Su Lihao, Wang Ya, Wang Zhongyu, Zhang Siyu, Xiao Zijun, Xia Deming, Chen Jingwen
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), Dalian Key Laboratory on Chemicals Risk Control and Pollution Prevention Technology, School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China.
Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, China.
Nanomaterials (Basel). 2022 Feb 9;12(4):590. doi: 10.3390/nano12040590.
Layered black phosphorus (BP) has exhibited exciting application prospects in diverse fields. Adsorption of organics onto BP may influence environmental behavior and toxicities of both organic pollutants and BP nanomaterials. However, contributions of various intermolecular interactions to the adsorption remain unclear, and values of adsorption parameters such as adsorption energies () and adsorption equilibrium constants () are lacking. Herein, molecular dynamic (MD) and density functional theory (DFT) was adopted to calculate and values. The calculated and values for organics adsorbed onto graphene were compared with experimental ones, so as to confirm the reliability of the calculation methods. Polyparameter linear free energy relationship (pp-LFER) models on and log were developed to estimate contributions of different intermolecular interactions to the adsorption. The adsorption in the gaseous phase was found to be more favorable than in the aqueous phase, as the adsorbates need to overcome cohesive energies of water molecules onto BP. The affinity of the aromatics to BP was comparable to that of graphene. The pp-LFER models performed well for predicting the and values, with external explained variance ranging from 0.90 to 0.97, and can serve as effective tools to rank adsorption capacities of organics onto BP.
层状黑磷（BP）在多个领域展现出了令人兴奋的应用前景。有机物在BP上的吸附可能会影响有机污染物和BP纳米材料的环境行为及毒性。然而，各种分子间相互作用对吸附的贡献仍不明确，且缺乏吸附能（）和吸附平衡常数（）等吸附参数的值。在此，采用分子动力学（MD）和密度泛函理论（DFT）来计算和值。将计算得到的有机物在石墨烯上的吸附和值与实验值进行比较，以确认计算方法的可靠性。建立了关于和log的多参数线性自由能关系（pp-LFER）模型，以评估不同分子间相互作用对吸附的贡献。发现气相中的吸附比水相中更有利，因为吸附质需要克服水分子在BP上的内聚能。芳烃对BP的亲和力与对石墨烯的相当。pp-LFER模型在预测和值方面表现良好，外部解释方差范围为0.90至0.97，可作为有效工具对有机物在BP上的吸附能力进行排序。
