中科院化学所韩布兴团队报道了通过原子镧掺杂剂诱导CuOx催化剂的拉伸应变提高CO₂至C₂₊产物的电还原效率。相关研究成果于2023年4月24日发表于国际一流学术期刊《美国化学会杂志》。

在CO₂还原反应（CO₂RR）中，Cu是一种很有前途的电催化剂，可制备高价值的C₂₊产物。然而，作为重要的C–C偶联活性位点，Cu⁺物种在还原条件下通常是不稳定的。原子掺杂剂如何影响铜基催化剂的性能是值得研究的。

该文中，研究人员首先计算了CO₂RR的热力学极限电位与析氢反应之间的差异，以及掺杂不同金属的Cu₂O上的*CO结合能，结果表明在Cu₂O中掺杂原子Gd可以有效地提高催化剂的性能。在理论研究的基础上，我们设计了Gd₁/CuO_x催化剂。Gd独特的电子结构和大的离子半径不仅使Cu⁺物种在反应过程中保持稳定，而且在Gd₁/CuO_x中引起拉伸应变，从而使催化剂在将CO₂电还原为C₂₊产物方面具有优异的性能。与可逆氢电极相比，在0.8 V下，C₂₊产物的部分电流密度为444.3 mA cm^–2，C2+产品的法拉第效率可达81.4%。

详细的实验和理论研究表明，Gd掺杂增强了催化剂上的CO₂活化，稳定了关键中间体O*CCO，并降低了C–C偶联反应的能垒。

附：英文原文

Title: Improving CO2-to-C2+ Product Electroreduction Efficiency via Atomic Lanthanide Dopant-Induced Tensile-Strained CuOx Catalysts

Author: Jiaqi Feng, Limin Wu, Shoujie Liu, Liang Xu, Xinning Song, Libing Zhang, Qinggong Zhu, Xinchen Kang, Xiaofu Sun, Buxing Han

Issue&Volume: April 24, 2023

Abstract: Cu is a promising electrocatalyst in CO2 reduction reaction (CO2RR) to high-value C2+ products. However, as important C–C coupling active sites, the Cu+ species is usually unstable under reduction conditions. How atomic dopants affect the performance of Cu-based catalysts is interesting to be studied. Herein, we first calculated the difference between the thermodynamic limiting potentials of CO2RR and the hydrogen evolution reaction, as well as the *CO binding energy over Cu2O doped with different metals, and the results indicated that doping atomic Gd into Cu2O could improve the performance of the catalyst effectively. On the basis of the theoretical study, we designed Gd1/CuOx catalysts. The distinctive electronic structure and large ion radii of Gd not only keep the Cu+ species stable during the reaction but also induce tensile strain in Gd1/CuOx, resulting in excellent performance of the catalysts for electroreduction of CO2 to C2+ products. The Faradic efficiency of C2+ products could reach 81.4% with a C2+ product partial current density of 444.3 mA cm–2 at 0.8 V vs a reversible hydrogen electrode. Detailed experimental and theoretical studies revealed that Gd doping enhanced CO2 activation on the catalyst, stabilized the key intermediate O*CCO, and reduced the energy barrier of the C–C coupling reaction.

DOI: 10.1021/jacs.3c02428

Source: https://pubs.acs.org/doi/10.1021/jacs.3c02428