Modulating Chloride Adsorption for Efficient Chloride-Mediated Methane Conversion over Tungsten Oxide Photoanode

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-03-30 DOI:10.1021/acscatal.4c07046

Jun Ma, Keke Mao, Jiayi Li, Guangyao Zhai, Di Wu, Dong Liu, Ran Long, Yujie Xiong

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Abstract

Utilizing alkali chlorides as the chloride source in chloride-mediated methane activation represents an efficient approach for CH₄ valorization. Nevertheless, great challenges remain due to the restricted catalytic activity and durability. Here, we present a photoelectrochemical approach for chloride-mediated methane conversion to C₁ products using WO₃ with surface oxygen vacancies (OV). Theoretical calculations indicate that oxygen vacancies play a crucial role in enhancing chloride adsorption to facilitate methane activation. The engineered WO₃–OV photoanode exhibits enhanced catalytic performance in comparison to the pristine counterparts, attaining a Faradaic efficiency of 94.5% for C₁ products (methyl chloride, methanol, formic acid, and formaldehyde) at 0.9 V vs RHE. This performance corresponds to a total production rate of 139.2 mmol g^–1 h^–1 for the C₁ products. Furthermore, the system is capable of achieving a high CH₄ conversion efficiency of 11.8%. This work emphasizes the pivotal role of photoanode design and surface engineering in facilitating methane conversion.

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调节氯化物吸附在氧化钨光阳极上的高效氯化物介导甲烷转化

利用碱氯化物作为氯化物源进行氯化物介导的甲烷活化是一种有效的甲烷活化途径。然而，由于催化活性和耐久性的限制，仍然存在很大的挑战。在这里，我们提出了一种利用表面氧空位（OV）的WO3将氯化物介导的甲烷转化为C1产物的光电化学方法。理论计算表明，氧空位在增强氯化物吸附以促进甲烷活化方面起着至关重要的作用。与原始的WO3-OV光阳极相比，工程WO3-OV光阳极表现出更强的催化性能，在0.9 V vs RHE下，对C1产物（氯甲烷、甲醇、甲酸和甲醛）的法拉第效率达到94.5%。这一性能对应于C1产品的总生产速率为139.2 mmol g-1 h-1。此外，该系统能够实现高达11.8%的CH4转化效率。这项工作强调了光阳极设计和表面工程在促进甲烷转化中的关键作用。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.