奇妙的金属有机骨架材料介绍和性质

1、奇妙的金属有机骨架材料介绍和性质根据联合国政府间气候变化专门委员会（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MOFs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MOFs的奇妙之处： 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

2、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Ferey, G. et al, Science, 2005,309,2040-2042MIL 100 and MIL 101MIL 101, H2, 77K, 6.1wt% pore size, 30-40 angstromsLangmuir surface area for N2, 5900m2/g CO2, 400m3

3、 per m3 MIL 101 气体吸附与存储Ferey, G. et al, Science, 2007,315,1828-1831MIL 88DSelectivity adsorption for CO2 over CH4 in MIL 53MOF-5, Zn4O(BDC)3MOF-177, Zn4O(BTB)3Secondary building units (SBUs)a, the squre “paddlewheel” cluster.b, the octahedral “basic zinc acetate” cluster.c, the trigonal prismatic ox

4、o-centered trimer.Shaped bodies made from MOF materialsYaghi, O.M., J. Am. Chem. Soc., 2008,130, 11580Yaghi, O.M., J. Am. Chem. Soc., 2008,130, 11580A large series of isoreticular metal-organic (IRMOFs) were produced by Yaghi groupYaghi, O.M., Science, 2008,319, 939-943Zeolitic imidazolate framework

5、s (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 273KYaghi, O.M., Science, 2008,319, 939-943N2 adsorption isotherms at 77KThe CO2/CO adsorption isotherms for ZIF

6、-69 at 273KGas adsorption isotherms of ZIF-95 (77K) and ZIF-100 (87K)Yaghi, O.M., Nature, 2008,453, 207-211Yaghi, O.M., Nature, 2008,453, 207-211Yaghi, O.M., Science, 2005,310, 1166-1170Covalent organic frameworks (COFs)COF 1, pore size 7 angstroms, 500 degree, 711m2/gCOF 5, pore size 27 angstroms,

7、600 degree, 1590m2/gYaghi, O.M., J. Am. Chem. Soc., 2009,8875-8883COF 102, 72mg/g H2 77K; 187mg/g CH4, 1180mg/g CO2, 298KLow-pressure H2 isotherms at 77KHigh-pressure H2 isotherms at 77KHigh-pressure CH4 isotherms at 298KH2-storage capacities for different MOFsYaghi, O.M., Science, 2010,329, 424-428

8、MOF-177MOF-180MOF-200MOF-205MOF-210Chen, X. M., Inorg. Chem., 2009, 3882-3889Langmuir surface area 195m2/gBET surface area 155m2/g1.56 CO2 molecules per unit poreLangmuir surface area, 1100m2/g,BET surface area, 914m2/g3/gN2 adsorbed in the pore, 337mg/g Bai, J. F. Chem. Commun., 2009, 7551-7553A sm

9、all cage 8.5 angA large pore 8.8*21.5 angMOF-505 analog.Cu2(EBTC)Langmuir surface area 2844m2/gBET surface area 1852m2/g286cm3/g H2 at 77K 2.58wt%178cm3/g CO2 at 273K 252cm3/g C2H2 at 273KC2H2Bu, X.H., Chem. J. Eur., 2008, 2771-2776The selective sorption of O2 and CO2 over N2Diameter, O2 3.46 ; CO2

10、3.3 ; N2 3.64 ; H2 2.8 ; CO 3.76 Langmuir surface area 279 and 390m2/g for O2 and CO2; BET surface area 246 and 313m2/g for O2 and CO2MOF作为发光材料Representation of emission possibilities in a porous MOFStructure and luminescence properties of Zn3L3(DMF)2(left) and Zn4OL3(right)Cd3L6(BF4)2(SiF6)(OH)22OL

11、 is 2,6-di(4-triazolyl)pyridineLuminescence spectra of complexes with increasing dehydration and partially rehydratedCu6L6+H2L 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)(dmf)(DMF)(H2O)pdc is py

12、ridine-3,5-dicarbrateCu(NO3)2 at different concentrationComparison of different metal ionsCoordination to metala, 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 1The framework structu

13、re of toluene-loaded 1Fluorescence (blue) and excitation (red) 1+1+TBAPyN2 adsorption isotherm of 1 at 77K and 1 barEffect of DMF molecules on the fluorescence of 1Guest-dependent fluorescence emission of 1Fujita, M. et al, J. Am.Chem.Soc., 2008, 1578-1579Direct observation of the labile imine forma

14、tion through single-crystal-to-single-crystal reaction in the pores of a Porous coordination networkChanges in color and magnetic properties of CoCr(CN)62/3+zH2O depend on the humidityUnsaturated metal connecting points as active catalytic sitesActive catalytic sites into the bridging ligands of MOF

15、sMOFs as catalyst1D triangular shape channel with a size of 13.4 ang, Showing the catalytic centre and the chiral pocketTransesterification reaction catalyzed by 82D infinite framework Cu2(L8)2(H2O)2MeOH.H2O.The water molecules terminating the copper were removed upon heating, allowing the exposed c

16、opper 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 aldehydesPaddle-wheel copper(II) tetracarboxylate building block for Cu

17、3(C9O6H3)2(H2O)3Showing nanochannels with fourfold symmetry and temperature dependent magnetic susceptibilityMOFs as magnetsCu3(PTMTC)2(py)6(EtOH)2(H2O)Reversible solvatomagnetic effects in dynamic porous magnetsReversible solvatomagnetic effects in dynamic porous magnetsCo3(OH)2(C2O4)23H2OFujita, M. et al, Chem. Commun., 2009, 1638-1640Fujita, M. et al, Science, 2006,313,1273-1276Kitagawa,S., et al, ., 2009, 12790-12800Cubic diamondoid,Hexagonal diamondoidOctahedral metal nodes,Square grid, o