Density functional theory of molecular and dissociative adsorption of hydrogen on supported palladium clusters

doi:10.11949/j.issn.0438-1157.20160910

Abstract

Abstract:

Molecular and dissociative adsorption of hydrogen at Pd_N clusters (N=1, 4, 8, 13) supported on AlOOH and ZrO₂ were investigated using density functional theory. Effects of cluster size and carrier were assessed through study of hydrogen adsorption energies and electron transfers among carrier, Pd_N cluster and adsorbed hydrogen. Molecular adsorption occurred preferentially at atop sites of the supported Pd_N clusters while dissociative adsorption favored face sites. With the increase of cluster size, both molecular and dissociative adsorption energies decreased as well as both amount and direction of electron transfer among carrier, Pd_N clusters and adsorbed hydrogen altered. The molecular and dissociative adsorption energies on ZrO₂ supported Pd_N clusters were higher than those on AlOOH supported Pd_N clusters, indicating that carrier was also important to hydrogen adsorption.

Key words: adsorption, multiphase reaction, molecular simulation, hydrogen dissociation, Pd catalysts

摘要：

基于密度泛函理论考察勃姆石（AlOOH）和氧化锆（ZrO₂）负载的钯团簇表面氢分子吸附和解离吸附过程，通过分析一系列不同尺寸的钯团簇上氢吸附能以及氢分子-钯团簇-载体三者之间的电荷转移系统地研究了粒径效应和载体效应。结果表明，顶点位和面位分别是分子吸附和解离吸附的最佳吸附位置。随着钯团簇粒径的上升，氢分子吸附能和解离吸附能都下降，载体-钯团簇-被吸附氢三者之间的电荷转移量和方向也改变。氧化锆载体负载的钯团簇上分子吸附能和解离吸附能均大于勃姆石载体负载的钯团簇，说明载体对氢分子吸附过程有重要影响。

关键词: 吸附, 多相反应, 分子模拟, 氢解离, 钯催化剂

CLC Number:

O641

ZHANG Chi, CHENG Hongye, CHEN Lifang, QI Zhiwen. Density functional theory of molecular and dissociative adsorption of hydrogen on supported palladium clusters[J]. CIESC Journal, 2017, 68(2): 694-701.

张弛, 成洪业, 陈立芳, 漆志文. 负载型钯团簇上氢分子吸附和解离吸附的密度泛函理论[J]. 化工学报, 2017, 68(2): 694-701.

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