1、金屬有機(jī)骨架材料（MOFs） 的后合成修飾,報(bào)告人：劉昌 2013年12月20日,2,MOFs材料簡介,20世紀(jì)90年代中期，第一代MOFs材料被合成出來,孔徑和穩(wěn)定性受到一定限制,1999年，Yaghi等人合成具有三維開放骨架結(jié)構(gòu)的MOF-5,去除孔道中的客體分子后仍然保持骨架完整,2002年，Yaghi科研組合成IRMOF系列材料,實(shí)現(xiàn)MOF材料從微孔到介孔的成功過渡,2008年，Yaghi研究組合成出上百種ZIF系列類分子篩材料,金屬離子,有機(jī)配體,配位,自組裝,周期性網(wǎng)狀骨架的多孔材料,MOFs,合成方法,特點(diǎn),應(yīng)用,分類,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