CH4,CO2和H2O在非金属原子修饰石墨烯表面的吸附_刘晓强.docxVIP

物理化学学报(Wuli Huaxue Xuebao)FebruaryActa Phys. -Chim. Sin. 2014, 30 (2), 251-256251[Article]doi: 10.3866/PKU.WHXB201312243CH4, CO2 和H2O 在非金属原子修饰石墨烯表面的吸附刘晓强1田之悦1储 伟2薛 英1,*(1 四川大学化学学院, 教育部绿色化学与技术重点实验室, 成都 610064;2 四川大学化学工程学院, 成都 610065)摘要: 煤层气(矿井瓦斯)是一种有望替代传统化石燃料, 如煤、石油和天然气的非常规气体. 作为可得的清洁 能源, 它的利用被认为是节能和经济的选择. 在本工作中, 非金属原子X (X=H, O, N, S, P, Si, F, Cl)修饰的石墨 烯(Gr)被用来代表具有结构异性的煤表面模型. 通过密度泛函理论系统地研究了煤层气组分Y (Y=CH4, CO2, H2O)在非金属原子修饰石墨烯上的吸附作用. 结果表明Y 在非金属原子修饰石墨烯上的吸附均为物理吸附. 态 密度和差分电荷密度共同表明了这种弱的相互作用. 其中, H 和Cl 对CH4 的作用较大; N、O、F、Cl 对CO2 的作用 较强; N, Cl 对H2O 的影响不容忽视. 总的来说, 吸附能大小依次为: H2OCO2CH4. 因此, 在CH4 富集的煤层里 注入H2O 或CO2 可以与CH4 形成竞争吸附, 进而提高煤层气采收率. 本工作提供了在分子水平下煤层气与非金 属原子修饰石墨烯之间的相互作用的详情, 并为煤层瓦斯的开采与分离提供了有用的信息.关键词: 密度泛函理论; 煤层气; 非金属原子修饰的石墨烯; 吸附中图分类号: O641CH4, CO2 and H2O Adsorption on Nonmetallic Atom-Decorated Graphene SurfacesLIU Xiao-Qiang1TIAN Zhi-Yue1CHU Wei2XUE Ying1,*(1Key Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China; 2College of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China)Abstract: As an unconventional gas, coalbed methane (CBM) is a desirable alternative energy source to conventional fossil fuels such as coal, oil, and natural gas. In this work, non-metallic atom X (X=H, O, N, S, P, Si, F, or Cl)- decorated Gr (graphene) (X-Gr) was used to represent the surface models of coal with structural heterogeneity. Using density functional theory, the adsorption of the CBM component Y (Y=CH4, CO2, H2O) on X-Gr was systematically investigated. The results indicate that CH4, CO2, and H2O are weakly bound to X-Gr, and the interactions between the adsorbate and the surface can be described as physisorption, which was identified through the density of states and electronic density difference analysis. Furthermore, CH4 has very large adsorption energies to H- and Cl- decorated graphene. The dopants X, such as N, O, F, and Cl, are very good adsorbents for CO2 and the influe