Regulating protonation paths for enhanced photocatalytic CO2 methanation by coupling Pt sites on WO2.9/TiO2†

IF 4.4 3区 化学 Q2 CHEMISTRY, PHYSICAL
Jiajun Du, Jun Deng, ChangAn Zhou, Hairong Yue, Chong Liu, Patrik Schmuki, Štěpán Kment and Xuemei Zhou
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Abstract

CO2 methanation via photocatalysis with water vapor is a sustainable technique for reducing CO2 emission but is challenged by the high energy barrier associated with the initial adsorption, activation and protonation of CO2 molecules. In this work, a substoichiometric WO2.9 thin film with strong Lewis acidity was coated on TiO2 microspheres, followed by the deposition of Pt cocatalysts on WO2.9 with controlled Pt single atoms and clusters (Pt–WO2.9/TiO2). The methane production rate reached 10.74 μmol h−1 g−1 with a selectivity of 99.8%, which was ∼40 times higher than that of bare TiO2 (0.27 μmol h−1 g−1). The high methane production rate was attributed to the synergy of Pt sites on the WO2.9/TiO2 heterojunction, where the Pt clusters facilitated water dissociation, thereby providing H* through hydrogen spillover on the surface, and the presence of a substoichiometric WO2.9 surface further enhanced the spillover process. The high density of active H* promoted the protonation pathway for CO2 activation (CO2 → COOH+ → *COOH), which improved the adsorption of the essential intermediate *CO on Pt single atoms and displayed a significantly reduced energy barrier for the protonation reaction of C1 intermediates, resulting in a mixed reaction pathway. This work provides new insights into a mechanism to regulate the reaction path to facilitate efficient photocatalytic CO2 methanation.

Abstract Image

通过偶联WO2.9/TiO2†上的Pt位点调节光催化CO2甲烷化的质子化路径
水蒸气光催化甲烷化是一种可持续的减少二氧化碳排放的技术,但由于二氧化碳分子的初始吸附、活化和质子化所带来的高能量势垒的挑战。在这项工作中,将具有强Lewis酸性的亚化学计量WO2.9薄膜涂覆在TiO2微球上,然后在WO2.9上沉积具有受控Pt单原子和簇的Pt共催化剂(Pt - WO2.9/TiO2)。甲烷的产率达到10.74 μmol h−1 g−1,选择性为99.8%,是裸TiO2 (0.27 μmol h−1 g−1)的约40倍。高甲烷产量归因于Pt位点在WO2.9/TiO2异质结上的协同作用,其中Pt团簇促进水解离,从而通过氢在表面的溢出提供H*,而亚化学计量的WO2.9表面的存在进一步增强了溢出过程。高密度的活性H*促进了CO2活化的质子化途径(CO2→COOH+→*COOH),提高了必需中间体*CO在Pt单原子上的吸附,显著降低了C1中间体质子化反应的能垒,形成混合反应途径。这项工作为调节反应路径的机制提供了新的见解,以促进有效的光催化CO2甲烷化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Catalysis Science & Technology
Catalysis Science & Technology CHEMISTRY, PHYSICAL-
CiteScore
8.70
自引率
6.00%
发文量
587
审稿时长
1.5 months
期刊介绍: A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis. Editor-in-chief: Bert Weckhuysen Impact factor: 5.0 Time to first decision (peer reviewed only): 31 days
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