Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction
Electrocatalytic carbon dioxide reduction (CO2RR) is a relatively feasible method to reduce the atmospheric concentration of CO2. Although a series of metal-based catalysts have gained interest for CO2RR, understanding the structure–activity relationship for Cu-based catalysts remains a great challe...
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| Format: | Article |
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Frontiers Media S.A.
2023-02-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/articles/10.3389/fchem.2023.1141453/full |
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| author | Runzhi An Xuanqi Chen Qi Fang Yuxiao Meng Yuxiao Meng Xi Li Yongyong Cao |
| author_facet | Runzhi An Xuanqi Chen Qi Fang Yuxiao Meng Yuxiao Meng Xi Li Yongyong Cao |
| author_sort | Runzhi An |
| collection | DOAJ |
| description | Electrocatalytic carbon dioxide reduction (CO2RR) is a relatively feasible method to reduce the atmospheric concentration of CO2. Although a series of metal-based catalysts have gained interest for CO2RR, understanding the structure–activity relationship for Cu-based catalysts remains a great challenge. Herein, three Cu-based catalysts with different sizes and compositions (Cu@CNTs, Cu4@CNTs, and CuNi3@CNTs) were designed to explore this relationship by density functional theory (DFT). The calculation results show a higher degree of CO2 molecule activation on CuNi3@CNTs compared to that on Cu@CNTs and Cu4@CNTs. The methane (CH4) molecule is produced on both Cu@CNTs and CuNi3@CNTs, while carbon monoxide (CO) is synthesized on Cu4@CNTs. The Cu@CNTs showed higher activity for CH4 production with a low overpotential value of 0.36 V compared to CuNi3@CNTs (0.60 V), with *CHO formation considered the potential-determining step (PDS). The overpotential value was only 0.02 V for *CO formation on the Cu4@CNTs, and *COOH formation was the PDS. The limiting potential difference analysis with the hydrogen evolution reaction (HER) indicated that the Cu@CNTs exhibited the highest selectivity of CH4 among the three catalysts. Therefore, the sizes and compositions of Cu-based catalysts greatly influence CO2RR activity and selectivity. This study provides an innovative insight into the theoretical explanation of the origin of the size and composition effects to inform the design of highly efficient electrocatalysts. |
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| language | English |
| last_indexed | 2024-04-10T16:24:06Z |
| publishDate | 2023-02-01 |
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| series | Frontiers in Chemistry |
| spelling | doaj.art-f5cf523cea3a43479c97bd1883296b8e2023-02-09T09:19:47ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462023-02-011110.3389/fchem.2023.11414531141453Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reactionRunzhi An0Xuanqi Chen1Qi Fang2Yuxiao Meng3Yuxiao Meng4Xi Li5Yongyong Cao6College of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaCollege of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaCollege of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaCollege of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaCollege of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou, ChinaCollege of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaCollege of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing, Zhejiang, ChinaElectrocatalytic carbon dioxide reduction (CO2RR) is a relatively feasible method to reduce the atmospheric concentration of CO2. Although a series of metal-based catalysts have gained interest for CO2RR, understanding the structure–activity relationship for Cu-based catalysts remains a great challenge. Herein, three Cu-based catalysts with different sizes and compositions (Cu@CNTs, Cu4@CNTs, and CuNi3@CNTs) were designed to explore this relationship by density functional theory (DFT). The calculation results show a higher degree of CO2 molecule activation on CuNi3@CNTs compared to that on Cu@CNTs and Cu4@CNTs. The methane (CH4) molecule is produced on both Cu@CNTs and CuNi3@CNTs, while carbon monoxide (CO) is synthesized on Cu4@CNTs. The Cu@CNTs showed higher activity for CH4 production with a low overpotential value of 0.36 V compared to CuNi3@CNTs (0.60 V), with *CHO formation considered the potential-determining step (PDS). The overpotential value was only 0.02 V for *CO formation on the Cu4@CNTs, and *COOH formation was the PDS. The limiting potential difference analysis with the hydrogen evolution reaction (HER) indicated that the Cu@CNTs exhibited the highest selectivity of CH4 among the three catalysts. Therefore, the sizes and compositions of Cu-based catalysts greatly influence CO2RR activity and selectivity. This study provides an innovative insight into the theoretical explanation of the origin of the size and composition effects to inform the design of highly efficient electrocatalysts.https://www.frontiersin.org/articles/10.3389/fchem.2023.1141453/fullelectrochemical CO2 reduction reaction (CO2RR)Cu-based catalystsdensity functional theory (DFT)size effectcompositional effect |
| spellingShingle | Runzhi An Xuanqi Chen Qi Fang Yuxiao Meng Yuxiao Meng Xi Li Yongyong Cao Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction Frontiers in Chemistry electrochemical CO2 reduction reaction (CO2RR) Cu-based catalysts density functional theory (DFT) size effect compositional effect |
| title | Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction |
| title_full | Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction |
| title_fullStr | Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction |
| title_full_unstemmed | Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction |
| title_short | Structure–activity relationship of Cu-based catalysts for the highly efficient CO2 electrochemical reduction reaction |
| title_sort | structure activity relationship of cu based catalysts for the highly efficient co2 electrochemical reduction reaction |
| topic | electrochemical CO2 reduction reaction (CO2RR) Cu-based catalysts density functional theory (DFT) size effect compositional effect |
| url | https://www.frontiersin.org/articles/10.3389/fchem.2023.1141453/full |
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