MOFPPT课件.ppt

1、.奇妙的金属有机骨架材料奇妙的金属有机骨架材料Magic Metal-Organic Frameworks.根据联合国政府间气候变化专合国政府间气候变化专门委员会门委员会（IPCC）规定，目前由人类活动引起的大量聚集在大气中的温室气体主要是二氧化碳、甲烷、一氧化氮、六氟化硫和两组工业气体氢氟烃(HFCs)和全氟烃(PFCs) 温室气体效应环境污染与能源危机.解决办法1，捕获并存储排放的气体2，开发基于氢的清洁能源新材料存储金属有机骨架材料金属有机骨架材料MOFs.什么是金属有机骨架材料什么是金属有机骨架材料MOFs ？CuAg.配体的种类.金属有机骨架材料金属有机骨架材料MOFs的奇妙之处：的

2、奇妙之处： 有大的表面积与质量比，能象海绵吸水那样吸收大量气体，比沸石和活性碳好，能用于气体存储、气体分离。 能用作传感器、缓释药品的给药载体。 能用作发光材料、磁性材料。 能将存储功能与催化作用结合，将捕获的二氧化碳转化为有用的燃料如甲醇，能用作车载储氢材料. 国际能源暑（IEA）提出的氢能源实用化的目标： 质量储氢率5%，体积储氢率50g/L， 美国能源部（DOE）提出的氢能源实用化的目标： 质量储氢率6.5%，体积储氢率62g/L，车用储氢能力3.1kg.Ferey, G. et al, Science, 2005,309,2040-2042MIL 100 and MIL 101MIL

3、101, H2, 77K, 6.1wt% pore size, 30-40 angstromsLangmuir surface area for N2, 5900m2/g CO2, 400m3 per m3 MIL 101 气体吸附与存储.Ferey, G. et al, Science, 2007,315,1828-1831NoImageMIL 88DSelectivity adsorption for CO2 over CH4 in MIL 53.MOF-5, Zn4O(BDC)3MOF-177, Zn4O(BTB)3Secondary building units (SBUs)a, th

4、e squre “paddlewheel” cluster.b, the octahedral “basic zinc acetate” cluster.c, the trigonal prismatic oxo-centered trimer.Shaped bodies made from MOF materialsYaghi, O.M., J. Am. Chem. Soc., 2008,130, 11580.Yaghi, O.M., J. Am. Chem. Soc., 2008,130, 11580.A large series of isoreticular metal-organic

5、 (IRMOFs) were produced by Yaghi group.Yaghi, O.M., Science, 2008,319, 939-943Zeolitic imidazolate frameworks (ZIFs)1, tetrahedral frameworks2, high thermal stability (up to 390 degree)3, high porosity (1970m2/g)4, unusual selectivity for CO2 capture from CO2/CO mixturesZIF-69, 83L CO2/per L at 273K

6、.Yaghi, O.M., Science, 2008,319, 939-943.N2 adsorption isotherms at 77KThe CO2/CO adsorption isotherms for ZIF-69 at 273KGas adsorption isotherms of ZIF-95 (77K) and ZIF-100 (87K)Yaghi, O.M., Nature, 2008,453, 207-211ZIF 95, 1240m2/g, 0.43cm3/gZIF 100, 780m2/g, 0.37cm3/g.Yaghi, O.M., Nature, 2008,45

7、3, 207-211.Yaghi, O.M., Science, 2005,310, 1166-1170Covalent organic frameworks (COFs)COF 1, pore size 7 angstroms, 500 degree, 711m2/g.COF 5, pore size 27 angstroms, 600 degree, 1590m2/g.Yaghi, O.M., J. Am. Chem. Soc., 2009,8875-8883.COF 102, 72mg/g H2 77K; 187mg/g CH4, 1180mg/g CO2, 298K.Low-press

8、ure H2 isotherms at 77KHigh-pressure H2 isotherms at 77KHigh-pressure CH4 isotherms at 298KH2-storage capacities for different MOFs.Yaghi, O.M., Science, 2010,329, 424-428MOF-177MOF-180.MOF-200MOF-205.MOF-210.Chen, X. M., Inorg. Chem., 2009, 3882-3889Langmuir surface area 195m2/gBET surface area 155

9、m2/g1.56 CO2 molecules per unit pore.Langmuir surface area, 1100m2/g,BET surface area, 914m2/gPore volume, 0.39cm3/gN2 adsorbed in the pore, 337mg/g .Bai, J. F. Chem. Commun., 2009, 7551-7553A small cage 8.5 angA large pore 8.8*21.5 angMOF-505 analog.Cu2(EBTC)Langmuir surface area 2844m2/gBET surfac

10、e area 1852m2/g286cm3/g H2 at 77K 2.58wt%178cm3/g CO2 at 273K 252cm3/g C2H2 at 273KC2H2.Bu, X.H., Chem. J. Eur., 2008, 2771-2776.The selective sorption of O2 and CO2 over N2Diameter, O2 3.46 ; CO2 3.3 ; N2 3.64 ; H2 2.8 ; CO 3.76 79.3cm3/g O2 at 77K98.8cm3/g CO2 at 195K Langmuir surface area 279 and

11、 390m2/g for O2 and CO2; BET surface area 246 and 313m2/g for O2 and CO2.MOF作为发光材料Representation of emission possibilities in a porous MOF.Structure and luminescence properties of Zn3L3(DMF)2(left) and Zn4OL3(right)Cd3L6(BF4)2(SiF6)(OH)2+13.5H2OL is 2,6-di(4-triazolyl)pyridineLuminescence spectra of

12、 complexes with increasing dehydration and partially rehydrated.Cu6L6+H2O+DMSO, 1D nanotubular channels 1.2nmL is 5,6-diphenyl-1,2,4-triazine-3-thiolLuminiscence spectra of the porous solid and afterImmersing this solid in an aqueous solution of tolueneEu(pdc)1.5(dmf)(DMF)0.5(H2O)0.5pdc is pyridine-

13、3,5-dicarbrateCu(NO3)2 at different concentrationComparison of different metal ionsCoordination to metal.a, 1D InO4(OH)2 Chain in 1b, four TBAPy to an In(III)c, eight In to one TBAPyd,e,f, 3D view along 001 010 directionsIn(NO3)3 850CDMF+dioxane+H2OIn2(OH)2(TBAPy)+guests 1.The framework structure of

14、 toluene-loaded 1Fluorescence (blue) and excitation (red) 1+1+TBAPy.N2 adsorption isotherm of 1 at 77K and 1 barEffect of DMF molecules on the fluorescence of 1Guest-dependent fluorescence emission of 1.Fujita, M. et al, J. Am.Chem.Soc., 2008, 1578-1579Direct observation of the labile imine formatio

15、n through single-crystal-to-single-crystal reaction in the pores of a Porous coordination network.Changes in color and magnetic properties of CoCr(CN)62/3+zH2O depend on the humidity.Unsaturated metal connecting points as active catalytic sitesActive catalytic sites into the bridging ligands of MOFs

16、MOFs as catalyst.1D triangular shape channel with a size of 13.4 ang, Showing the catalytic centre and the chiral pocketTransesterification reaction catalyzed by 8.2D infinite framework Cu2(L8)2(H2O)2MeOH.H2O.The water molecules terminating the copper were removed upon heating, allowing the exposed

17、copper centers to function as Lewis acid catalytic reaction centersThe asymmetric ring-opening of epoxides with amines, Yield 54%, enantiomeric excess 45%Cd3Cl6(L14)3, Enantioselectively catalyze diethylzine additions to aromatic aldehydes.Paddle-wheel copper(II) tetracarboxylate building block for

18、Cu3(C9O6H3)2(H2O)3Showing nanochannels with fourfold symmetry and temperature dependent magnetic susceptibilityMOFs as magnets.Cu3(PTMTC)2(py)6(EtOH)2(H2O)Reversible solvatomagnetic effects in dynamic porous magnets.Reversible solvatomagnetic effects in dynamic porous magnetsCo3(OH)2(C2O4)23H2O.Fuji

19、ta, M. et al, Chem. Commun., 2009, 1638-1640Fujita, M. et al, Science, 2006,313,1273-1276.Kitagawa,S., et al, J.Am.Chem.Soc., 2009, 12790-12800.Cubic diamondoid,Hexagonal diamondoidOctahedral metal nodes,Square grid, octahedral networkMetal-organic octahedral joined through Perchlorate anions into a

20、 cyclohexane-like motifFaceted polyhedraTetrahedral and octahedral coordination modelMOFs as arts.美丽而多才多艺的晶体美丽而多才多艺的晶体 金刚石，三维骨架结构，坚硬，不导电石墨，层状结构，柔软，导电球烯，60个碳组成足球结构，具超导性碳纳米管，细管径小至1个纳米左右，硬度极高，导体、半导体认识晶体认识晶体开发晶体开发晶体设计晶体设计晶体.石墨烯晶体石墨烯晶体已知材料中最薄的一种，还非常牢固坚硬；作为单质，它在室温下传递电子的速度比已知导体都快 ,石墨烯结构非常稳定，迄今为止，研究者仍未发现石墨烯中有碳原子缺失的情况。石墨烯中各碳原子之间的连接非常柔韧，当施加外部机械力时，碳原子面就弯曲变形,石墨烯最大的特性是其中电子的运动速度达到了光速的1/300 .