Li Xiaoyao, Wang Min, Wang Rongyan, Wang Yang, Zhu Min, Zhang Lingxia, Shi Jianlin
Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road, Shanghai 200050, P. R. China.
School of Materials and Chemistry, University of Shanghai for Science and Technology, 516 Jun-gong Road, Shanghai 200093, P. R. China.
ACS Nano. 2024 Feb 11. doi: 10.1021/acsnano.3c12001.
Highly selective production of CH from photocatalytic CO reduction is still a great challenge which involves the kinetically unfavorable transfers of 8 protons and 8 electrons. Herein, CeO photocatalysts incorporated with isolated Ru single-atoms have been fabricated, which demonstrate dramatically elevated selectivity of CH from CO reduction. The introduced Ru single-atoms promote carrier separation and accelerate electron transfer, which efficiently enhances the photocatalytic activity. Density functional theory (DFT) calculations and FT-IR analysis manifest that the Ru single-atom active sites play an indispensable role in strengthening the adsorption of *CO intermediate on the catalyst surface and promoting HO oxidation to generate abundant protons, thus favoring *CO protonation into *CHO ( = 1, 2, 3) species and final deoxygenation into CH. This work provides an effective strategy by constructing single-atom active sites to modulate and stabilize the key intermediates of CO photoreduction to improve the selectivity of the target products.
通过光催化CO还原高选择性地生产CH仍然是一个巨大的挑战,这涉及到8个质子和8个电子在动力学上不利的转移。在此,制备了负载孤立Ru单原子的CeO光催化剂,其在CO还原反应中对CH的选择性显著提高。引入的Ru单原子促进了载流子分离并加速了电子转移,从而有效地提高了光催化活性。密度泛函理论(DFT)计算和傅里叶变换红外光谱(FT-IR)分析表明,Ru单原子活性位点在增强CO中间体在催化剂表面的吸附以及促进H₂O氧化以产生大量质子方面发挥了不可或缺的作用,从而有利于CO质子化生成*CHOₓ(x = 1, 2, 3)物种并最终脱氧生成CH₄。这项工作通过构建单原子活性位点提供了一种有效的策略,以调节和稳定CO光还原的关键中间体,从而提高目标产物的选择性。