Fan Wen-Jie, Liu Na, Zhu Wei-Qiang, Mao Yin-Bu, Tan Da-Zhi
College of Marine Science and Environment Engineering, Dalian Ocean University, Dalian, 116023, People's Republic of China.
College of Marine Science and Environment Engineering, Dalian Ocean University, Dalian, 116023, People's Republic of China.
J Mol Graph Model. 2020 Dec;101:107734. doi: 10.1016/j.jmgm.2020.107734. Epub 2020 Sep 3.
This paper presents a computational study of the adsorptive desulfurization of small aromatic sulfur compounds by conjugated microporous polymers (CMPs). The density-functional tight-binding method augmented with an R dispersion correction is employed to investigate the physisorption binding mechanism and electronic properties of the CMP-aromatic sulfur complexes. We show that the widely extended π conjugation in the CMP skeletons is favorable for the non-covalent adsorption of aromatic thiophene and dibenzothiophene via π-π, H-π, and S-π interactions. The average binding energies are calculated to be -6.2 ∼ -15.2 kcal/mol for CMP- thiophene/dibenzothiophene systems. For the dibenzothiophene molecule with larger size and more extended conjugation, it binds more than twice stronger to CMP than the thiophene molecule. We show that the replacement of quinoline unit to the phenylene group in the network linker effectively enhances the average binding capacities by around 0.8-1.8 kcal/mol. Our calculations theoretically demonstrate that CMPs materials are kind of promising candidates for the adsorptive desulfurization of small aromatic sulfur compounds. This paper provides useful theoretical guidance for design of novel carbon-based adsorbents for adsorptive desulfurization.
本文介绍了共轭微孔聚合物（CMPs）对小分子芳香族含硫化合物吸附脱硫的计算研究。采用密度泛函紧束缚方法并结合R色散校正，研究了CMP-芳香族硫配合物的物理吸附结合机理和电子性质。我们表明，CMP骨架中广泛延伸的π共轭有利于通过π-π、H-π和S-π相互作用对芳香族噻吩和二苯并噻吩进行非共价吸附。计算得出CMP-噻吩/二苯并噻吩体系的平均结合能为-6.2∼-15.2 kcal/mol。对于尺寸更大、共轭延伸更长的二苯并噻吩分子，其与CMP的结合强度是噻吩分子的两倍多。我们表明用亚苯基取代网络连接体中的喹啉单元可有效提高平均结合能力约0.8-1.8 kcal/mol。我们的计算从理论上证明了CMPs材料是小分子芳香族含硫化合物吸附脱硫的一类有前景的候选材料。本文为设计用于吸附脱硫的新型碳基吸附剂提供了有用的理论指导。
