金屬-有機骨架材料(MOF)的分類課件

1、金屬-有機骨架材料（MOF）的分類及其在計算化學(xué)的發(fā)展和前景李鵬 李芳2022/10/15ContentA.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(Universi

2、ty of Oslo)通過使用含更長的二羧酸配體反應(yīng)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(jié)構(gòu)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 Design of Pore S

3、ize 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(yīng)，合成出的類沸石結(jié)構(gòu)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,FERNAN

4、DO J. URIBE-ROMO, CAROLYN B. KNOBLER,MICHAEL OKEEFFE, AND OMAR M. YAGHI*. ACCOUNTS OF CHEMICAL RESEARCH. 2010(43).58-67.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(jié)構(gòu)會在大孔和窄孔兩種形態(tài)之間轉(zhuǎn)變，即呼吸現(xiàn)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(jié)構(gòu)。這種材料在氣體存儲方面有巨大潛力。J. AM. CHEM. SOC. 2008, 130, 101

5、2-1016B.MOF材料的計算化學(xué)研究方法及應(yīng)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(xué)方法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

6、 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, 10326

7、10335The 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_ja3Adsorption sitesAt 1 bar and 77 K, a little amount of H

8、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 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 di

9、fferent 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