金属有机骨架材料(MOF)的分类.pptx

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2024/5/8 2024/5/8 周三周三1.ContentA.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2.A.常常见的金属的金属-有机骨架材料分有机骨架材料分类a.IRMOF系列材料系列材料(Isoreticular Metal-Organic Framework)b.ZIF系列材料系列材料(Zeolitic imidazolate framework)c.CPL系列材料系列材料(Coordination Pillared-Layer)d.MIL系列材料系列材料(Materials of Institut Lavoisier)e.PCN系列材料系列材料(Porous Coordination Network)f.UiO系列材料系列材料(University of Oslo)3.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Zn4O6+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,2003,300,11274.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.Cote,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).58-67.5.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.1-2,140-143Angew.Chem.Int.Ed.2008,120,3978 39826.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。7.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.2008,130,1012-10168.UiO系列材料UiO材料由含Zr（锆）的正八面体Zr6O4(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.2008,130,1385013851Chem.Commun.,2011,47,960396059.B.MOF材料的材料的计算化学研究方算化学研究方法法及及应用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10.ExperimentalComputational 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 2013,117,103261033511.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_ja317.Adsorption sitesAt 1 bar and 77 K,a little amount of H2 molecules are adsorbed on ZIF-8 framework and their preferential adsorption sites are close to the imidazole rings.With increasing of gas pressure,more H2 molecules are adsorbed in the middle of the faces of the accessible surface area of ZIF-8 framework.18.The CH4 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 CH4,H2,CO2 and N2 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 H2,the probability density distribution profiles indicate that the preferential adsorption sites of H2 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).Conclusions19.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20.21.