Li Pengsong, Liu Jiyuan, Wang Yong, Zhang Xiang-Da, Hou Yuqing, Zhang Yichao, Sun Xiaofu, Kang Xinchen, Zhu Qinggong, Han Buxing
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, PR China.
J Am Chem Soc. 2024 Sep 25;146(38):26525-26533. doi: 10.1021/jacs.4c10472. Epub 2024 Sep 10.
Rational regulation of the electrochemical CO reduction reaction (CORR) pathway to produce desired products is particularly interesting, yet designing economical and robust catalysts is crucial. Here, we report an antimony-modified copper (CuSb) catalyst capable of selectively producing both CO and multicarbon (C) products in the CORR. At a current density of 0.3 A/cm, the faradaic efficiency (FE) of CO was as high as 98.2% with a potential of -0.6 V vs reversible hydrogen electrode (RHE). When the current density increased to 1.1 A/cm at -1.1 V vs RHE, the primary products shifted to C compounds with a FE of 75.6%. Experimental and theoretical studies indicate that tuning the potential could manipulate the oxygen species on the CuSb surface, which determined the product selectivity in the CORR. At a more positive potential, the existence of oxygen species facilitates the potential-limiting step involving *COOH formation and reduces the adsorption of *CO intermediates, thereby promoting CO production. At a more negative potential, the localized high CO concentration coupled with the enhanced adsorption of *CO intermediates due to Sb incorporation facilitates C-C coupling and deep hydrogenation processes, resulting in an increased C selectivity.
合理调控电化学CO还原反应（CORR）途径以生成所需产物极具吸引力，但设计经济且耐用的催化剂至关重要。在此，我们报道了一种锑修饰的铜（CuSb）催化剂，其能够在CORR中选择性地生成CO和多碳（C）产物。在电流密度为0.3 A/cm²时，相对于可逆氢电极（RHE），CO的法拉第效率（FE）高达98.2%，电位为-0.6 V。当电流密度在相对于RHE为-1.1 V时增加到1.1 A/cm²时，主要产物转变为C化合物，FE为75.6%。实验和理论研究表明，调节电位可以操控CuSb表面的氧物种，这决定了CORR中的产物选择性。在更正的电位下，氧物种的存在促进了涉及COOH形成的电位限制步骤，并减少了CO中间体的吸附，从而促进了CO的生成。在更负的电位下，局部高CO浓度加上由于掺入Sb而增强的*CO中间体吸附促进了C-C偶联和深度氢化过程，导致C选择性增加。
