Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO2 Electroreduction to Ethylene

Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO2 Electroreduction to Ethylene

Journal of the American Chemical Society

10.1021/jacs.4c00475

https://doi.org/10.1021/jacs.4c00475

Junjun Li, Yu Chen, Bingqing Yao, Wenjuan Yang, Xiaoya Cui, Huiling Liu, Sheng Dai, Shibo Xi, Zhiyi Sun, Wenxing Chen, Yuchen Qin, Jinlan Wang, Qian He, Chongyi Ling, Dingsheng Wang, Zhicheng Zhang

09 February 2024

Li, J., Chen, Y., Yao, B., Yang, W., Cui, X., Liu, H., Dai, S., Xi, S., Sun, Z., Chen, W., Qin, Y., Wang, J., He, Q., Ling, C., Wang, D., Zhang, Z. (2024). Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO2 Electroreduction to Ethylene. Journal of the American Chemical Society, 146(8), 5693–5701. https://doi.org/10.1021/jacs.4c00475

Rationally modulating the binding strength of reaction intermediates on surface sites of copper-based catalysts could facilitate C–C coupling to generate multicarbon products in an electrochemical CO2 reduction reaction. Herein, theoretical calculations reveal that cascade Ag–Cu dual sites could synergistically increase local CO coverage and lower the kinetic barrier for CO protonation, leading to enhanced asymmetric C–C coupling to generate C2H4. As a proof of concept, the Cu3N-Ag nanocubes (NCs) with Ag located in partial Cu sites and a Cu3N unit center are successfully synthesized. The Faraday efficiency and partial current density of C2H4 over Cu3N-Ag NCs are 7.8 and 9.0 times those of Cu3N NCs, respectively. In situ spectroscopies combined with theoretical calculations confirm that Ag sites produce CO and Cu sites promote asymmetric C–C coupling to *COCHO, significantly enhancing the generation of C2H4. Our work provides new insights into the cascade catalysis strategy at the atomic scale for boosting CO2 to multicarbon products.

Publisher Copyright

This research / project is supported by the Agency for Science, Technology and Research (A*STAR) - Low Carbon Energy Research Finding Initiative (LCERFI01-0033 | U2102d2006)
Grant Reference no. : U2102d2006

This research / project is supported by the National Research Foundation - National Research Foundation Fellowship
Grant Reference no. : NRF-NRFF11-2019-0002

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/jacs.4c00475

https://oar.a-star.edu.sg/communities-collections/articles/22701

0002-7863
1520-5126

Institute of Sustainability for Chemicals, Energy and Environment