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Title: Highly Selective Electrocatalytic Reduction of CO2 into Methane on Cu–Bi Nanoalloys

Abstract

Methane (CH4), the main component of natural gas, is one of the most valuable products facilitating energy storage via electricity conversion. However, the poor selectivity and high overpotential for CH4 formation with metallic Cu catalysts prevent realistic applications. Introducing a second element to tune the electronic state of Cu has been widely used as an effective method to improve catalytic performance, but achieving high selectivity and activity toward CH4 remains challenging. Here, we successfully synthesized Cu–Bi NPs, which exhibit a CH4 Faradaic efficiency (FE) as high as 70.6% at -1.2 V versus reversible hydrogen electrode (RHE). The FE of Cu–Bi NPs has increased by approximately 25-fold compared with that of Cu NPs. DFT calculations showed that alloying Cu with Bi significantly decreases the formation energy of *COH formation, the rate-determining step, which explains the improved performance. Further analysis showed that Cu that has been partially oxidized because of electron withdrawal by Bi is the most possible active site.

Authors:
ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [1];  [3]; ORCiD logo [3]; ORCiD logo [4];  [1]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [6]
+ Show Author Affiliations
  1. Harbin Institute of Technology (China)
  2. Soochow University, Suzhou (China)
  3. Canadian Light Source (CLS), Saskatoon, SK (Canada)
  4. Harbin Medical University (China)
  5. Soochow University, Suzhou (China); California Institute of Technology (CalTech), Pasadena, CA (United States)
  6. California Institute of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Natural Science Foundation of China (NSFC); National Science Foundation (NSF)
OSTI Identifier:
1801625
Grant/Contract Number:  
SC0004993; 51572062; 81771903; 21972034; ACI-1053575
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 17; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; science & technology; materials science; physics; alloying; alloys; catalysts; energy; selectivity

Citation Formats

Wang, Zhijiang, Yuan, Qi, Shan, Jingjing, Jiang, Zhaohua, Xu, Ping, Hu, Yongfeng, Zhou, Jigang, Wu, Lina, Niu, Zhuangzhuang, Sun, Jianmin, Cheng, Tao, and Goddard, William A. Highly Selective Electrocatalytic Reduction of CO2 into Methane on Cu–Bi Nanoalloys. United States: N. p., 2020. Web. doi:10.1021/acs.jpclett.0c01261.
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Wang, Zhijiang, Yuan, Qi, Shan, Jingjing, Jiang, Zhaohua, Xu, Ping, Hu, Yongfeng, Zhou, Jigang, Wu, Lina, Niu, Zhuangzhuang, Sun, Jianmin, Cheng, Tao, & Goddard, William A. Highly Selective Electrocatalytic Reduction of CO2 into Methane on Cu–Bi Nanoalloys. United States. https://doi.org/10.1021/acs.jpclett.0c01261
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Wang, Zhijiang, Yuan, Qi, Shan, Jingjing, Jiang, Zhaohua, Xu, Ping, Hu, Yongfeng, Zhou, Jigang, Wu, Lina, Niu, Zhuangzhuang, Sun, Jianmin, Cheng, Tao, and Goddard, William A. Thu . "Highly Selective Electrocatalytic Reduction of CO2 into Methane on Cu–Bi Nanoalloys". United States. https://doi.org/10.1021/acs.jpclett.0c01261. https://www.osti.gov/servlets/purl/1801625.
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@article{osti_1801625,
title = {Highly Selective Electrocatalytic Reduction of CO2 into Methane on Cu–Bi Nanoalloys},
author = {Wang, Zhijiang and Yuan, Qi and Shan, Jingjing and Jiang, Zhaohua and Xu, Ping and Hu, Yongfeng and Zhou, Jigang and Wu, Lina and Niu, Zhuangzhuang and Sun, Jianmin and Cheng, Tao and Goddard, William A.},
abstractNote = {Methane (CH4), the main component of natural gas, is one of the most valuable products facilitating energy storage via electricity conversion. However, the poor selectivity and high overpotential for CH4 formation with metallic Cu catalysts prevent realistic applications. Introducing a second element to tune the electronic state of Cu has been widely used as an effective method to improve catalytic performance, but achieving high selectivity and activity toward CH4 remains challenging. Here, we successfully synthesized Cu–Bi NPs, which exhibit a CH4 Faradaic efficiency (FE) as high as 70.6% at -1.2 V versus reversible hydrogen electrode (RHE). The FE of Cu–Bi NPs has increased by approximately 25-fold compared with that of Cu NPs. DFT calculations showed that alloying Cu with Bi significantly decreases the formation energy of *COH formation, the rate-determining step, which explains the improved performance. Further analysis showed that Cu that has been partially oxidized because of electron withdrawal by Bi is the most possible active site.},
doi = {10.1021/acs.jpclett.0c01261},
journal = {Journal of Physical Chemistry Letters},
number = 17,
volume = 11,
place = {United States},
year = {Thu Jul 23 00:00:00 EDT 2020},
month = {Thu Jul 23 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpclett.0c01261
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