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Predicting H2S Oxidative Dehydrogenation over Graphene Oxides from First Principles
Bin Huang, Bi-bo Chen, Rong Chen
Department of Materials Science and Engineering, East China Institute of Technology, Nanchang 331000, China
Abstract:
Spin-polarized periodic density functional theory was performed to characterize H2S adsorption and dissociation on graphene oxides (GO) surface. The comprehensive reaction network of H2S oxidation with epoxy and hydroxyl groups of GO was discussed. It is shown that the reduction reaction is mainly governed by epoxide ring opening and hydroxyl hydrogenation which is initiated by H transfer from H2S or its derivatives. Furthermore, the presence of another OH group at the opposite side relative to the adsorbed H2S activates the oxygen group to facilitate epoxide ring opening and hydroxyl hydrogenation. For H2S interaction with -O and -OH groups adsorption on each side of graphene, the pathway is a favorable reaction path by the introduction of intermediate states, the predicted energy barriers are 3.2 and 10.4 kcal/mol, respectively, the second H transfer is the rate-determining step in the whole reaction process. In addition, our calculations suggest that both epoxy and hydroxyl groups can enhance the binding of S to the C-C bonds and the effect of hydroxyl group is more local than that of the epoxy.
Key words:  First principles  H2S  Adsorption  Dissociation
FundProject:
H2S在氧化石墨烯表面的吸附和分解的理论研究
黄斌, 陈碧波, 陈荣
东华理工大学材料系,南昌331000
摘要:
用周期性密度泛函方法对H2S在氧化石墨烯(GO)上的吸附和分解进行了理论计算, 讨论了H2S和GO上的羟基和环氧基团的反应过程.结果表明,反应过程是通过H2S或-SH上的H转移使得GO的环氧基开环和羟基氢化,当GO相反面存在羟基时有助于环氧基团的开环和羟基氢化反应.H2S在GO上吸附和分解到S原子的反应机理中引入了相应的中间态,计算两次脱氢过程能垒分别为3.2和10.4 kcal/mol,第二个H原子的转移是GO还原过程的速率决定步骤.结果还表明GO上的羟基和环氧基团有助于加强S原子和石墨烯的结合.
关键词:  第一性原理  H2S  吸附  分解
DOI:10.1063/1674-0068/28/cjcp1410187
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