Mechanistic Insights into OC–COH Coupling in CO2 Electroreduction on Fragmented Copper

Yao, Kaili, Li, Jun, Wang, Haibin, Lu, Ruihu, Yang, Xiaotao, Luo, Mingchuan, Wang, Ning, Wang, Ziyun, Liu, Changxu, Jing, Tan, Chen, Songhua, Cortés, Emiliano, Maier, Stefan A., Zhang, Sheng, Li, Tieliang, Yu, Yifu, Liu, Yongchang, Kang, Xinchen and Liang, Hongyan (2022) Mechanistic Insights into OC–COH Coupling in CO2 Electroreduction on Fragmented Copper. Journal of the American Chemical Society, 144 (31). pp. 14005-14011. ISSN 0002-7863

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The carbon–carbon (C–C) bond formation is essential for the electroconversion of CO2 into high-energy-density C2+ products, and the precise coupling pathways remain controversial. Although recent computational investigations have proposed that the OC–COH coupling pathway is more favorable in specific reaction conditions than the well-known CO dimerization pathway, the experimental evidence is still lacking, partly due to the separated catalyst design and mechanistic/spectroscopic exploration. Here, we employ density functional theory calculations to show that on low-coordinated copper sites, the *CO bindings are strengthened, and the adsorbed *CO coupling with their hydrogenation species, *COH, receives precedence over CO dimerization. Experimentally, we construct a fragmented Cu catalyst with abundant low-coordinated sites, exhibiting a 77.8% Faradaic efficiency for C2+ products at 300 mA cm–2. With a suite of in situ spectroscopic studies, we capture an *OCCOH intermediate on the fragmented Cu surfaces, providing direct evidence to support the OC–COH coupling pathway. The mechanistic insights of this research elucidate how to design materials in favor of OC–COH coupling toward efficient C2+ production from CO2 reduction.

Item Type: Article
Additional Information: Funding information: This work was supported by the National Natural Science Foundation of China (NSFC No. 51771132), the Program for Young and Middle-aged Teachers in Science Research of Fujian Province (No. JAT210433). We also acknowledge funding and support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy, EXC 2089/1-390776260, the Bavarian program Solar Energies Go Hybrid (SolTech), the Center for NanoScience (CeNS), and the European Commission through the ERC Starting Grant CATALIGHT (802989). We acknowledge the Paul Scherrer Institut, Villigen, Switzerland, for the provision of synchrotron radiation beam time at the beamline SuperXAS of the SLS and would like to thank M. Nachtegaal for the assistance. The computational study is supported by the Marsden Fund Council from Government funding and managed by the Royal Society Te Apa̅rangi. Z.W. and R.L. wish to acknowledge the use of New Zealand eScience Infrastructure (NeSI) high-performance computing facilities, consulting support, and/or training services as part of this research. S.A.M. additionally acknowledges the EPSRC (EP/W017075/1) and the Lee-Lucas Chair in Physics.
Uncontrolled Keywords: adsorption, catalysts, Chemical reactions, copper, energy
Subjects: F100 Chemistry
H800 Chemical, Process and Energy Engineering
Department: Faculties > Engineering and Environment > Mathematics, Physics and Electrical Engineering
Depositing User: Rachel Branson
Date Deposited: 09 Aug 2022 10:50
Last Modified: 29 Jul 2023 03:30

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