Li Junjun, Chen Yu, Yao Bingqing, Yang Wenjuan, Cui Xiaoya, Liu Huiling, Dai Sheng, Xi Shibo, Sun Zhiyi, Chen Wenxing, Qin Yuchen, Wang Jinlan, He Qian, Ling Chongyi, Wang Dingsheng, Zhang Zhicheng
Department of Chemistry, School of Science; Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin 300072, China.
Key Laboratory of Quantum Materials and Devices of Ministry of Education, School of Physics, Southeast University, Nanjing 211189, China.
J Am Chem Soc. 2024 Feb 28;146(8):5693-5701. doi: 10.1021/jacs.4c00475. Epub 2024 Feb 9.
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 CO 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 CH. As a proof of concept, the CuN-Ag nanocubes (NCs) with Ag located in partial Cu sites and a CuN unit center are successfully synthesized. The Faraday efficiency and partial current density of CH over CuN-Ag NCs are 7.8 and 9.0 times those of CuN 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 CH. Our work provides new insights into the cascade catalysis strategy at the atomic scale for boosting CO to multicarbon products.
合理调节反应中间体在铜基催化剂表面位点上的结合强度，有助于在电化学CO还原反应中实现C-C偶联以生成多碳产物。在此，理论计算表明，级联的Ag-Cu双位点可协同增加局部CO覆盖率并降低CO质子化的动力学势垒，从而增强不对称C-C偶联以生成CH。作为概念验证，成功合成了Ag位于部分Cu位点且具有CuN单元中心的CuN-Ag纳米立方体（NCs）。CuN-Ag NCs上CH的法拉第效率和分电流密度分别是CuN NCs的7.8倍和9.0倍。原位光谱结合理论计算证实，Ag位点产生CO，Cu位点促进向*COCHO的不对称C-C偶联，显著增强了CH的生成。我们的工作为在原子尺度上促进CO生成多碳产物的级联催化策略提供了新的见解。
