中科院化学所韩步兴团队报道了p块金属掺杂Cu诱导的p-d轨道杂化促进安培级CO₂电还原中C2+产物的形成。相关研究成果发表在2023年2月17日出版的《美国化学会杂志》。

大电流电解CO₂生成多碳（C2+）产品对于实现CO₂转化的工业应用至关重要。然而，*CO中间体在催化剂表面上的低结合强度导致了多种竞争途径，这阻碍了C2+的产生。

该文中，研究人员报道了Ga掺杂的Cu（CuGa）诱导的p–d轨道杂交可以在安培级电流密度下促进CO₂制备C2+产物的有效电催化。发现CuGa在0.9A/cm²的电流密度下表现出最高的C2+生产率，具有81.5%的显著法拉第效率（FE），并且在这样的高电流密度下的电势相对于可逆氢电极为1.07V。在1.1 A/cm²时，催化剂仍保持较高的C2+产率，FE为76.9%。

实验和理论研究表明，CuGa的优异性能源自Cu和Ga的p–d杂交，这不仅丰富了反应位点，还增强了*CO中间体的结合强度，促进了C–C偶联。p–d杂交策略可以扩展到其他p嵌段金属掺杂的Cu催化剂，如CuAl和CuGe，以促进CO₂电还原以产生C2+。这是第一项使用p嵌段金属掺杂Cu催化剂通过p–d轨道杂交相互作用促进电化学CO₂还原反应生成C2+产物的工作。

附：英文原文

Title: p–d Orbital Hybridization Induced by p-Block Metal-Doped Cu Promotes the Formation of C2+ Products in Ampere-Level CO2 Electroreduction

Author: Pengsong Li, Jiahui Bi, Jiyuan Liu, Yong Wang, Xinchen Kang, Xiaofu Sun, Jianling Zhang, Zhimin Liu, Qinggong Zhu, Buxing Han

Issue&Volume: February 17, 2023

Abstract: Large-current electrolysis of CO2 to multi-carbon (C2+) products is critical to realize the industrial application of CO2 conversion. However, the poor binding strength of *CO intermediates on the catalyst surface induces multiple competing pathways, which hinder the C2+ production. Herein, we report that p–d orbital hybridization induced by Ga-doped Cu (CuGa) could promote efficient CO2 electrocatalysis to C2+ products at ampere-level current density. It was found that CuGa exhibited the highest C2+ productivity with a remarkable Faradaic efficiency (FE) of 81.5% at a current density of 0.9 A/cm2, and the potential at such a high current density was 1.07 V versus reversible hydrogen electrode. At 1.1 A/cm2, the catalyst still maintained a high C2+ productivity with an FE of 76.9%. Experimental and theoretical studies indicated that the excellent performance of CuGa results from the p–d hybridization of Cu and Ga, which not only enriches reactive sites but also enhances the binding strength of the *CO intermediate and facilitates C–C coupling. The p–d hybridization strategy can be extended to other p-block metal-doped Cu catalysts, such as CuAl and CuGe, to boost CO2 electroreduction for C2+ production. As far as we know, this is the first work to promote electrochemical CO2 reduction reaction to generate the C2+ product by p–d orbital hybridization interaction using a p-block metal-doped Cu catalyst.

DOI: 10.1021/jacs.2c12743

Source: https://pubs.acs.org/doi/10.1021/jacs.2c12743