Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production

Xiao Chen; Shuaiqiang Jia; Jianxin Zhai; Jiapeng Jiao; Mengke Dong; Cheng Xue; Ting Deng; Hailian Cheng; Zhanghui Xia; Chunjun Chen; Xueqing Xing; Jianrong Zeng; Haihong Wu; Mingyuan He; Buxing Han

doi:10.1038/s41467-024-51928-z

Nature Communications (Sep 2024)

Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production

Xiao Chen,
Shuaiqiang Jia,
Jianxin Zhai,
Jiapeng Jiao,
Mengke Dong,
Cheng Xue,
Ting Deng,
Hailian Cheng,
Zhanghui Xia,
Chunjun Chen,
Xueqing Xing,
Jianrong Zeng,
Haihong Wu,
Mingyuan He,
Buxing Han

Affiliations

Xiao Chen: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Shuaiqiang Jia: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Jianxin Zhai: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Jiapeng Jiao: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Mengke Dong: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Cheng Xue: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Ting Deng: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Hailian Cheng: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Zhanghui Xia: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Chunjun Chen: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Xueqing Xing: Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences
Jianrong Zeng: Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences
Haihong Wu: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Mingyuan He: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University
Buxing Han: Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University

DOI: https://doi.org/10.1038/s41467-024-51928-z
Journal volume & issue: Vol. 15, no. 1
pp. 1 – 9

Abstract

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Abstract Copper (Cu)-based catalysts show promise for electrocatalytic CO2 reduction (CO2RR) to multi-carbon alcohols, but thermodynamic constraints lead to competitive hydrocarbon (e.g., ethylene) production. Achieving selective ethanol production with high Faradaic efficiency (FE) and current density is still challenging. Here we show a multivalent Cu-based catalyst, Cu-2,3,7,8-tetraaminophenazine-1,4,6,9-tetraone (Cu-TAPT) with Cu2+ and Cu+ atomic ratio of about 1:2 for CO2RR. Cu-TAPT exhibits an ethanol FE of 54.3 ± 3% at an industrial-scale current density of 429 mA cm−2, with the ethanol-to-ethylene ratio reaching 3.14:1. Experimental and theoretical calculations collectively unveil that the catalyst is stable during CO2RR, resulting from suitable coordination of the Cu2+ and Cu+ with the functional groups in TAPT. Additionally, mechanism studies show that the increased ethanol selectivity originates from synergy of multivalent Cu sites, which can promote asymmetric C–C coupling and adjust the adsorption strength of different carbonaceous intermediates, favoring hydroxy-containing C2 intermediate (*HCCHOH) formation and formation of ethanol.

Published in Nature Communications

ISSN: 2041-1723 (Online)
Publisher: Nature Portfolio
Country of publisher: United Kingdom
LCC subjects: Science
Website: https://www.nature.com/ncomms/

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