MOF材料48414.ppt

1、金属有机骨架材料（MOFs） 的后合成修饰,报告人：刘昌 2013年12月20日,2,MOFs材料简介,20世纪90年代中期，第一代MOFs材料被合成出来,孔径和稳定性受到一定限制,1999年，Yaghi等人合成具有三维开放骨架结构的MOF-5,去除孔道中的客体分子后仍然保持骨架完整,2002年，Yaghi科研组合成IRMOF系列材料,实现MOF材料从微孔到介孔的成功过渡,2008年，Yaghi研究组合成出上百种ZIF系列类分子筛材料,金属离子,有机配体,配位,自组装,周期性网状骨架的多孔材料,MOFs,合成方法,特点,应用,分类,Eddaoudi, M. Kim, J. Rosi, N. V

2、odak, D. OKeeffe, M. Yaghi, O. M. science 295, 469-472 (2002),The choice of metal ions and organic ligand can dictate the framework topology (affecting pore and shape) and influence the overall chemical functionality of the framework.,Kyo Sung Park, Zheng Ni, Adrien P. PNAS 2006;103;10186-10191,IRMO

3、F-3 (Isoreticular MetalOrganic Framework-3) is one such MOF, which contains amine groups lining the pores of the framework.,Generic scheme for the preparation of a functionalized MOF by using direct solvothermal synthesis .,M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter,M. OKeeffe and O. M. Yagh

4、i, Science, 2002, 295, 469472.,Organic ligands (linkers, left), scaffold representation (middle), and lattice structure (from X-ray data, right),A generic scheme for the postsynthetic modification (PSM) of MOFs (top). A specific example of PSM on IRMOF-3 with benzoic anhydride (bottom).,New PSM reac

5、tions,Increasing and controlling functionality via PSM,1.How many different functional groups can be incorporated into a MOF 2.How the spatial localization can be controlled,S. J. Garibay, Z. Wang, K. K. Tanabe and S. M. Cohen, Inorg.Chem., 2009, 48, 73417349.,T. Gadzikwa, O. K. Farha, C. D. Malliak

6、as, M. G. Kanatzidis, J. T. Hupp and S. T. Nguyen, J. Am. Chem. Soc., 2009, 131,1361313615.,By taking advantage of solvent molecules trapped within the framework, the ability to distinguish the exterior and interior of the MOF was achieved.,17,Metals and coordinate covalent modification via PSM,K. O

7、isaki, Q. Li, H. Furukawa, A. U. Czaja and O. M. Yaghi,J. Am. Chem. Soc., 2010, 132, 92629264.,In this strategy, the MOF is appended with a chelating group and metallated afterwards.,19,Improving and modulating gas sorption via PSM,Z. Wang, K. K. Tanabe and S. M. Cohen, Chem.Eur. J., 2010, 16,212217.,MOF catalysts via PSM,Coordinate covalent modification of MIL-101(Cr) with chiral proline ligands. Coordinate covalent modification of MIL-101(Cr) at vacant m