Ce0.875Zr0.125O2 (110) 表面的甲苯催化氧化机制

IF 3.8 3区 化学 Q2 CHEMISTRY, PHYSICAL
Catalysts Pub Date : 2023-12-27 DOI:10.3390/catal14010022
Yuning Leng, X. Cao, Xiaomin Sun, Chenxi Zhang
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引用次数: 0

摘要

芳香族挥发性有机化合物(VOCs)对公众健康有毒,并造成全球空气污染;因此,控制 VOC 排放迫在眉睫。催化氧化技术已被广泛研究用于消除芳香族挥发性有机化合物;该技术即使在低温条件下也具有很高的催化效率。然而,芳香族 VOC 在金属氧化物催化剂上的全氧化反应机理尚不清楚,这对催化剂的设计具有重要意义。本研究利用密度泛函理论(DFT)系统计算了甲苯在 Ce0.875Zr0.125O2 催化剂上的催化氧化机理。结果表明,甲苯首先通过氧脱氢从甲基失去氢,然后在晶格或吸附氧的作用下,按照 Mars-van Krevelen(MVK)机理逐渐氧化成苯甲醇、苯甲醛和苯甲酸。然后,经过脱羧步骤生成苯基,再进一步氧化为苯醌。决定速率的步骤随后通过开环反应进行,形成小分子中间产物,最后氧化成 CO2 和 H2O。这项研究可从原子尺度深入了解晶格和吸附氧在催化氧化反应中的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Catalytic Oxidation Mechanism of Toluene on the Ce0.875Zr0.125O2 (110) Surface
Aromatic volatile organic compounds (VOCs) are toxic to public health and contribute to global air pollution; thus, it is urgent to control VOC emissions. Catalytic oxidation technology has been widely investigated to eliminate aromatic VOCs; this technology exhibits high catalytic efficiency even at low temperatures. However, the reaction mechanism of aromatic VOCs’ total oxidation over metal-oxide-based catalysts, which is of great significance in the design of catalysts, is not yet clear. In this study, we systemically calculated the catalytic oxidation mechanism of toluene over the Ce0.875Zr0.125O2 catalyst using density functional theory (DFT). The results show that toluene first loses hydrogen from the methyl group via oxy-dehydrogenation and is gradually oxidized by lattice or adsorbed oxygen to benzyl alcohol, benzaldehyde, and benzoic acid following the Mars-van Krevelen (MVK) mechanism. Afterwards, there is a decarboxylation step to produce phenyl, which is further oxidized to benzoquinone. The rate-determining step then proceeds via the ring-opening reaction, leading to the formation of small molecule intermediates, which are finally oxidized to CO2 and H2O. This work may provide atomic-scale insight into the role of lattice and adsorbed oxygen in catalytic oxidation reactions.
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来源期刊
Catalysts
Catalysts CHEMISTRY, PHYSICAL-
CiteScore
6.80
自引率
7.70%
发文量
1330
审稿时长
3 months
期刊介绍: Catalysts (ISSN 2073-4344) is an international open access journal of catalysts and catalyzed reactions. Catalysts publishes reviews, regular research papers (articles) and short communications. Our aim is to encourage scientists to publish their experimental and theoretical results in as much detail as possible. Therefore, there is no restriction on the length of the papers. The full experimental details must be provided so that the results can be reproduced.
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