济源二叠系高岭石晶体结构模型的构建与电子结构量化计算
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摘要
以济源二叠系高岭石为例,基于X射线衍射,结合分子动力学模拟的方法,在MS软件Visualizer模块下构建高岭石晶体结构模型,利用CASTEP模块进行了电子结构量化计算。研究结果表明:济源二叠系高岭石主要为三斜晶系高岭石,其空间群为C_1,化学键长度以及键角与实验值符合较好;高岭石是一种具有宽能隙的绝缘体,其上价带区主要由O的s轨道电子决定,下价带区由Al和O的p轨道电子决定,而导带区则由Al的p轨道电子和Si、H的s轨道电子决定;Al—O键比Si—O键长,在外部环境改变时,更易吸附非极性分子。
Taking Jiyuan Permian kaolinite as an example,based on the X-ray diffraction and molecular dynamics simulation,the crystal structure model of kaolinite is constructed with the MS software Visualizer module,and the electronic structure is quantized by using CASTEP module.The results show that Jiyuan Permian kaolinite is mainly triclinic crystal kaolinite and its spatial group is C_1.Kaolinite is an insulator with wide energy gap.The upper valence band is mainly determined by the s orbital electrons of O,while the lower valence band is determined by the p orbital electrons of Al and O.And the guide band is determined by the p orbital electrons of Al and the s orbital electrons of Si and H.The Al—O bond is longer than the Si—O bond.When the external environment changes,it is easier to absorb non-polar molecules.
Taking Jiyuan Permian kaolinite as an example,based on the X-ray diffraction and molecular dynamics simulation,the crystal structure model of kaolinite is constructed with the MS software Visualizer module,and the electronic structure is quantized by using CASTEP module.The results show that Jiyuan Permian kaolinite is mainly triclinic crystal kaolinite and its spatial group is C_1.Kaolinite is an insulator with wide energy gap.The upper valence band is mainly determined by the s orbital electrons of O,while the lower valence band is determined by the p orbital electrons of Al and O.And the guide band is determined by the p orbital electrons of Al and the s orbital electrons of Si and H.The Al—O bond is longer than the Si—O bond.When the external environment changes,it is easier to absorb non-polar molecules.
引文
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[17]HU Yuehua,SUN Wei,JIANG Hao,et al.The anomalous behavior of kaolinite flotation with dodecyl aminecollector as explained from crystal structure considerations[J].International Journal of Mineral Processing,2005,76:163-172.
[18]HU Y,LIU X,XU Zhenghe.Role of crystal structure in flotation separation of diasporefrom kaolinite,pyrophyllite and illite[J].Minerals Engineering,2003,16:219-227.
[19]JAWAD N.HSE functional,and GW approaches[J].Physical Review B,2011,84(7):075120.
[2]CHENG Ailing,HUANG Wuliang.Selective adsorption of hydrocarbon gases on clays and organic matter[J].Organic Geochemistry,2004,35(4):413-423.
[3]ZHANG Bin,KANG Jianting,KANG Tianhe.Monte Carlo simulations of methane adsorption on kaolinite as a function of pore size[J].Natural Gas Science and Engineering,2018,49(1):410-416.
[4]黄海帆,李希建,李维维,等.页岩中气体吸附分子模拟中宏观因素微观化[J].煤炭学报,2017,36(6):40-42.HUANG Haifan,LI Xijian,LI Weiwei,et al.Macro factor microcosm in gas adsorption molecular simulation in shale[J].Journal of Coal,2017,36(6):40-42.(in Chinese)
[5]黄美鑫,林晓英,李健,等.自由体积的校正及其对煤与泥页岩等温吸附量的影响[J].中国科技论文,2017,12(3):279-282.HUANG Meixin,LIN Xiaoying,LI Jian,et al.Calibration of free volume and its effect on isothermal adsorption content of coal and shale[J].China Science and Technology Paper,2017,12(3):279-282.(in Chinese)
[6]GRUNER J W.The crystal structure of kaolinite[J].Zeitschrift für Kristallographie-Crystalline Materials,1932,83(1):75-88.
[7]SUITCH P,YOUNG R.Atom positions in highly ordered kaolinite[J].Clays and Clay Minerals,1983,31(5):357-366.
[8]HOBBS J D,CYGAN R T,NAGY K L,et al.All-atom ab initio energy minimization of the kaolinite crystal structure[J].American Mineralogist,1997,82(7):657-662.
[9]SATO H,ONO K,JOHNSTON C T,et al.Firstprinciple study of polytype structures of 1∶1dioctahedralphyllosilicates[J].American Mineralogist,2004,89(11/12):1581-1585.
[10]熊健,刘向君,梁利喜.甲烷在黏土矿物狭缝孔中吸附的分子模拟研究[J].煤炭学报,2017,42(4):959-968.XIONG Jian,LIU Xiangjun,LIANG Lixi.Molecular simulation of the adsorption of methane in clay mineral slits by Kongzhong[J].Journal of Coal,2017,42(4):959-968.(in Chinese)
[11]田玉玺.尿素和水体系在高岭石层间插层过程的分子动力学模拟[D].北京:北京化工大学,2007.TIAN Yuxi.Molecular dynamics simulation of urea and water system intercalation process in kaolinite layer[D].Beijing:Beijing Chemical University,2007.(in Chinese)
[12]周苏阳.季铵盐与铝硅矿物的界面作用基础[D].长沙:中南大学,2011.ZHOU Suyang.The interface basis of quaternary ammonium salt and aluminum Silicon minerals[D].Changsha:Central South University,2011.(in Chinese)
[13]李海涛.黏土矿物微观结构及其弹性性质的第一性原理研究[D].太原:太原理工大学,2016.LI Haitao.Study on the first principle of the microstructure and elastic properties of clay minerals[D].Taiyuan:Taiyuan University of Technology,2016.(in Chinese)
[14]周俊杰,李文静.高岭石电子结构的量化计算[J].工业技术创新,2014,1(3):258-262.ZHOU Junjie,LI Wenjing.Quantitative calculation of the electronic structure of kaolinite[J].Industrial Technological Innovation,2014,1(3):258-262.(in Chinese)
[15]BIS H,DAVID L.Rietveld refinement of the kaolinite structure at 1.5K[J].Clays and Clay Minerals,1993,41(6):738-744
[16]TAMS Kristf,ZSFIA Sarkadi,ZOLTN Hat,et al.Simulation study of intercalation complexes of kaolinite with simpleamides as primary intercalation reagents[J].Computational Materials Science,2018,143:118-125.
[17]HU Yuehua,SUN Wei,JIANG Hao,et al.The anomalous behavior of kaolinite flotation with dodecyl aminecollector as explained from crystal structure considerations[J].International Journal of Mineral Processing,2005,76:163-172.
[18]HU Y,LIU X,XU Zhenghe.Role of crystal structure in flotation separation of diasporefrom kaolinite,pyrophyllite and illite[J].Minerals Engineering,2003,16:219-227.
[19]JAWAD N.HSE functional,and GW approaches[J].Physical Review B,2011,84(7):075120.