不同硫组分在菱锌矿表面吸附的计算研究
|
摘要
采用量子化学计算的第一性原理模拟了不同硫组分在菱锌矿(001)解离面上的吸附,研究了硫组分在菱锌矿表面的吸附机理。吸附能计算结果显示:相比HS-,S2-在菱锌矿(001)解离面的吸附更加稳定,吸附能的绝对值更大,同时发现硫组分主要吸附在Zn位上;吸附前后的态密度对比分析表明,硫组分在菱锌矿表面的吸附形成了新的Zn—S化学键;布居分析发现:硫组分吸附在菱锌矿表面新形成Zn—S键的过程中,Zn、S之间发生了明显的电荷转移。研究结果阐释了菱锌矿的硫化机理,为菱锌矿硫化浮选研究提供了理论依据。
The first principle of quantum chemical calculation is used to simulate the adsorption of different sulfur components on the dissociation surface of smithsonite(001).The adsorption mechanism of sulfur components on the surface of smithsonite is studied.The calculation results of adsorption energy show that the adsorption of S2-on smithsonite(001)surface is more stable than that of HS-adsorption,and the absolute value of the adsorption energy is larger.The sulfur components are mainly adsorbed on the Zn site.The comparison of density of states before and after adsorption shows that the adsorption of sulfur components on the surface of the smithsonite forms a new Zn-S chemical bond.The Mulliken population analysis shows that the sulfur component is adsorbed on the surface of the smithsonite to form a new Zn-S bond,and the charge is mainly transferred from Zn to S.The research results illustrate the vulcanization mechanism of the smithsonite and provide a theoretical basis for the research of the vulcanization flotation of the smithsonite.
The first principle of quantum chemical calculation is used to simulate the adsorption of different sulfur components on the dissociation surface of smithsonite(001).The adsorption mechanism of sulfur components on the surface of smithsonite is studied.The calculation results of adsorption energy show that the adsorption of S2-on smithsonite(001)surface is more stable than that of HS-adsorption,and the absolute value of the adsorption energy is larger.The sulfur components are mainly adsorbed on the Zn site.The comparison of density of states before and after adsorption shows that the adsorption of sulfur components on the surface of the smithsonite forms a new Zn-S chemical bond.The Mulliken population analysis shows that the sulfur component is adsorbed on the surface of the smithsonite to form a new Zn-S bond,and the charge is mainly transferred from Zn to S.The research results illustrate the vulcanization mechanism of the smithsonite and provide a theoretical basis for the research of the vulcanization flotation of the smithsonite.
引文
[1]邓昕.全球铅锌资源概况[J].中国铅锌锡锑,2008(11):41-46.DENG Xin.Overview of global lead and zinc resources[J].China's Lead,Zinc,Tin and Antimony,2008(11):41-46.
[2]李来顺.硫化-胺法浮选菱锌矿的理论与工艺研究[D].长沙:中南大学,2013.LI Laishun.Study on the theory and technology of sulfide-amine flotation of smithsonite:[D].Changsha:Central South University,2013.
[3]戴自希,盛继福,白冶,等.世界铅锌资源的分布与潜力[M].北京:地震出版社,2005.DAI Zixi,SHENG Jifu,BAI Ye,et al.Distribution and potential of world lead and zinc resources[M].Beijing:Seismological Press,2005.
[4]李迪恩,彭明生.闪锌矿的标型特征、形成条件与电子结构[J].矿床地质,1989,8(3):77-82.LI Dian,PENG Mingsheng.Typomorphic characteristics,formation conditions and electronic structure of sphalerite[J].Deposit geology,1989,8(3):77-82.
[5]张瑞兵,李占军.铅锌矿的成矿类型及成因探讨[J].内蒙古科技与经济,2011(13):57-58.ZHANG Ruibing,LI Zhanjun.Metallogenic types and genesis of lead-zinc deposits[J].Inner Mongolia Science and Technology and Economy,2011(13):57-58.
[6]陈晔.阳离子胺类捕收剂浮选异极矿氧化锌及其作用机理研究[D].南宁:广西大学,2006.CHEN Ye.Study on flotation of zinc oxide from heteropolar ores by cationic amine collectors and its mechanism[D].Nanning:Guangxi University,2006.
[7]杨少燕.菱锌矿的浮选理论与工艺研究[D].长沙:中南大学,2010.YANG Shaoyan.Study on flotation theory and technology of smithsonite[D].Changsha:Central South University,2010.
[8]王福良.铜铅锌铁主要硫化氧化矿物浮选的基础理论研究[D].沈阳:东北大学,2008.WANG Fuliang.Basic theoretical study on flotation of copper,lead,zinc and iron sulfide oxides[D].Shenyang:Northeast University,2008.
[9]WU D,WEN S,DENG J,et al.Study on the sulfidat ion behavior of smithsonite[J].Applied Surface Science,2015,329:315-320.
[10]HAMID H S,ERIC F.XPS&FTIR study of adsorption characteristics using cationic and anionic collectors on smithsonite[J].Journal of Minerals and Materials Characterization and Engineering,2006,5(1):21-45.
[11]MARABINI A M,ALESSE V,GARBASSI F.Role of sodium sulphide,xanthate and amine in flotation of lead-zinc oxidized ores[J].Inst of Mining&Metallurgy,1984:125-136.
[12]WANG Z.Physicochemical aspects of smithsonite flotat ion[D].The University of Utah,2014.
[13]李振宇,贾瑞强,周国旭.硫化钠在矿浆中的多种化学行为[J].价值工程,2015,34(1):292-293.LI Zhenyu,JIA Ruiqiang,ZHOU Guoxu.Various chemical behaviors of sodium sulfide in pulp[J].Value Engineering,2015,34(1):292-293.
[14]LYKOS P,PRATT G W.Discussion on the HartreeFock approximation[J].Reviews of Modern Physics,1963,35(3):496.
[15]OCHKUR V I.The Born-Oppenheimer method in the theory of atomic collisions[J].Soviet Physics-JETP,1964,18(2):503-508.
[16]BECKE A D.Density-functional exchange-energy approximation with correct asymptotic behavior[J].Physical Review A,1988,38(6):3098-3100.
[17]HOHENBERG P,KOHN W.Inhomogeneous electron gas[J].Physical Review,1964,136(3B):B864-B871.
[18]KOHN W,BECKE A D,PARR R G.Density functional theory of electronic structure[J].The Journal of Physical Chemistry,1996,100(31):12974-12980.
[19]PERDEW J P,BURKE K,ERNZERHOF M.Generalized gradient approximation made simple[J].Physical Review Letters,1996,77(18):3865-3868.
[20]PERDEW J P,CHEVARY J A,VOSKO S H,et al.Atoms,molecules,solids,and surfaces:Applications of the generalized gradient approximation for exchange and correlation[J].Physical Review B,1992,46(11):6671-6687.
[21]BECKE A D.A new mixing of Hartree-Fock and local density-functional theories[J].The Journal of Chemical Physics,1993,98:1372-1377.
[22]NOVAK P,KUNES J,CHAPUT L,et al.Exact exchange for correlated electrons[J].Physica Status solidi(b),2006,243(3):563-572.
[23]PERDEW J P,WANG Y.Accurate and simple analytic representation of the electron-gas correlation energy[J].Physical Review B,1992,45(23):13244-13249.
[24]PERDEW J P,YUE W.Accurate and simple density functional for the electronic exchange energy:Generalized gradient approximation[J].Physical Review B,1986,33(12):8800-8802.
[2]李来顺.硫化-胺法浮选菱锌矿的理论与工艺研究[D].长沙:中南大学,2013.LI Laishun.Study on the theory and technology of sulfide-amine flotation of smithsonite:[D].Changsha:Central South University,2013.
[3]戴自希,盛继福,白冶,等.世界铅锌资源的分布与潜力[M].北京:地震出版社,2005.DAI Zixi,SHENG Jifu,BAI Ye,et al.Distribution and potential of world lead and zinc resources[M].Beijing:Seismological Press,2005.
[4]李迪恩,彭明生.闪锌矿的标型特征、形成条件与电子结构[J].矿床地质,1989,8(3):77-82.LI Dian,PENG Mingsheng.Typomorphic characteristics,formation conditions and electronic structure of sphalerite[J].Deposit geology,1989,8(3):77-82.
[5]张瑞兵,李占军.铅锌矿的成矿类型及成因探讨[J].内蒙古科技与经济,2011(13):57-58.ZHANG Ruibing,LI Zhanjun.Metallogenic types and genesis of lead-zinc deposits[J].Inner Mongolia Science and Technology and Economy,2011(13):57-58.
[6]陈晔.阳离子胺类捕收剂浮选异极矿氧化锌及其作用机理研究[D].南宁:广西大学,2006.CHEN Ye.Study on flotation of zinc oxide from heteropolar ores by cationic amine collectors and its mechanism[D].Nanning:Guangxi University,2006.
[7]杨少燕.菱锌矿的浮选理论与工艺研究[D].长沙:中南大学,2010.YANG Shaoyan.Study on flotation theory and technology of smithsonite[D].Changsha:Central South University,2010.
[8]王福良.铜铅锌铁主要硫化氧化矿物浮选的基础理论研究[D].沈阳:东北大学,2008.WANG Fuliang.Basic theoretical study on flotation of copper,lead,zinc and iron sulfide oxides[D].Shenyang:Northeast University,2008.
[9]WU D,WEN S,DENG J,et al.Study on the sulfidat ion behavior of smithsonite[J].Applied Surface Science,2015,329:315-320.
[10]HAMID H S,ERIC F.XPS&FTIR study of adsorption characteristics using cationic and anionic collectors on smithsonite[J].Journal of Minerals and Materials Characterization and Engineering,2006,5(1):21-45.
[11]MARABINI A M,ALESSE V,GARBASSI F.Role of sodium sulphide,xanthate and amine in flotation of lead-zinc oxidized ores[J].Inst of Mining&Metallurgy,1984:125-136.
[12]WANG Z.Physicochemical aspects of smithsonite flotat ion[D].The University of Utah,2014.
[13]李振宇,贾瑞强,周国旭.硫化钠在矿浆中的多种化学行为[J].价值工程,2015,34(1):292-293.LI Zhenyu,JIA Ruiqiang,ZHOU Guoxu.Various chemical behaviors of sodium sulfide in pulp[J].Value Engineering,2015,34(1):292-293.
[14]LYKOS P,PRATT G W.Discussion on the HartreeFock approximation[J].Reviews of Modern Physics,1963,35(3):496.
[15]OCHKUR V I.The Born-Oppenheimer method in the theory of atomic collisions[J].Soviet Physics-JETP,1964,18(2):503-508.
[16]BECKE A D.Density-functional exchange-energy approximation with correct asymptotic behavior[J].Physical Review A,1988,38(6):3098-3100.
[17]HOHENBERG P,KOHN W.Inhomogeneous electron gas[J].Physical Review,1964,136(3B):B864-B871.
[18]KOHN W,BECKE A D,PARR R G.Density functional theory of electronic structure[J].The Journal of Physical Chemistry,1996,100(31):12974-12980.
[19]PERDEW J P,BURKE K,ERNZERHOF M.Generalized gradient approximation made simple[J].Physical Review Letters,1996,77(18):3865-3868.
[20]PERDEW J P,CHEVARY J A,VOSKO S H,et al.Atoms,molecules,solids,and surfaces:Applications of the generalized gradient approximation for exchange and correlation[J].Physical Review B,1992,46(11):6671-6687.
[21]BECKE A D.A new mixing of Hartree-Fock and local density-functional theories[J].The Journal of Chemical Physics,1993,98:1372-1377.
[22]NOVAK P,KUNES J,CHAPUT L,et al.Exact exchange for correlated electrons[J].Physica Status solidi(b),2006,243(3):563-572.
[23]PERDEW J P,WANG Y.Accurate and simple analytic representation of the electron-gas correlation energy[J].Physical Review B,1992,45(23):13244-13249.
[24]PERDEW J P,YUE W.Accurate and simple density functional for the electronic exchange energy:Generalized gradient approximation[J].Physical Review B,1986,33(12):8800-8802.