DFT Study of VOC Pollutants Catalyzed by Optimal MoxOy: Exploration of Reaction Mechanism of CH3COOH + MoO2

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摘要 We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations. The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways (Channels I, II and III) are reported and analyzed. All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds (VOCs) in previous studies. The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time. Channels I (IA and IB) and II are both addition reactions and channel III is hydrogen abstraction reaction by producing a leaving group. The barrier energies of reaction are also compared with other catalytic reactions, showing that MoO2 catalyst expresses a lower barrier energy (8.22 kcal/mol) by addition reaction, which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances. This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids, so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.

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	高小珍
	庞雨
	杨静
	杨笑春
	沈玉龙
	贾静娴
	孟祥军

关键词 ： reaction mechanism, acetic acid elimination, molybdenum dioxide, addition reaction, hydrogen abstraction reaction

Abstract：We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations. The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways (Channels I, II and III) are reported and analyzed. All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds (VOCs) in previous studies. The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time. Channels I (IA and IB) and II are both addition reactions and channel III is hydrogen abstraction reaction by producing a leaving group. The barrier energies of reaction are also compared with other catalytic reactions, showing that MoO2 catalyst expresses a lower barrier energy (8.22 kcal/mol) by addition reaction, which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances. This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids, so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.

Key words： reaction mechanism acetic acid elimination molybdenum dioxide addition reaction hydrogen abstraction reaction

收稿日期: 2019-06-03 出版日期: 2020-05-14

基金资助:Supported by the Shanxi Provincial Education Department (2019L0986), the 2016 annual major science and technology projects of Shanxi Province (MC2016-02/5), the Shanxi Advantageous and Characteristic Disciplines of “Project 1331”, the school fund of Shanxi Institute of Technology (2016050001, 20180010012 and 20190040013), the major project of Tangshan Normal College (Nos. 2017B01 and 2017B02), and the abroad training project fund of Tangshan excellent young and middle-aged experts

通讯作者: yjlzddove@gmail.com E-mail: yjlzddove@gmail.com

引用本文:

高小珍;庞雨;杨静;杨笑春;沈玉龙;贾静娴;孟祥军. DFT Study of VOC Pollutants Catalyzed by Optimal Mo_xO_y: Exploration of Reaction Mechanism of CH3COOH + MoO₂[J]. 结构化学, 2020, 39(5): 861-872.
GAO Xiao-Zhen;PANG Yu;YANG Jing;YANG Xiao-Chun;SHEN Yu-Long;JIA Jing-Xian;MENG Xiang-Jun. DFT Study of VOC Pollutants Catalyzed by Optimal Mo_xO_y: Exploration of Reaction Mechanism of CH3COOH + MoO₂. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(5): 861-872.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2020/V39/I5/861

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