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1、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,2022/11/25,Content,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(Uni
2、versity 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
3、 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. Cote, Hiroyasu Furukawa, Michael OKeeffe& Omar M. Yaghi. Nature, 2008,(453)207.ANH PHAN, CHRISTIAN J.
4、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. 1-2,140-143An
5、gew. 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
6、八个四面体角笼的三维微孔结构。,J. AM. CHEM. SOC. 2008, 130, 1385013851Chem. Commun., 2011,47, 96039605,B.MOF材料的计算化学研究方法及应用,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,ExperimentalComputational combination,The methane molecule using the Transferable Potentials for Phase Equilibria United Atom (TraPPE-UA) force field, in which CH
7、4 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 At
8、omic/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 -9
9、3 -96 -25. These results suggest that the dominant influence on adsorption of CH4 in the ZIFs is BET surface area or free volume, consistent with results obtained by the Snurr group and Wang et al.,低压 高压,RSC Adv., 2014, 4, 16503,GCMC simulation methods,Program: Multipurpose Simulation Code (MuSiC-4.
10、0) developed by the Snurr group.Interconversion of fugacity and pressure: PengRobinson equation of state (PREOS).Model: ZIF-8 frameworks were treated as rigid with frozen atom, H2 and CH4 were represented by a united atom model, N2 and CO2 were mimicked as a three-site rigid model.Cutoff radius of L
11、J interactions: 1.4nmLong-range electrostatic interactions: Ewald methodSteps: 107, 50% for equilibration, 50% for calculating the ensemble averages.Force field parameters: =0.635UFF and =1.0UFF,Force field validation,The effect of structure on the excess CH4 uptake follows the order ZIF8HL ZIF-8 ZI
12、F8_55CH4UC ZIF8_ja3,Adsorption sites,At 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 accessib
13、le surface area of ZIF-8 framework.,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 usi
14、ng 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).,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,
