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Research Article

Electron transfer in Cu/Cu2O generated by disproportionation promoting efficient CO2 photoreduction

Qian Zhu1,§, Kainan Zhu1,§, Minmin Cai1, Yaowen Zhang1, Zhiyu Shao1, Mengpei Jiang1, Xiyang Wang1, Zhibin Geng1, Xiaofeng Wu1, Manrong Li2, Keke Huang1( ), Shouhua Feng1
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin Provincial International Cooperation Key Laboratory of Advanced Inorganic Solid Functional Materials College of Chemistry, Jilin University, Changchun 130012, China
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China

§ Qian Zhu and Kainan Zhu contributed equally to this work.

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Graphical Abstract

By constructing Cu/Cu2O composite, the charge transfer between the two phases is realized. Density functional theory calculations prove that the amount of charge change of Cu in Cu/Cu2O has a linear relationship with the adsorption of the CO2 reduction intermediates, and further affects the Gibbs free energy of the reaction steps. Finally, the rate-determining step of CO2 photoreduction and the charge change on Cu form an inverse volcano curve.

Abstract

Constructing a high-efficiency composite material for CO2 photoreduction is a key step to the achievement of carbon neutralization, but a comprehensive understanding of the factors that dictate CO2 reduction activity remains elusive. Here, we constructed a series of Cu in situ combined on Cu2O (Cu/Cu2O-1, -2, -3) via an acid disproportionation method with various processing time. The optimal photocatalyst (Cu/Cu2O-2) affords CO at a rate of 10.43 μmol·g−1·h−1​​​​​​​, which is more than fourfold to that of pristine Cu2O. Electron transfer in the samples was detected by X-ray absorption spectroscopy (XAS) as well as X-ray photoelectron spectroscopy (XPS). Interestingly, the best photoreduction performance was not achieved by the sample possessing the most electron transfer (Cu/Cu2O-1) but by the one with moderate electron transfer (Cu/Cu2O-2). By virtue of density functional theory (DFT) calculations, a linear relationship between Bader charge variation (Δq) of the active sites and adsorption energy of CO2 reduction intermediates was discovered, wherein the moderate charge transfer corresponds to appropriate adsorption energy, which benefits CO2 photoreduction activity substantially. This work provides guidance for the construction of composite catalysts for efficient CO2 photoreduction in a perspective of the quantity of electron transfer.

Keywords

CO2 photocatalytic conversion charge transfercompositedensity functional theory (DFT)

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Nano Research
Volume 15 Issue 8,
August 2022
Pages 7099-7106
DOI: 10.1007/s12274-022-4397-0
Cite this article:
Zhu Q, Zhu K, Cai M, et al. Electron transfer in Cu/Cu2O generated by disproportionation promoting efficient CO2 photoreduction. Nano Research, 2022, 15(8): 7099-7106. https://doi.org/10.1007/s12274-022-4397-0
Topics:
Photocatalysis

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Received: 12 March 2022
Revised: 03 April 2022
Accepted: 05 April 2022
Published: 31 May 2022
© Tsinghua University Press 2022
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