Revolutionizing CO2 conversion for single-carbon products: Unveiling the photocatalytic magic of M6@TiO2 via First-Principles insights

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Applied Surface Science Pub Date : 2024-12-12 DOI:10.1016/j.apsusc.2024.162085

Qiang Chen , Hongyang Xu , Chuan Liu , Xihong Ding , Yuanzheng Zhu , Shixia Wang , Chunguang Chen , Ping Cheng

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Abstract

Metal clusters can be loaded as cocatalysts on the surface of TiO₂ to promote the photocatalytic reduction of CO₂. However, the specific mechanism of this reaction is still unclear. This study systematically investigates the performance of metal cluster (M₆, M = Au, Ag, Mn, Cu, Sn, Ga, Mo and Bi) as the cocatalytic on the TiO₂(101) surface towards the CO₂ reduction reaction through density functional theory (DFT) calculations. Metal clusters as co-catalysts supported on TiO₂ can improve the light absorption intensity of photocatalysts. Moreover, it was found that these metal clusters significantly improved the electron transport efficiency of TiO₂, thereby enhancing the efficiency of photocatalytic CO₂ reduction. Cu₆@TiO₂ showed the highest photocatalytic activity, with a maximum Gibbs free energy change (ΔG_max) of 0.46 eV. The study also revealed a strong correlation between catalytic activity and the adsorption strength of key intermediates, indicating that enhancing the adsorption differences of key intermediates can improve the efficiency of photocatalysts. In addition, Mn₆@TiO₂, Cu₆@TiO₂, Mo₆@TiO₂, Au₆@TiO₂, and Ga₆@TiO₂ can effectively suppress the hydrogen evolution reaction (HER), demonstrating excellent photocatalytic performance and high selectivity. This work provides useful insights into the reduction of CO₂ to form single carbon products on TiO₂ catalysts loading metal clusters.

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革新单碳产品的二氧化碳转化：通过第一原理的见解揭示M6@TiO2的光催化魔力

金属团簇可以作为助催化剂负载在TiO2表面，促进CO2的光催化还原。然而，这种反应的具体机制尚不清楚。本研究通过密度泛函理论（DFT）计算，系统地考察了金属团簇（M6, M = Au, Ag, Mn, Cu, Sn, Ga， Mo和Bi）作为TiO2（101）表面CO2还原反应的共催化剂的性能。在TiO2上负载金属团簇作为共催化剂，可以提高光催化剂的光吸收强度。此外，研究发现这些金属团簇显著提高了TiO2的电子传递效率，从而提高了光催化CO2还原的效率。Cu6@TiO2的光催化活性最高，Gibbs自由能变化（ΔGmax）最大值为0.46 eV。研究还揭示了催化活性与关键中间体的吸附强度之间存在较强的相关性，表明提高关键中间体的吸附差异可以提高光催化剂的效率。此外，Mn6@TiO2、Cu6@TiO2、Mo6@TiO2、Au6@TiO2和Ga6@TiO2可以有效抑制析氢反应（HER），表现出优异的光催化性能和高选择性。这项工作为在负载金属簇的TiO2催化剂上减少二氧化碳形成单碳产物提供了有用的见解。

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来源期刊

Applied Surface Science 工程技术-材料科学：膜

CiteScore

12.50

自引率

7.50%

发文量

3393

审稿时长

67 days

期刊介绍： Applied Surface Science covers topics contributing to a better understanding of surfaces, interfaces, nanostructures and their applications. The journal is concerned with scientific research on the atomic and molecular level of material properties determined with specific surface analytical techniques and/or computational methods, as well as the processing of such structures.