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单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,2016/4/4,#,金,属,-,有机骨架材料（,MOF,）的分类,及其在计算化学的发展和,前景,李鹏,李芳,2024/10/5,Content,A.,常见的金属,-,有机骨架材料分类及其特点,B.MOF,材料的计算化学研究方法及应用,C.MOF,材料应用的前景,A,.,常,见的金属,-,有机骨架材料分类,a.IRMOF,系列材料,(Isoreticular Metal-Organic Framework),b.ZIF,系列材料,(Zeolitic imidazolate framework),c.CPL,系列材料,(Coordination Pillared-Layer),d.MIL,系列材料,(Materials of Institut Lavoisier),e.PCN,系列材料,(Porous Coordination Network),f.UiO,系列材料,(University of Oslo),通,过使用含更长的二羧酸配体反应物，,IRMOF,系列化合物的孔道尺寸可以增大到,28.8,，孔隙率从,55.8%,增大到,91.1%,，大大超过了沸石的孔隙率。,IRMOF,材料,用于合成,IRMOF,系列材料的不同配体,IRMOF,是由分离的次级结构单元,Zn,4,O,6+,无机基团与一系列芳香羧酸配体，以八面体形式桥连自组装而成的微孔晶体材料。,Mohamed,Eddaoudi,Jaheon Kim,Nathaniel,Rosi,David,Vodak,Joseph Wachter,Michael,OKeeffe,Omar,M.,Yaghi*.,Systematic Design of Pore,Size and,Functionality in,Isoreticular MOFs,and Their Application,in Methane,Storage.,Science,2003,300,1127,ZIF,材料,ZIF,，即类沸石咪唑酯骨架材料，是利用,Zn(),或,Co(),与咪唑配体反应，合成出的类沸石结构的,MOF,材料。,Bo,Wang,Adrien P.Co,te,Hiroyasu,Furukawa,Michael OKeeffe&,Omar M.,Yaghi.Nature,2008,(453)207.,ANH PHAN,CHRISTIAN J.,DOONAN,FERNANDO,J.URIBE-ROMO,CAROLYN B.,KNOBLER,MICHAEL,OKEEFFE,AND OMAR M.YAGHI,*.,ACCOUNTS OF CHEMICAL,RESEARCH.2010(43).58-67.,CPL,系列材料,CPL,材料的结构由六配位金属元素与中性的含氮杂环类的,2,2-,联吡啶、,4,4-,联吡啶、苯酚等配体配位而成。,其,中的四个配位位置是金属和吡嗪类羧酸配体链接而成的二维平面结构，剩下的两个位置是金属与线形二齿有机配体配位形成。,Angew.Chem.Int.Ed.1999,38,No.,1-2,140-143,Angew.Chem.,Int.Ed.2008,120,3978,3982,MIL,系列材料,MIL,材料是使用不同的过渡金属元素和琥珀酸、戊二酸等二羧酸配体合成。,其最大的一个特点就是在外界因素的刺激下，材料结构会在大孔和窄孔两种形态之间转变，即呼吸现象。,PCN,材料,PCN,系列材料含有多个立方八面体纳米孔笼，并在空间上形成孔笼,-,孔道状拓扑结构。这种材料在气体存储方面有巨大潜力。,J.AM.CHEM.SOC.2008,130,1012-1016,UiO,系列材料,UiO,材料由含,Zr,（锆）的正八面体,Zr,6,O,4,(OH),4,与,12,个对苯二甲酸,(BDC),有机配体相连，形成包含八面体中心孔笼和八个四面体角笼的三维微孔结构。,J.AM.CHEM.SOC.2008,130,1385013851,Chem.Commun.,2011,47,96039605,B.MOF,材料的计算化学研究方,法,及应用,量子力学方法,分子模拟方法,分子力学方法,第一性原理方法、密度泛函理论,蒙特卡罗方法、分子动力学方法,Experimental,Computational,combination,The,methane molecule using,the Transferable,Potentials for Phase Equilibria United,Atom(TraPPE-UA,)force field,in which CH4 is modeled as,a single,uncharged LJ sphere located on the carbon atom.,For the,ZIF atoms,we use LJ parameters taken from the,Optimized Potentials,for Liquid Simulations All Atom(OPLS-AA),force field,UFF for Zn.,GCMC Complex,Chemical,Systems(MCCCS)Towhee program,.,Binding energies,Large-scale Atomic/Molecular Massively Parallel,Simulator,(LAMMPS),J.Phys.Chem.C 2013,117,1032610335,The,corresponding,isotherms from,the,GCMC simulation,which agree with,experimentally measured,values to within 13%,validating our chosen,OPLS parameters,for these systems,.,The,CH4,adsorptions:,ZIF-71,-97 -93 -96,ZIF-8 ZIF8_55CH4UC,ZIF8_ja3,Adsorption sites,At 1,bar and,77 K,a little amount of H,2,molecules are adsorbed on,ZIF-8 framework,and their preferential adsorption sites are close,to the,imidazole rings.With increasing of gas pressure,more,H,2,molecules,are adsorbed in the middle of the faces of,the,accessible surface area of ZIF-8 framework.,The,CH,4,adsorption,isotherms for four different initial structures of,ZIF-8,at 298 K have been computed using GCMC simulations,with the,proposed force,field adsorption,isotherms for four gases such as CH,4,H,2,CO,2,and,N,2,at different temperatures were computed using,GCMC simulation,and were found to be in a good agreement with,the experimental,data,.,In,the case of H,2,the probability,density distribution profiles,indicate that the preferential,adsorption,sites,of H,2,molecules in ZIF-8 are located close to the,MeIM,rings,where the hostguest VDW interactions are maximal,as revealed,by the potential energy surfaces(PES,).,Conclusions,MOF,材料模拟的,前景,在氢储领域的应用,在气体吸附与分离领域的应用,在催化反应中的应用,在药物缓释方面的应用,
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