Boosting Solar-Driven CO2 Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N2 Motif
Dr. Hainan Shi
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 China
Contribution: Conceptualization (lead), Data curation (lead), Funding acquisition (supporting), Investigation (lead), Resources (lead), Writing - original draft (lead)
Search for more papers by this authorYan Liang
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Investigation (lead), Writing - original draft (supporting)
Search for more papers by this authorProf. Jungang Hou
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Conceptualization (supporting), Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Haozhi Wang
State Key Laboratory of Marine Resource Utilization in South China Sea, School of Materials Science and Engineering, Hainan University, Haikou, 570228 China
Contribution: Conceptualization (equal), Investigation (equal), Software (lead), Supervision (equal), Writing - review & editing (equal)
Search for more papers by this authorZhenghao Jia
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Division of Energy Research Resources, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023 China
Contribution: Investigation (lead)
Search for more papers by this authorJiaming Wu
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Investigation (equal)
Search for more papers by this authorCorresponding Author
Prof. Fei Song
Shanghai Synchrotron Radiation Faciality, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204 China
Contribution: Conceptualization (supporting), Investigation (supporting), Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Hong Yang
School of Engineering, The University of Western Australia, Perth, WA 6009 Australia
Contribution: Conceptualization (supporting), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorCorresponding Author
Prof. Xinwen Guo
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorDr. Hainan Shi
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 China
Contribution: Conceptualization (lead), Data curation (lead), Funding acquisition (supporting), Investigation (lead), Resources (lead), Writing - original draft (lead)
Search for more papers by this authorYan Liang
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Investigation (lead), Writing - original draft (supporting)
Search for more papers by this authorProf. Jungang Hou
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Conceptualization (supporting), Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Haozhi Wang
State Key Laboratory of Marine Resource Utilization in South China Sea, School of Materials Science and Engineering, Hainan University, Haikou, 570228 China
Contribution: Conceptualization (equal), Investigation (equal), Software (lead), Supervision (equal), Writing - review & editing (equal)
Search for more papers by this authorZhenghao Jia
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Division of Energy Research Resources, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023 China
Contribution: Investigation (lead)
Search for more papers by this authorJiaming Wu
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Contribution: Investigation (equal)
Search for more papers by this authorCorresponding Author
Prof. Fei Song
Shanghai Synchrotron Radiation Faciality, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204 China
Contribution: Conceptualization (supporting), Investigation (supporting), Supervision (supporting), Writing - review & editing (supporting)
Search for more papers by this authorCorresponding Author
Hong Yang
School of Engineering, The University of Western Australia, Perth, WA 6009 Australia
Contribution: Conceptualization (supporting), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorCorresponding Author
Prof. Xinwen Guo
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, Dalian University of Technology, Dalian, 116024 China
Search for more papers by this authorAbstract
Cu-based catalysts have been shown to selectively catalyze CO2 photoreduction to C2+ solar fuels. However, they still suffer from poor activity and low selectivity. Herein, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol and delivers 69.8 μmol g−1 h−1 ethanol production rate, 97.8 % electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with DFT calculations, the superior photoactivity of Cu-N2-V stems from its defected Cu-N2 configuration, in which the Cu sites are electron enriched and enhance electron delocalization. Importantly, Cu in Cu-N2-V exist in both Cu+ and Cu2+ valence states, although predominantly as Cu+. The Cu+ sites support the CO2 activation, while the co-existence of Cu+/Cu2+ sites are highly conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C−C coupling. Furthermore, the hollow microstructure of the catalyst also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for the solar-driven CO2 conversion to ethanol. This study also elucidates the C-C coupling reaction path via *CO-*CO to *COCOH and rate-determining step, and reveals the valence state change of partial Cu species from Cu+ to Cu2+ in Cu-N2-V during CO2 photoreduction reaction.
Conflict of interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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