MB)

Name	Size	Download all
41467_2019_11292_MOESM1_ESM.pdf md5:2cfbddc09172b40d9aaeab87d293686c	6.4 MB	Preview Download
s41467-019-11292-9.pdf md5:a7c69db3e1e82ed78befec16c2e4a163	1.7 MB	Preview Download

Additional details

	All versions	This version
Views	0	0
Downloads	0	0
Data volume	0 Bytes	0 Bytes