DFT study of non-covalent interaction mechanisms of solvents with GO surfaces and the solvent-mediated GO interaction
DFT study of non-covalent interaction mechanisms of solvents with GO surfaces and the solvent-mediated GO interaction
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溶剂与GO表面非共价相互作用机制以及溶剂介导的GO相互作用的DFT研究
DOI：
10.1016/j.apsusc.2019.143926
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发表时间：
2020-01-01
影响因子：
6.7
通讯作者：
Yang, Xiaoning
中科院分区：
文献类型：
--
作者：
Miao, Shuanshuan;Xu, Zhijun;Yang, Xiaoning
了解溶剂与氧化石墨烯之间的非共价相互作用对氧化石墨烯的应用具有重要意义。本文利用密度泛函理论研究了几种典型溶剂与氧化石墨烯表面的吸附相互作用，其中包括非（非）极性、质子极性和非质子极性溶剂。对其相互作用能、几何特性和成键性质进行了表征。原子-分子理论和化学价分析的自然轨道表明，溶剂分子与氧化石墨烯表面之间存在多种非共价相互作用机制，包括从非（低）极性溶剂的vdW （pi-pi）相互作用到极性溶剂的中等和强氢键相互作用的变化。相互作用能与界面电子密度拓扑参数之间存在近似线性相关关系。轨道相互作用机理和电荷转移性能也得到了揭示。我们进一步尝试建立溶剂中GO-GO相互作用自由能与溶剂- go相互作用之间的相关性，说明溶剂- go相互作用的增加可以减弱溶剂介质中GO-GO的聚集程度。我们的模拟结果不仅对氧化石墨烯的溶剂相处理有价值，而且提供了氧化石墨烯表面上新的结合机制，为氧化石墨烯纳米材料的功能改性奠定了基础。
Understanding the non-covalent interaction between solvent and graphene oxide (GO) is of significance to the application of GOs. Herein, the adsorption interactions of several typical solvents with GO surfaces were studied by density functional theory, in which non(less)-polar, protic polar, and aprotic polar solvents were included. The interaction energies, geometrical characteristics, and bonding natures have been characterized. The atomsin-molecule theory and the natural orbitals for chemical valence analysis reveal that miscellaneous non-covalent interaction mechanisms appear between solvent molecules and GO surfaces, covering a change from vdW (pi-pi) interaction for non(less)-polar solvents to moderate and strong hydrogen bonding interactions for polar solvents. There exists an approximately linear correlation between the interaction energies and the interfacial electron density topological parameters. The orbital interaction mechanisms and charge transfer performances have also been disclosed. We further attempt to establish a correlation between the GO-GO interaction free energies in solvents and the solvent-GO interactions, which illustrates that increasing the solvent-GO interaction can weaken the aggregative degree of GOs in the solvent media. Our simulation results not only are valuable to the solventphase processing of GOs, but also provide new binding mechanisms on GO surfaces, which lays a foundation on the functional modification of GO nanomaterials.