Hydrogenation of o-cresol on platinum catalyst: Catalytic experiments and first-principles calculations

被引:27
作者
Li, Yaping [1 ]
Liu, Zhimin [2 ]
Xue, Wenhua [1 ]
Crossley, Steven P. [2 ]
Jentoft, Friederike C. [2 ,3 ]
Wang, Sanwu [1 ]
机构
[1] Univ Tulsa, Dept Phys & Engn Phys, Tulsa, OK 74104 USA
[2] Univ Oklahoma, Sch Chem Biol & Mat Engn, Norman, OK 73019 USA
[3] Univ Massachusetts, Dept Chem Engn, Amherst, MA 01003 USA
基金
美国能源部;
关键词
Hydrogenation; Cresol; Platinum catalyst; ab initio calculations; Activation energies; DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; AUGMENTED-WAVE METHOD; ELASTIC BAND METHOD; FAST PYROLYSIS; BIO-OILS; HYDRODEOXYGENATION MECHANISM; MOLECULAR-DYNAMICS; SADDLE-POINTS; CONVERSION;
D O I
10.1016/j.apsusc.2016.10.028
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Catalytic experiments were performed for the hydrogenation of o-cresol in n-dodecane over a platinum catalyst. Batch reactions analyzed with an in-situ ATR IR probe suggest that the hydrogenation results in the formation of the final product, 2-methyl-cyclohexanol, with 2-methyl-cyclohexanone as the intermediate product. Ab initio density-functional theory was employed to investigate the atomic-scale mechanism of o-cresol hydrogenation on the Pt(111) surface. The formation of 2-methyl-cyclohexanone was found to involve two steps. The first step is a hydrogen abstraction, that is, the H atom in the hydroxyl group migrates to the Pt surface. The second step is hydrogenation, that is, the pre-existing H atoms on Pt react with the carbon atoms in the aromatic ring. On the other hand, 2-methyl-cyclohexanonol may be produced through two paths, with activation energies slightly greater than that for the formation of 2-methyl-cyclohexanone. One path involves direct hydrogenation of the aromatic ring. Another path involves three steps, with the partial hydrogenation of the ring as the first step, hydrogen abstraction of the OH group as the second, and hydrogenation of remaining C atoms and the O atom the last. (C) 2016 Elsevier B.V. All rights reserved.
引用
收藏
页码:212 / 220
页数:9
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