Adsorption of Small Organic Molecules on Graphene
Adsorption of Small Organic Molecules on Graphene
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DOI：
10.1021/ja403162r
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发表时间：
2013-04-24
影响因子：
15
通讯作者：
Otyepka, Michal
中科院分区：
文献类型：
--
作者：
Lazar, Petr;Karlicky, Frantisek;Otyepka, Michal
我们提出了一个结合的实验和理论定量的吸附七个有机分子（丙酮，乙腈，二氯甲烷，乙醇，乙酸乙酯，己烷和甲苯）的石墨烯。通过反相气相色谱法测量吸附量，其范围为二氯甲烷的-5.9千卡/摩尔至甲苯的-13.5千卡/摩尔。石墨烯和有机分子之间的相互作用的强度通过密度泛函理论（PBE、B 97 D、M06-2X和optB 88-vdW）、波函数理论（MP2、SCS（MI）-MP2、MP2.5、MP2.X和CCSD（T））和经验计算（OPLS-AA）使用两种石墨烯模型：晕苯和无限石墨烯来估计。对称性适应微扰理论计算表明，相互作用由伦敦色散力（相当于60%的吸引力），即使是极性分子。结果还表明，吸附速率在很大程度上受相互作用能控制。采用非局部optB 88-vdW泛函从从头算分子动力学获得的吸附焓与实验数据非常一致，表明该泛函可以足够好地涵盖有机分子在石墨烯上吸附背后的物理现象。
We present a combined experimental and theoretical quantification of the adsorption enthalpies of seven organic molecules (acetone, acetonitrile, dichloromethane, ethanol, ethyl acetate, hexane, and toluene) on graphene. Adsorption enthalpies were measured by inverse gas chromatography and ranged from -5.9 kcal/mol for dichloromethane to -13.5 kcal/mol for toluene. The strength of interaction between graphene and the organic molecules was estimated by density functional theory (PBE, B97D, M06-2X, and optB88-vdW), wave function theory (MP2, SCS(MI)-MP2, MP2.5, MP2.X, and CCSD(T)), and empirical calculations (OPLS-AA) using two graphene models: coronene and infinite graphene. Symmetry-adapted perturbation theory calculations indicated that the interactions were governed by London dispersive forces (amounting to similar to 60% of attractive interactions), even for the polar molecules. The results also showed that the adsorption enthalpies were largely controlled by the interaction energy. Adsorption enthalpies obtained from ab initio molecular dynamics employing non-local, optB88-vdW functional were in excellent agreement with the experimental data, indicating that the functional can cover physical phenomena behind adsorption of organic molecules on graphene sufficiently well.