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1、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 ？,Cu,Ag,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
2、。,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, 2005,309,2040-2042,MIL 100 and MIL 101,MIL 101, H2, 77K, 6.1wt% pore size, 30-40 angstromsLangm
3、uir surface area for N2, 5900m2/g CO2, 400m3 per m3 MIL 101,气体吸附与存储,Ferey, G. et al, Science, 2007,315,1828-1831,MIL 88D,Selectivity adsorption for CO2 over CH4 in MIL 53,MOF-5, Zn4O(BDC)3,MOF-177, Zn4O(BTB)3,Secondary building units (SBUs)a, the squre “paddlewheel” cluster.b, the octahedral “basic
4、zinc acetate” cluster.c, the trigonal prismatic oxo-centered trimer.,Shaped bodies made from MOF materials,Yaghi, 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 (IRMOFs) were produced by Yaghi group,Yaghi, O.M., S
5、cience, 2008,319, 939-943,Zeolitic 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 mixtures,ZIF-69, 83L CO2/per L at 273K,Yaghi, O.M., Science, 2008,319, 939-943,N2 adsorpt
6、ion isotherms at 77K,The CO2/CO adsorption isotherms for ZIF-69 at 273K,Gas adsorption isotherms of ZIF-95 (77K) and ZIF-100 (87K),Yaghi, O.M., Nature, 2008,453, 207-211,ZIF 95, 1240m2/g, 0.43cm3/gZIF 100, 780m2/g, 0.37cm3/g,Yaghi, O.M., Nature, 2008,453, 207-211,Yaghi, O.M., Science, 2005,310, 1166
7、-1170,Covalent 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-pressure H2 isotherms at 77K,High-pressure H2 isot
8、herms at 77K,High-pressure CH4 isotherms at 298K,H2-storage capacities for different MOFs,Yaghi, O.M., Science, 2010,329, 424-428,MOF-177,MOF-180,MOF-200,MOF-205,MOF-210,Chen, X. M., Inorg. Chem., 2009, 3882-3889,Langmuir surface area 195m2/gBET surface area 155m2/g,1.56 CO2 molecules per unit pore,
9、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, 7551-7553,A small cage 8.5 angA large pore 8.8*21.5 angMOF-505 analog.Cu2(EBTC),Langmuir surface area 2844m2/gBET surface area 1852m2/g,286cm3/g H2 at 77K 2
10、.58wt%178cm3/g CO2 at 273K 252cm3/g C2H2 at 273K,C2H2,Bu, X.H., Chem. J. Eur., 2008, 2771-2776,The selective sorption of O2 and CO2 over N2,Diameter, 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 390m2/g for O2 and CO2; BET sur
11、face 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)pyridine,Luminescence spectra of complexes with increasing de
12、hydration and partially rehydrated,Cu6L6+H2O+DMSO, 1D nanotubular channels 1.2nmL is 5,6-diphenyl-1,2,4-triazine-3-thiol,Luminiscence spectra of the porous solid and afterImmersing this solid in an aqueous solution of toluene,Eu(pdc)1.5(dmf)(DMF)0.5(H2O)0.5pdc is pyridine-3,5-dicarbrate,Cu(NO3)2 at
13、different concentration,Comparison of different metal ions,Coordination 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 directions,In(NO3)3 850C,DMF+dioxane+H2O,In2(OH)2(TBAPy)+guests 1,The framework structure of toluene-loaded 1,Flu
14、orescence (blue) and excitation (red) 1+1+TBAPy,N2 adsorption isotherm of 1 at 77K and 1 bar,Effect of DMF molecules on the fluorescence of 1,Guest-dependent fluorescence emission of 1,Fujita, M. et al, J. Am.Chem.Soc., 2008, 1578-1579,Direct observation of the labile imine formation through single-
15、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 sites,Active catalytic sites into the bridging ligands of MOFs,MOFs as catalys
16、t,1D triangular shape channel with a size of 13.4 ang, Showing the catalytic centre and the chiral pocket,Transesterification 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 copper centers
17、 to function as Lewis acid catalytic reaction centers,The 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 Cu3(C9O6H3)2
18、(H2O)3Showing nanochannels with fourfold symmetry and temperature dependent magnetic susceptibility,MOFs as magnets,Cu3(PTMTC)2(py)6(EtOH)2(H2O),Reversible solvatomagnetic effects in dynamic porous magnets,Reversible solvatomagnetic effects in dynamic porous magnets,Co3(OH)2(C2O4)23H2O,Fujita, M. et
19、 al, Chem. Commun., 2009, 1638-1640,Fujita, 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 network,Metal-organic octahedral joined through Perchlorate anions into a cycloh
20、exane-like motif,Faceted polyhedra,Tetrahedral and octahedral coordination model,MOFs as arts,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,开发晶体,设计晶体,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,
