1、金屬-有機骨架材料（MOF）的分類及其在計算化學的發展和前景李鵬 李芳2021-10-13ContentA.常見的金屬-有機骨架材料分類及其特點B.MOF材料的計算化學研究方法及應用C.MOF材料應用的前景A.常常見的金屬見的金屬-有機骨架材料分類有機骨架材料分類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

2、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)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,D

3、avid 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, 1127ZIF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, Mi

4、chael 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材料的結構由六配位金屬元素與中性的含氮雜環類的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

5、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. 1-2,140-143Angew. Chem. Int. Ed. 2008, 120, 3978 3982MIL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, 1012-10

6、16UiO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個四面體角籠的三維微孔結構。J. AM. CHEM. SOC. 2008, 130, 1385013851Chem. Commun., 2011,47, 96039605B.MOF材料的計算化學研究方材料的計算化學研究方法法及應用及應用量子力學方法分子模擬方法分子力學方法第一性原理方法、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 t

7、he 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,

8、 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, 1032610335The corresponding isotherms from the GCMC simulation, which agree with experimentally measured values to within 13

9、%, validating our chosen OPLS parameters for these systems.The CH4 adsorptions: ZIF-71 -97 -93 -96 ZIF-8 ZIF8_55CH4UC ZIF8_ja3Adsorption 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. W

10、ith increasing of gas pressure, more H2 molecules are adsorbed in the middle of the faces of the accessible 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 ad

11、sorption 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 t