Tang Zheng, Li Chenxi, Yan Chenyu, Zhang Qian, Piao Zhe, Wang Honggui, Zhang Ya
School of Environmental Science and Engineering, Yangzhou University, Yangzhou, Jiangsu 225127, China.
School of Environmental Science and Engineering, Yangzhou University, Yangzhou, Jiangsu 225127, China.
J Colloid Interface Sci. 2025 Feb;679(Pt B):50-59. doi: 10.1016/j.jcis.2024.10.055. Epub 2024 Oct 18.
Electrocatalytic carbon dioxide reduction reaction (eCORR) is one of the attractive approaches to CO utilization. Nevertheless, it remains a challenge to prepare highly efficient and selective electrocatalysts to realize deep conversion of multi-carbon products. The absence of active sites due to the reconfiguration of copper-based catalysts leads to migration deactivation during catalysis, rendering low catalytic efficiency. In this work, CuSe nanowires (NWs) were obtained from the Cu foam. After further electroreduction for 90 s, Ag nanoparticles (NPs) were modified on the flower rod-shaped CuSe NWs (Ag/CuSe NWs). This interfacial modification strategy, balanced the Cu active valence state on the surface of the Ag/CuSe NWs, led to a high Faradaic efficiency (FE) of ethanol (∼70 %) at -0.52 V (vs. reversible hydrogen electrode (RHE)). Besides, the Ag/CuSe NWs achieved a high partial current (∼13.9 mA) for ethanol, 18.5 μmol/h ethanol yield and an energy efficiency of 47.1 % in the H-type electrolytic cell. The reaction mechanism was investigated at the molecular level through density functional theory (DFT) calculation. The interface-modified Ag NPs provided stable *COOH intermediates during the reaction process, effectively achieving surface *CO enrichment. Besides, the presence of Ag NPs resulted in the generation of abundant Cu active species. The *CO migrated to the Cu active sites to accelerate the asymmetric coupling of *CO and *CHO, which significantly improved the FE of CO electroreduction to ethanol. Our work offers a promising approach for designing CuSe-based nanowires electrocatalysts for CO reduction with excellent activity and selectivity.
电催化二氧化碳还原反应（eCORR）是二氧化碳利用的一种有吸引力的方法。然而，制备高效且选择性的电催化剂以实现多碳产物的深度转化仍然是一个挑战。铜基催化剂的重新构型导致活性位点的缺失，从而在催化过程中导致迁移失活，使得催化效率较低。在这项工作中，从泡沫铜中获得了硒化铜纳米线（NWs）。在进一步电还原90秒后，在花杆状硒化铜纳米线（Ag/CuSe NWs）上修饰了银纳米颗粒（NPs）。这种界面修饰策略平衡了Ag/CuSe NWs表面的铜活性价态，在-0.52 V（相对于可逆氢电极（RHE））下导致乙醇的法拉第效率（FE）高达约70%。此外，Ag/CuSe NWs在H型电解池中实现了乙醇的高偏电流（约13.9 mA）、18.5 μmol/h的乙醇产率和47.1%的能量效率。通过密度泛函理论（DFT）计算在分子水平上研究了反应机理。界面修饰的Ag NPs在反应过程中提供了稳定的COOH中间体，有效地实现了表面CO富集。此外，Ag NPs的存在导致产生了丰富的铜活性物种。CO迁移到铜活性位点以加速CO和*CHO的不对称偶联，这显著提高了CO电还原为乙醇的FE。我们的工作为设计具有优异活性和选择性的用于CO还原的基于硒化铜的纳米线电催化剂提供了一种有前景的方法。
