三水铝石矿物颗粒表面吸附芳香族污染物的计算模拟与预测  

Computational simulation and prediction for adsorption of aromatic pollutants on gibbsite mineral particle surface

作　　者：刘治山 马芳芳 徐倩 谢宏彬 LIU Zhishan;MA Fangfang;XU Qian;XIE Hongbin(School of Environmental Science and Technology,Dalian University of Technology,Dalian,116024,China)

机构地区：[1]大连理工大学环境学院,大连116024

出　　处：《环境化学》2024年第9期3021-3031,共11页Environmental Chemistry

基　　金：国家自然科学基金(22176022,22206020);中国博士后科学基金(2022M720640)资助.

摘　　要：了解芳香族污染物在矿物颗粒表面的吸附行为对于评估其大气归趋及影响具有重要意义.吸附能(E_(ads))是描述芳香族污染物在矿物颗粒表面吸附行为的重要参数,然而,目前该数据十分匮乏.考虑到大气中存在大量的芳香族污染物,逐个揭示芳香族污染物在矿物颗粒表面的E_(ads)值需要巨大的计算资源和工作量.因此,亟需建立一种能够快速预测芳香族污染物在矿物颗粒表面E_(ads)值的预测模型.本研究采取第一性原理的方法,探究了21个芳香族污染物在矿物颗粒三水铝石(001)面上的吸附机制.结果发现,21个芳香族污染物与三水铝石(001)面主要形成氢键、O—H…π键以及O—H…X(X=Cl/Br)相互作用,其E_(ads)值的范围在-12 kcal·mol^(-1)至-30 kcal·mol^(-1)之间.基于计算得到的21个E_(ads)值,采用多元线性回归分析方法,建立了预测芳香族污染物在三水铝石(001)面上E_(ads)值的定量结构-活性关系模型.该模型具有很好的拟合优度、稳健性和预测能力,能够用来预测含有—CH_(3)、—OH、—COOH、—NO_(2)、—NH_(2)、—CHO、—F、—Cl、—Br官能团的芳香族污染物.本研究结果对于提高目前对芳香族污染物在矿物颗粒表面上吸附行为的理解具有重要意义,并且为进一步揭示芳香族污染物在三水铝石(001)面上的大气转化奠定了基础.Understanding the adsorption behavior of aromatic pollutants on the surface of mineral particles is significant for evaluating their atmospheric fate and impacts.The adsorption energy(E_(ads))is a crucial parameter to describe the adsorption behavior of aromatic pollutants on the surface of mineral particles.However,only limited aromatic pollutants(i.e.,naphthalene,anthracene,toluene,phenol,et al.)have so far been studied.In view of the large amounts of aromatic pollutants in the atmosphere,it takes lots of work to evaluate the E_(ads) values of aromatic pollutants on the surface of mineral particles one by one.Therefore,it is necessary to establish a high-throughput prediction model to predict the E_(ads) values of aromatic pollutants on the surface of mineral particles.Herein,we employed first-principles calculations to investigate the adsorption mechanism of 21 aromatic pollutants on gibbsite(001)surface.Results indicated that three types of interactions including hydrogen bonds,O—H…πbonds and O—H…X(X=Cl/Br)are formed between 21 aromatic pollutants and gibbsite(001)surface.The calculated E_(ads) values are in the range of-12—-30 kcal·mol^(-1).Based on the calculated 21 E_(ads) values,a quantitative structure-activity relationship(QSAR)model for predicting the E_(ads) values of aromatic pollutants on gibbsite(001)surface was established.The model has good goodness of fit,robustness and predictive ability,which can be used to predict the E_(ads) values of aromatic pollutants containing—CH_(3),—OH,—COOH,—NO_(2),—NH_(2),—CHO,—F,—Cl and—Br functional groups.The results expand current understanding of the adsorption mechanism of aromatic pollutants on the surface of mineral particles,and provide a foundation for investigating the atmospheric transformation of aromatic pollutants on gibbsite(001)surface in the further.

关 键 词：芳香族污染物 三水铝石 吸附能 第一性原理计算 定量结构-活性关系 

分 类 号：X-1[环境科学与工程] O6[理学—化学]