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在二氧化铈上构建钌单原子以优化一氧化碳光还原产物

Construction of Ru Single-Atoms on Ceria to Reform the Products of CO Photoreduction.

作者信息

Li Xiaoyao, Wang Min, Wang Rongyan, Wang Yang, Zhu Min, Zhang Lingxia, Shi Jianlin

机构信息

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.

出版信息

ACS Nano. 2024 Feb 11. doi: 10.1021/acsnano.3c12001.

Abstract

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.

摘要

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。

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