【作者】 陈毅飞； 袁月； 王文毅； 张敏华；

【Author】 Chen Yifei;Yuan Yue;Wang Wenyi;Zhang Minhua;Key Laboratory for Green Synthesis and Conversion of China Education Department,R&D Center for Petrochemical Technology,Tianjin University;Collaborative Innovation Center of Chemical Science and Engineering;

【机构】 天津大学石油化工技术开发中心绿色合成与转化教育部重点实验室； 天津化学化工协同创新中心；

【摘要】 基于密度泛函理论(DFT),采用量子化学的计算方法,研究了甲烷部分氧化反应制合成气过程中镍基催化剂表面C物种生长到C6物种的可能反应路径,通过计算得到了每步反应的活化能以及其空间构型数据。计算结果表明,CH物种解离后生成的C物种,逐个累积生长成为C2、C3、C4、C5物种,最终形成结果为石墨六碳环物种。与C物种逐个累积过程中C4和C6物种的生成相比,C2和C2物种直接结合生成C4、C3和C3物种直接结合生成C6物种的活化能比较大。更多还原

【Abstract】 Quantum chemical calculation based on density functional theory(DFT) has been used for Ni catalyst which is used in the partial oxidation of methane to syngas. The possible reactions from C species to C6 species on Ni(111) surface were studied. The data on activity energy and spatial configurations of adsorbed Cx species on Ni(111) surface were calculated. The results indicated that the graphite formation could start from the dissociation of CH species, then C species were accumulatively growing up to C2, C3,C4, C5 species and finally the cyclic C6 species steps wise. Because the activation energy barriers of C2+C2→C4 and C3+C3→C6reactions were slightly higher than those of C4 and C6 species formation through the accumulative growth route, the latter two reactions might also take place during POM process.更多还原