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⁻⁶ 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（CMP）对小芳族硫化合物的吸附脱硫的计算研究。R ^-6增强的密度泛函紧密结合方法分散校正用于研究CMP-芳族硫配合物的物理吸附结合机理和电子性能。我们表明，在CMP骨架中广泛扩展的π共轭通过π–π，H–π和S–π相互作用有利于芳香族噻吩和二苯并噻吩的非共价吸附。对于CMP-噻吩/二苯并噻吩系统，平均结合能经计算为-6.2〜-15.2kcal / mol。对于具有更大尺寸和更广泛共轭作用的二苯并噻吩分子，它与CMP的结合力是噻吩分子的两倍以上。我们表明，将喹啉单元替换为网络连接器中的亚苯基可有效地将平均结合能力提高约0.8-1.8 kcal / mol。我们的计算从理论上证明了CMPs材料是小芳族硫化合物吸附脱硫的一种有前途的候选材料。本文为吸附型脱硫用新型碳基吸附剂的设计提供了有用的理论指导。