H2 production from the photocatalytic reforming of ethylene glycol: Effect of TiO2 crystalline phase on photo-oxidation mechanism

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2024-11-28 DOI:10.1016/j.jcat.2024.115876

Luke Roebuck, Helen Daly, Lan Lan, Joseph Parker, Angus Gostick, Nathan Skillen, Sarah J. Haigh, Marta Falkowska, Christopher Hardacre

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Abstract

In this work, the mechanism of H₂ production from ethylene glycol as a model compound for photoreforming over platinized TiO₂ is presented with particular focus on the effect of the TiO₂ polymorph. It was found that Pt/anatase and Pt/anatase:rutile (P25) had similar H₂ production activities and both catalysts followed an indirect oxidation pathway where ethylene glycol was oxidised via hydroxyl radicals to glycolaldehyde. In contrast, Pt/rutile primarily oxidised ethylene glycol directly into formaldehyde. The formaldehyde was unable to react further, which significantly reduced the formation of hydrogen despite similar conversion of ethylene glycol compared with the other supports used. We propose that these differences are due to different adsorption behaviour and hole transfer mechanism on the different TiO₂ crystalline phases. In particular, ethylene glycol complexation on Ti_5c sites on the dominant (110) facet of rutile leads to a direct hole transfer and an oxidative C–C cleavage mechanism prevailing.

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乙二醇光催化转化产生 H2：二氧化钛晶相对光氧化机理的影响

在这项研究中，我们介绍了乙二醇作为一种模型化合物在铂化二氧化钛上进行光转化产生 H2 的机理，并特别关注二氧化钛多晶体的影响。研究发现，铂/金红石和铂/金红石：金红石（P25）具有相似的 H2 生成活性，两种催化剂都遵循间接氧化途径，即乙二醇通过羟基自由基氧化成乙二醇醛。相比之下，Pt/rutile 主要是将乙二醇直接氧化成甲醛。尽管乙二醇的转化率与所使用的其他支持物相似，但甲醛无法进一步反应，这大大减少了氢气的形成。我们认为，这些差异是由于不同二氧化钛晶相上的吸附行为和空穴传输机制不同造成的。特别是，乙二醇在金红石主要（110）面上的 Ti5c 位点上的络合导致了直接的空穴传输，而氧化 C-C 裂解机制则占主导地位。

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

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.