金屬-有機骨架材料(MOF)的分類ppt課件

1、金屬-有機骨架材料（MOF）的分類 及其在計算化學的發(fā)展和前景,李鵬 李芳,2021/2/1,Content,A.常見的金屬-有機骨架材料分類,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

2、(University of Oslo,通過使用含更長的二羧酸配體反應物，IRMOF系列化合物的孔道尺寸可以增大到28.8，孔隙率從55.8%增大到91.1%，大大超過了沸石的孔隙率,IRMOF材料,用于合成IRMOF系列材料的不同配體,IRMOF是由分離的次級結構單元Zn4O6+無機基團與一系列芳香羧酸配體，以八面體形式橋連自組裝而成的微孔晶體材料,Mohamed Eddaoudi, Jaheon Kim, Nathaniel Rosi,David Vodak, Joseph Wachter, Michael OKeeffe, Omar M. Yaghi*. Systematic Desig

3、n of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage. Science, 2003, 300, 1127,ZIF材料,ZIF，即類沸石咪唑酯骨架材料，是利用Zn()或Co()與咪唑配體反應，合成出的類沸石結構的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材料的結構由六配位金屬元素與中性的含氮雜環(huán)類的2,2-聯吡啶、4,4-聯吡啶、苯酚等配體配位而成。其中的四個配位位置是金屬和吡嗪類羧酸配體鏈接而成的二維平面結構，剩下的兩個位置是金屬與線形二齒有機配體配位形成,Angew. Chem. Int. Ed. 1999, 38, No. 1-2,140-143 An

5、gew. Chem. Int. Ed. 2008, 120, 3978 3982,MIL系列材料,MIL材料是使用不同的過渡金屬元素和琥珀酸、戊二酸等二羧酸配體合成。 其最大的一個特點就是在外界因素的刺激下，材料結構會在大孔和窄孔兩種形態(tài)之間轉變，即呼吸現象,PCN材料,PCN系列材料含有多個立方八面體納米孔籠，并在空間上形成孔籠-孔道狀拓撲結構。這種材料在氣體存儲方面有巨大潛力,J. AM. CHEM. SOC. 2008, 130, 1012-1016,UiO系列材料,UiO材料由含Zr（鋯）的正八面體Zr6O4(OH)4與12個對苯二甲酸(BDC)有機配體相連，形成包含八面體中心孔籠和八

6、個四面體角籠的三維微孔結構,J. AM. CHEM. SOC. 2008, 130, 1385013851 Chem. Commun., 2011,47, 96039605,B.MOF材料的計算化學研究方法及應用,第一性原理方法、密度泛函理論,蒙特卡羅方法、分子動力學方法,ExperimentalComputational combination,The methane molecule using the Transferable Potentials for Phase Equilibria United Atom (TraPPE-UA) force field, in which CH4

7、 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 -93

9、-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,低壓 高壓,RSC Adv., 2014, 4, 16503,GCMC simulation methods,Program: Multipurpose Simulation Code (MuSiC-4.0)

10、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: 1.4nm Long-range electrostatic interactions: Ewald method Steps: 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

12、 ZIF8_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 acces

13、sible 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 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 molec