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:
-
- Harbin Institute of Technology (China)
- Soochow University, Suzhou (China)
- Canadian Light Source (CLS), Saskatoon, SK (Canada)
- Harbin Medical University (China)
- Soochow University, Suzhou (China); California Institute of Technology (CalTech), Pasadena, CA (United States)
- 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.
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
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.
@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}
}
Works referenced in this record:
CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films
journal, April 2012
- Li, Christina W.; Kanan, Matthew W.
- Journal of the American Chemical Society, Vol. 134, Issue 17, p. 7231-7234
Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates
journal, May 2018
- Wang, Zhijiang; Wu, Lina; Sun, Kun
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 11
A Highly Selective Copper-Indium Bimetallic Electrocatalyst for the Electrochemical Reduction of Aqueous CO 2 to CO
journal, December 2014
- Rasul, Shahid; Anjum, Dalaver H.; Jedidi, Abdesslem
- Angewandte Chemie International Edition, Vol. 54, Issue 7
Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst
journal, October 2018
- Morales-Guio, Carlos G.; Cave, Etosha R.; Nitopi, Stephanie A.
- Nature Catalysis, Vol. 1, Issue 10
Unveiling the Active Structure of Single Nickel Atom Catalysis: Critical Roles of Charge Capacity and Hydrogen Bonding
journal, March 2020
- Zhao, Xunhua; Liu, Yuanyue
- Journal of the American Chemical Society, Vol. 142, Issue 12
Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2
journal, September 2018
- Liang, Zhi-Qin; Zhuang, Tao-Tao; Seifitokaldani, Ali
- Nature Communications, Vol. 9, Issue 1
Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns
journal, December 2016
- Ma, Sichao; Sadakiyo, Masaaki; Heima, Minako
- Journal of the American Chemical Society, Vol. 139, Issue 1
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
journal, April 2014
- Li, Christina W.; Ciston, Jim; Kanan, Matthew W.
- Nature, Vol. 508, Issue 7497
Nanostructured electrocatalysts with tunable activity and selectivity
journal, March 2016
- Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie
- Nature Reviews Materials, Vol. 1, Issue 4
Structure- and Electrolyte-Sensitivity in CO 2 Electroreduction
journal, October 2018
- Arán-Ais, Rosa M.; Gao, Dunfeng; Roldan Cuenya, Beatriz
- Accounts of Chemical Research, Vol. 51, Issue 11
Ionic Liquid-Mediated Selective Conversion of CO2 to CO at Low Overpotentials
journal, September 2011
- Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R.
- Science, Vol. 334, Issue 6056, p. 643-644
Electrochemical Reduction of CO 2 Using Copper Single-Crystal Surfaces: Effects of CO* Coverage on the Selective Formation of Ethylene
journal, February 2017
- Huang, Yun; Handoko, Albertus D.; Hirunsit, Pussana
- ACS Catalysis, Vol. 7, Issue 3
Dynamic Changes in the Structure, Chemical State and Catalytic Selectivity of Cu Nanocubes during CO 2 Electroreduction: Size and Support Effects
journal, April 2018
- Grosse, Philipp; Gao, Dunfeng; Scholten, Fabian
- Angewandte Chemie International Edition, Vol. 57, Issue 21
Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction
journal, January 2018
- De Luna, Phil; Quintero-Bermudez, Rafael; Dinh, Cao-Thang
- Nature Catalysis, Vol. 1, Issue 2
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014
- Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
- Journal of the American Chemical Society, Vol. 136, Issue 40
Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts
journal, March 2015
- Ren, Dan; Deng, Yilin; Handoko, Albertus Denny
- ACS Catalysis, Vol. 5, Issue 5
Structure-Sensitive CO 2 Electroreduction to Hydrocarbons on Ultrathin 5-fold Twinned Copper Nanowires
journal, January 2017
- Li, Yifan; Cui, Fan; Ross, Michael B.
- Nano Letters, Vol. 17, Issue 2
Materials for solar fuels and chemicals
journal, December 2016
- Montoya, Joseph H.; Seitz, Linsey C.; Chakthranont, Pongkarn
- Nature Materials, Vol. 16, Issue 1
Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration
journal, August 2016
- Liu, Min; Pang, Yuanjie; Zhang, Bo
- Nature, Vol. 537, Issue 7620
Enhanced Electrochemical Methanation of Carbon Dioxide with a Dispersible Nanoscale Copper Catalyst
journal, September 2014
- Manthiram, Karthish; Beberwyck, Brandon J.; Alivisatos, A. Paul
- Journal of the American Chemical Society, Vol. 136, Issue 38
Activity Descriptors for CO 2 Electroreduction to Methane on Transition-Metal Catalysts
journal, January 2012
- Peterson, Andrew A.; Nørskov, Jens K.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water
journal, October 2016
- Cheng, Tao; Xiao, Hai; Goddard, William A.
- Journal of the American Chemical Society, Vol. 138, Issue 42
Single-Atomic Cu with Multiple Oxygen Vacancies on Ceria for Electrocatalytic CO 2 Reduction to CH 4
journal, June 2018
- Wang, Yifei; Chen, Zheng; Han, Peng
- ACS Catalysis, Vol. 8, Issue 8
Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2 , the first step in reduction of CO 2
journal, June 2017
- Favaro, Marco; Xiao, Hai; Cheng, Tao
- Proceedings of the National Academy of Sciences
Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene
journal, June 2016
- Mistry, Hemma; Varela, Ana Sofia; Bonifacio, Cecile S.
- Nature Communications, Vol. 7, Issue 1
Recycling of carbon dioxide to methanol and derived products – closing the loop
journal, January 2014
- Goeppert, Alain; Czaun, Miklos; Jones, John-Paul
- Chem. Soc. Rev., Vol. 43, Issue 23
Synergistic Chemisorbing and Electronic Effects for Efficient CO 2 Reduction Using Cysteamine-Functionalized Gold Nanoparticles
journal, December 2018
- Wang, Zhijiang; Sun, Kun; Liang, Caiyun
- ACS Applied Energy Materials, Vol. 2, Issue 1
Substantial Impact of Charge on Electrochemical Reactions of Two-Dimensional Materials
journal, June 2018
- Kim, Donghoon; Shi, Jianjian; Liu, Yuanyue
- Journal of the American Chemical Society, Vol. 140, Issue 29
Enhanced electrochemical reduction of CO 2 to CO on Ag electrocatalysts with increased unoccupied density of states
journal, January 2016
- Sun, Kun; Wu, Lina; Qin, Wu
- Journal of Materials Chemistry A, Vol. 4, Issue 32
Organosulfur-Functionalized Au, Pd, and Au−Pd Nanoparticles on 1D Silicon Nanowire Substrates: Preparation and XAFS Studies
journal, August 2005
- Zhang, Peng; Zhou, Xingtai; Tang, Yuanhong
- Langmuir, Vol. 21, Issue 18
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles
journal, September 2014
- Kim, Dohyung; Resasco, Joaquin; Yu, Yi
- Nature Communications, Vol. 5, Issue 1
Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel
journal, January 2016
- Gao, Shan; Lin, Yue; Jiao, Xingchen
- Nature, Vol. 529, Issue 7584
Anthropogenic Chemical Carbon Cycle for a Sustainable Future
journal, August 2011
- Olah, George A.; Prakash, G. K. Surya; Goeppert, Alain
- Journal of the American Chemical Society, Vol. 133, Issue 33
Ag L -edge x-ray-absorption near-edge-structure study of charge redistribution at the Ag site in Au-Ag alloys
journal, May 1994
- Bzowski, A.; Sham, T. K.; Yiu, Y. M.
- Physical Review B, Vol. 49, Issue 19
Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO 2 Conversion
journal, January 2018
- Lee, Chan Woo; Yang, Ki Dong; Nam, Dae-Hyun
- Advanced Materials, Vol. 30, Issue 42
Ultrahigh Mass Activity for Carbon Dioxide Reduction Enabled by Gold–Iron Core–Shell Nanoparticles
journal, October 2017
- Sun, Kun; Cheng, Tao; Wu, Lina
- Journal of the American Chemical Society, Vol. 139, Issue 44
Tin Oxide Dependence of the CO 2 Reduction Efficiency on Tin Electrodes and Enhanced Activity for Tin/Tin Oxide Thin-Film Catalysts
journal, January 2012
- Chen, Yihong; Kanan, Matthew W.
- Journal of the American Chemical Society, Vol. 134, Issue 4
Electrochemical Fragmentation of Cu 2 O Nanoparticles Enhancing Selective C–C Coupling from CO 2 Reduction Reaction
journal, January 2019
- Jung, Hyejin; Lee, Si Young; Lee, Chan Woo
- Journal of the American Chemical Society, Vol. 141, Issue 11
Tuning the electrocatalytic properties of a Cu electrode with organic additives containing amine group for CO 2 reduction
journal, January 2019
- Qiu, Yanling; Zhong, Hexiang; Xu, Wenbin
- Journal of Materials Chemistry A, Vol. 7, Issue 10
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts
journal, July 2015
- Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.
- Journal of the American Chemical Society, Vol. 137, Issue 31
Trace Levels of Copper in Carbon Materials Show Significant Electrochemical CO 2 Reduction Activity
journal, December 2015
- Lum, Yanwei; Kwon, Youngkook; Lobaccaro, Peter
- ACS Catalysis, Vol. 6, Issue 1
Free-Energy Barriers and Reaction Mechanisms for the Electrochemical Reduction of CO on the Cu(100) Surface, Including Multiple Layers of Explicit Solvent at pH 0
journal, November 2015
- Cheng, Tao; Xiao, Hai; Goddard, William A.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 23