Organic frameworks confined Cu single atoms and nanoclusters for tandem electrocatalytic CO2 reduction to methane
Qinglan Zhao,
Yian Wang,
Meng Li,
Shangqian Zhu,
Tiehuai Li,
Jixiang Yang,
Ting Lin,
Ernest P. Delmo,
Yinuo Wang,
Juhee Jang,
Meng Gu,
Minhua Shao
Affiliations
Qinglan Zhao
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Yian Wang
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Meng Li
Guangdong Provincial Research Center for Environment Pollution Control and Remediation Materials, College of Life Science and Technology Jinan University Guangzhou China
Shangqian Zhu
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Tiehuai Li
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Jixiang Yang
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Ting Lin
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Ernest P. Delmo
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Yinuo Wang
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Juhee Jang
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Meng Gu
Department of Materials Science and Engineering Southern University of Science and Technology Shenzhen China
Minhua Shao
Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Hong Kong China
Abstract The electrochemical reduction reaction of carbon dioxide (CO2RR) is considered to be an effective way to realize carbon neutrality. As a type of intensively studied materials, covalent organic frameworks (COFs) with a tunable pore structure and various functional groups are promising catalysts for CO2RR. Herein, COF synthesized by 2,6‐diaminoanthraquinone and 2,4,6‐triformylphloroglucinol is employed to assist the synthesis of electrocatalysts from Cu single atoms (SAs) to nanoclusters by controlling the electrodeposition. A tandem catalyst for CO2‐to‐CH4 conversion is thus achieved by the Cu nanoclusters dispersed among the isolated Cu SAs in the COF network. It is proposed that CO2 is first reduced to CO over the atomically isolated Cu SAs, followed by diffusion onto the neighboring Cu nanoclusters for further reduction into CH4. In addition, mechanistic analysis suggests that the coordinated K+ ions on the COF network promote the activation of CO2 and the adsorption of reaction intermediates, thus realizing the suppressed hydrogen evolution reaction and selective production of CH4. This study presents a new insight of COFs for the confined synthesis of a tunable SA to nanocluster electrocatalysts, disclosing the great potential of COFs in electrocatalysis.