Asymmetric Cu-N-La Species Enabling Atomic-Level Donor-Acceptor Structure and Favored Reaction Thermodynamics for Selective CO2 Photoreduction to CH4

Wenke Xie; Yushen Liu; Xing Zhang; Huijuan Yan; Xuan-He Liu; Xiaoyu Zhang; Qinglan Zhao; Hongwei Huang

doi:10.1002/anie.202314384

Asymmetric Cu-N-La Species Enabling Atomic-Level Donor-Acceptor Structure and Favored Reaction Thermodynamics for Selective CO₂ Photoreduction to CH₄

Angew Chem Int Ed Engl. 2024 Jan 25;63(5):e202314384. doi: 10.1002/anie.202314384. Epub 2023 Dec 28.

Authors

Wenke Xie¹, Yushen Liu², Xing Zhang³, Huijuan Yan³, Xuan-He Liu¹, Xiaoyu Zhang³, Qinglan Zhao², Hongwei Huang⁴

Affiliations

¹ School of Science, China University of Geosciences (Beijing), Beijing, 100083, China.
² Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
³ CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institution of Chemistry, Chinese Academy of Sciences (CAS), Beijing, 100190, China.
⁴ Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing, 100083, China.

PMID: 38100253
DOI: 10.1002/anie.202314384

Abstract

Photocatalytic CO₂ reduction into ideal hydrocarbon fuels, such as CH₄ , is a sluggish kinetic process involving adsorption of multiple intermediates and multi-electron steps. Achieving high CH₄ activity and selectivity therefore remains a great challenge, which largely depends on the efficiency of photogenerated charge separation and transfer as well as the intermediate energy levels in CO₂ reduction. Herein, we construct La and Cu dual-atom anchored carbon nitride (LaCu/CN), with La-N₄ and Cu-N₃ coordination bonds connected by Cu-N-La bridges. The asymmetric Cu-N-La species enables the establishment of an atomic-level donor-acceptor structure, which allows the migration of electrons from La atoms to the reactive Cu atom sites. Simultaneously, intermediates during CO₂ reduction on LaCu/CN demonstrate thermodynamically more favorable process for CH₄ formation based on theoretical calculations. Eventually, LaCu/CN exhibits a high selectivity (91.6 %) for CH₄ formation with a yield of 125.8 μmol g^-1 , over ten times of that for pristine CN. This work presents a strategy for designing multi-functional dual-atom based photocatalysts.

Keywords: CH4 Formation; CO2 Reduction; Carbon Nitride; Donor-Acceptor Interaction; Metal Dual-Atom.

Abstract

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