奇妙的金属有机骨架材料

The asymmetric ring-opening of epoxides with amines, Yield 54%, enantiomeric excess 45%
[Cd3Cl6(L14)3], Enantioselectively catalyze diethylzine
Transesterification reaction catalyzed by 8
2D infinite framework [Cu2(L8)2(H2O)2]MeOH.H2O.The water molecules terminating the copper were removed upon heating, allowing the exposed copper centers to function as Lewis acid catalytic reaction centers
Active catalytic sites into the bridging ligands of MOFs
1D triangular shape channel with a size of 13.4 ang, Showing the catalytic centre and the chiral pocket
奇妙的金属有机骨架材料
Magic Metal-Organic Frameworks
环境污染与能源危机
温室气体效应
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)
MIL 88D
HO
O
O
OH
Ferey, G. et al, Science, 2007,315,1828-1831
Selectivity adsorption for CO2 over CH4 in MIL 53
Yaghi, O.M., J. Am. Chem. Soc., 2008,130, 11580
Chen, X. M., Inorg. Chem., 2009, 3882-3889
Langmuir surface area 195m2/g BET surface area 155m2/g
1.56 CO2 molecules per unit pore
Langmuir surface area, 1100m2/g, BET surface area, 914m2/g Pore volume, 0.39cm3/g
Fluorescence (blue) and excitation (red) 1+1`+TBAPy
N2 adsorption isotherm of 1` at 77K and 1 bar
Guest-dependent fluorescence emission of 1
Effect of DMF molecules on the fluorescence of 1
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
C2H2
286cm3/g H2 at 77K 2.58wt% 178cm3/g CO2 at 273K 252cm3/g C2H2 at 273K
Bu, X.H., Chem. J. Eur., 2008, 2771-2776
The selective sorption of O2 and CO2 over N2
Changes in color and magnetic
properties of Co[Cr(CN)6]2/3+zH2O depend on the humidity
MOFs as catalyst
Unsaturated metal connecting points as active catalytic sites
N2 adsorbed in the pore, 337mg/g
A small cage 8.5 ang A large pore 8.8*21.5 ang MOF-505 analog.Cu2(EBTC)
Bai, J. F. Chem. Commun., 2009, 7551-7553
Langmuir surface area 2844m2/g BET surface area 1852m2/g
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。
能用作传感器、缓 释药品的给药载体。
气体吸附与存储
Ferey, G. et al, Science, 2005,309,2040-2042
MIL 100 and MIL 101
MIL 101, H2, 77K, 6.1wt% pore size, 30-40 angstroms
Langmuir surface area for N2, 5900m2/g CO2, 400m3 per m3 MIL 101
Secondary building units (SBUs) a, the squre “paddlewheel” cluster. b, the octahedral “basic zinc acetate” cluster. c, the trigonal prismatic oxo-centered trimer.
Structure and luminescence properties of Zn3L3(DMF)2(left) and Zn4OL3(right)
Cu6L6+H2O+DMSO, 1D nanotubular channels 1.2nm L is 5,6-diphenyl-1,2,4-triazine-3-thiol
Coordination to metal
Luminiscence spectra of the porous solid and after Immersing this solid in an aqueous solution of toluene
[Eu(pdc)1.5(dmf)](DMF)0.5(H2O)0.
MOF作为发光材料
Representation of emission possibilities in a porous MOF
[Cd3L6](BF4)2(SiF6)(OH)2+13.5H2 O
L is 2,6-di(4-triazolyl)pyridine
Luminescence spectra of complexes with increasing dehydration and partially rehydrated
a, 1D InO4(OH)2 Chain in 1 b, four TBAPy to an In(III) c, eight In to one TBAPy
d,e,f, 3D view along [001] [010] directions
The framework structure of toluene-loaded 1`
5
pdc is pyridine-3,5-dicarbrate
Cu(NO3)2 at different concentration
Comparison of different metal ions
In(NO3)3 850C DMF+dioxane+H2O
[In2(OH)2(TBAPy)]+guests 1
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
Covalent organic frameworks (COFs)
Yaghi, O.M., Science, 2005,310, 1166-1170
COF 1, pore size 7 angstroms, 500 degree, 711m2/g
COF 5, pore size 27 angstroms, 600 degree, 1590m2/g
ZIF-69, 83L CO2/per L at 273K
Yaghi, O.M., Science, 2008,319, 939-943
Yaghi, O.M., Nature, 2008,453, 207-211
N2 adBiblioteka Baiduorption isotherms at 77K
The CO2/CO adsorption isotherms for ZIF-69 at 273K
Shaped bodies made from MOF materials
MOF-5, Zn4O(BDC)3 MOF-177, Zn4O(BTB)3
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., Science, 2008,319, 939-943
Zeolitic imidazolate frameworks (ZIFs) 1, tetrahedral frameworks 2, high thermal stability (up to 390 degree) 3, high porosity (>1970m2/g) 4, unusual selectivity for CO2 capture from CO2/CO mixtures
Fujita, M. et al, J. Am.Chem.Soc., 2008, 1578-1579
Direct observation of the labile imine formation through single-crystal-tosingle-crystal reaction in the pores of a Porous coordination network
79.3cm3/g O2 at 77K 98.8cm3/g CO2 at 195K
Langmuir surface area 279 and 390m2/g for O2 and CO2; BET surface area 246 and 313m2/g for O2 and CO2
Diameter, O2 3.46 Å; CO2 3.3 Å; N2 3.64 Å; H2 2.8 Å; CO 3.76 Å
ZIF 95, 1240m2/g, 0.43cm3/g ZIF 100, 780m2/g, 0.37cm3/g
Gas adsorption isotherms of ZIF-95 (77K) and ZIF-100 (87K)
Yaghi, O.M., Nature, 2008,453, 207-211
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 isotherms at 77K