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Boosting CO2 electroreduction to multicarbon products via tuning of the copper surface charge
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Wang, Di, Li, Lifen, Xia, Qineng, Hong, Song, Hao, Leiduan, Robertson, Alex W. and Sun, Zhenyu (2022) Boosting CO2 electroreduction to multicarbon products via tuning of the copper surface charge. ACS Sustainable Chemistry & Engineering, 10 (34). pp. 11451-11458. doi:10.1021/acssuschemeng.2c03963 ISSN 2168-0485.
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WRAP-Boosting-CO2-electroreduction-multicarbon-products-tuning-copper-surface-charge-22.pdf - Accepted Version - Requires a PDF viewer. Download (1801Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/acssuschemeng.2c03963
Abstract
Electrochemical CO2 reduction (ECR) to multicarbon compounds holds great potential but remains plagued with large overpotential, low Faradaic efficiency (FE), and debilitating competition from the evolution of hydrogen and the C1 product. The design and development of advanced catalytic systems is required to overcome these problems. Here, we demonstrate the selective cathodic CO2 conversion to C2+ chemicals (C2H4, C2H5OH, and n-C3H7OH) by optimizing the surface charge of Cu via fine-tuned annealing of CuSiO3@SiO2. Stabilization of Cu+ by forming Cu–O–Si bonds is attained, as predicted by density functional theory (DFT) calculations and evidenced by multiple experiments. The C2+ selectivity is readily regulated by adjusting the surface content of Cu+, underpinning its significance during the ECR. The resulting Cuδ+@SiO2 with a Cu0-to-Cu+ surface ratio of ∼0.5 achieves a remarkable C2+ FE as high as ∼70%, C2+ partial geometric current density of about 9 mA cm–2, and large C2+-to-C1 ratio of ∼10, using an H-type cell in aqueous CsBr electrolytes at mild overpotentials. The high C2+ FE and current density persist over 12 h of continuous CO2 electrolysis. In addition, a respectable C2+ FE of ∼52% can still be attained even at a large current density (500 mA cm–2) in a flow reactor system. DFT computations reveal that the oxidized copper species Cu+ boosts C–C coupling by lessening the formation energy of the critical *OCCOH intermediate. This work underscores the prominent role of the support–catalyst interaction and the modulation of Cu oxidation states in steering the ECR selectivity.
Item Type: | Journal Article | |||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TP Chemical technology |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | |||||||||
Library of Congress Subject Headings (LCSH): | Carbon dioxide, Carbon dioxide mitigation, Electrolytic reduction, Carbon dioxide -- Environmental aspects, Carbon dioxide -- Industrial applications, Electrocatalysis | |||||||||
Journal or Publication Title: | ACS Sustainable Chemistry & Engineering | |||||||||
Publisher: | American Chemical Society | |||||||||
ISSN: | 2168-0485 | |||||||||
Official Date: | 29 August 2022 | |||||||||
Dates: |
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Volume: | 10 | |||||||||
Number: | 34 | |||||||||
Page Range: | pp. 11451-11458 | |||||||||
DOI: | 10.1021/acssuschemeng.2c03963 | |||||||||
Status: | Peer Reviewed | |||||||||
Publication Status: | Published | |||||||||
Reuse Statement (publisher, data, author rights): | This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry & Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see ACS Articles on Request ].” | |||||||||
Access rights to Published version: | Restricted or Subscription Access | |||||||||
Copyright Holders: | Copyright © 2022 American Chemical Society | |||||||||
Date of first compliant deposit: | 18 October 2022 | |||||||||
Date of first compliant Open Access: | 16 August 2023 | |||||||||
RIOXX Funder/Project Grant: |
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