Mechanism of Dibenzofuran Hydrodeoxygenation on the Surface of Pt(111): A DFT Study
Mechanism of Dibenzofuran Hydrodeoxygenation on the Surface of Pt(111): A DFT Study
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Pt(111)表面二苯并呋喃加氢脱氧机理：DFT研究
DOI：
10.1016/j.cattod.2020.04.044
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发表时间：
2020-04
期刊：
影响因子：
5.3
通讯作者：
Wen-Ying Li
中科院分区：
文献类型：
--
作者：
Xing-Bao Wang;Zi-Zheng Xie;Liang Guo;Zhen-Yi Du;Wen-Ying Li
催化加氢脱氧是提高低温煤焦油和煤液化油质量的有效方法。然而，只有有限的研究进行加氢脱氧的机制，因此，更有效和更稳定的催化剂的创新是进展较少，仍然是一个具有挑战性的课题。本研究采用密度泛函理论计算方法对二苯并呋喃在Pt（111）表面加氢脱氧反应的机理进行了深入的研究。计算的能量和活化能表明四氢二苯并呋喃的五元环开环比六氢二苯并呋喃容易。然后，所产生的中间体可以通过非连续途径优先氢化成2-环己基苯酚，并且将产生多个自由基物质。通过向2-环己基苯酚的苯环上添加5个氢原子形成的中间体的脱羟基反应显示出1.07 eV的中等反应势垒;而环己基环己醇的脱羟基反应需要2.04 eV的更高的能垒。对于二苯并呋喃在Pt（111）表面上的加氢脱氧，目标产物双环己烷最有可能通过自由基中间体形成。该研究为设计新型煤加氢脱氧催化剂提供了有力的理论指导。
Catalytic hydrodeoxygenation is an efficient method to upgrade the quality of low-temperature coal tar and coal liquefied oil. However, only limited researches are performed on the mechanism of hydrodeoxygenation and, therefore, innovation of more efficient and stable catalysts is less progressed and still remains a challenging subject. In this study, density functional theory calculations are carried out to get a deeper insight in the mechanism of dibenzofuran hydrodeoxygenation on the Pt(111) surface. Calculated energies and activation barriers indicate that five-membered-ring opening of tetrahydrodibenzofuran is easier than that of hexahydrodibenzofuran. Then, the generated intermediate can be preferentially hydrogenated through a non-consecutive pathway to 2-cyclohexylphenol, and would result in multiple radical species. The dehydroxylation of that intermediate formed by adding five hydrogen atoms to the phenyl ring of 2-cyclohexylphenol shows a moderate reaction barrier of 1.07 eV; whereas, dehydroxylation of cyclohexylcyclohexanol needs a higher energy barrier of 2.04 eV. For the hydrodeoxygenation of dibenzofuran on the Pt(111) surface, the target product bicyclohexane is most likely to be formed through a radical intermediate. This investigation may provide a potent theoretical guidance to design new catalyst for hydrodeoxygenation of coal to liquid.
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影响因子：
5
作者：
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