MOFs金属有机材料的制备与应用(课堂PPT).ppt

Click to edit Master text styles,Second level,Third level,Fourth level,Fifth level,*,Click to edit Master title stylea,金属-有机骨架材料（MOFs）,多孔材料家族的新成员,Seminar,1,2,2,MOFs材料简介,制备方法,应用领域,小结与展望,参考文献,目 录,一,二,三,四,五,MOFs材料简介,3,20,世纪,90,年代中期，第一代,MOFs,材料被合成出来,孔径和稳定性受到一定限制,1999,年，,Yaghi,等人合成具有三维开放骨架结构的,MOF-5,去除孔道中的客体分子后仍然保持骨架完整,2002,年，,Yaghi,科研组合成,IRMOF,系列材料,实现,MOF,材料从微孔到介孔的成功过渡,2008,年，,Yaghi,研究组合成出上百种,ZIF,系列类分子筛材料,金属离子,有机配体,配位,自组装,周期性网状骨架的多孔材料,3,4,4,MOFs材料简介,比表面积大,孔道可调控,可功能化,气体储存,吸附分离,催化,光学材料,磁性材料,药物传输,5,制备方法,5,制备方法,原位溶剂热法,6,自组装膜修饰基底,Hermes,S.et al.,J.Am.Chem.Soc.2005,127,13744-13745,设备简单,对合成条件敏感,自组装层影响膜性能,基底,Au,自组装膜,MOF-5,6,7,制备方法,晶种法,把晶体的成核和生长过程分离开,更好地控制晶体的生长和膜的微结构,Liu,Y.,et al.J.Membr.Sci.2011,379,46-51.,7,8,制备方法,晶种法,8,Falcaro,P.et al,.,Nat.Commun.,2011,2,237.,MOF,晶种,-,磷锌矿,晶体合成,晶膜制备,三维表面成膜,选择性催化,功能化,-,磷锌矿具有促使,MOF-5,成核的特殊功能,9,制备方法,微波法,9,Yoo,Y.et al.Microporous Mesoporous Mater.,2009,123,100-106,Yoo,Y.et al.Chem.Commun.,2008,21,2441-2443,微波,快速结晶,溶剂热,二次生长,微波法,30s,微波辅助快速晶种法,节约制备时间,晶体颗粒较小,10,制备方法,分层法,10,Shekhah,O.Materials,2010,3,13021315,Shekhah,O.et al.Nat.Mater.,2009,8,481-484,高度有序、均匀、平整的,MOF,膜,实现晶体的高度取向性,合成其他方法无法得到的,MOF,结构,分层法图解,11,11,应用领域,气体储存,11,氢气,二氧化碳,甲烷,突破,DOE,储氢目标：,7.5wt.%,Furukawa,H.et al.J.Materi.Chem.,2007,17,3197-3204,Gassensmith,J.J.et al.J.Am.Chem.Soc.,2011,133,1531215315,;Ma,S.et al.J.Am.Chem.Soc.2008,130,1012-1016,超过,DOE,室温体积,CH4,储存目标（,180v/v,）,28%,CO,2,MOF-177,CD-MOF-2,PCN-14,12,应用领域,吸附分离,12,Liu,X.-L.et al.Angew.Chem.Int.Ed.2011,50,1-5,ZIF-8,吸附异丁醇过程中的,“,gate-opening,”,效应,+,表面超疏水性,优先透过醇类大分子而阻止水分子的高性能,ZIF-8,纳米复合膜,分离系数：,34.9-40.1,透量：,6.4-8.6,kgh,-1,m,-2,13,应用领域,催化,13,方法,特点,利用骨架自身活性位,MOF中的活性金属位或活性结构模块，可直接作为催化剂使用，但该法易导致骨架坍塌,引入活性物质,合成过程中引入具有催化活性的金属纳米粒子，即将MOF作为一种高比表面积的载体使用,后合成法,先合成MOF材料，再向MOF中引入活性基团或者活性物质,在,MOF,中构建特殊催化位点的方法,14,应用领域,催化,14,Wang,C.et al.J.Am.Chem.Soc.2011,133,13445-13454,催化剂,TOF,（,h,-1,）,MOF 1,4.8,MOF 2,1.9,MOF 3,0.4,转化率（%）,MOF 5,MOF 6,Ar=H,59,86,Ar=Br,62,68,Ar=OCH3,96,97,光催化剂,TOF（h,-1,）,MOF-4,0.8,水氧化和光催化剂,MOF UiO-67,Ir,、,Re,或,Ru,的复合物,分子催化与,MOF,材料相结合,为光催化提供一种新的异相催化剂,15,应用领域,发光材料,15,选择合适的配体或金属离子，可使,MOFs,具有发光性能,生色团,溶剂不同结构不同荧光性不同,Bauer,C.A.et al.,J.Am.Chem.Soc.,2007,129,7136,16,应用领域,其他,磁性材料 顺磁性、反磁性,传感器 客体影响,MOFs,光学和磁学性能,药物传输 药物包埋,孔口修饰官能团,在不同的外界条件下打开或关闭孔口,药物控制释放,16,17,总结及展望,17,功能化材料,MOFS,晶体尺寸、形状和取向的可控生长,高质量连续生长、均相无缺陷的,MOFs,膜,不同领域的科学家,相互合作,开发,MOF,的综合性能,18,参考文献,1.C.Wang,Z.Xie,K.E.deKrafft et al.,Doping MetalOrganic Frameworks for Water Oxidation,Carbon Dioxide Reduction,and Organic Photocatalysis,.J.Am.Chem.Soc.2011,133,13445-13454,2.J.J.Gassensmith,H.Furukawa,R.A.Smaldone et al.,Strong and Reversible Binding of Carbon Dioxide in a Green MetalOrganic Framework,.J.Am.Chem.Soc.,2011,133,15312-15315,3.P.Falcaro,A.J.Hill,K.M.Nnairn et al.,A new method to position and functionalize metal-organic framework crystals.Nat.Commun.,2011,2,237-244,4.X.-L.Liu,Y.-S.Li,G.-Q.Zhu et al.,An Organophilic Pervaporation Membrane Derived from MetalOrganic Framework Nanoparticles for Efficient Recovery of Bio-Alcohols,.Angew.Chem.Int.Ed.2011,50,1-5,5.Y.Liu,G.Zeng,Y.Pan et al.,Synthesis of highly c-oriented ZIF-69 membranes by secondary growth and their gas permeation properties.,J.Membr.Sci.,2011.379,46-51,6.O.Shekhah,Layer-by-Layer Method for the Synthesis and Growth of Surface Mounted Metal-Organic Frameworks(SURMOFs),.Materials,2010,3,13021315,7.O.Shekhah,H.Wang,M.Paradinas et al.,Controlling interpenetration in metalorganic frameworks by liquid-phase epitaxy,.Nat.Mater.,2009,8,481-484,8.Y.Yoo,Z.Lai,and H.-K.Jeong,Fabrication of MOF-5 membranes using microwave-induced rapid seeding and solvothermal secondary growth,.Microporous Mesoporous Materi.,2009,123,100-106,9.S.Ma,D.Sun,D.M.Simmons et al.,Metal-Organic Framework from an Anthracene Derivative,Containing Nanoscopic Cages Exhibiting High Methane Uptake,.J.Am.Chem.Soc.2008,130,1012-1016,18,参考文献,19,10.Y.Yoo,and H.-K.Jeong,Rapid fabrication of metal organic framework thin films using microwave-induced thermal deposition,.Chem.Commun.,2008,21,2441-2443,11.C.A.Bauer,T.V.Timofeeva,T.B.Settersten,B.D.Patterson,V.H.Liu,B.A.Simmons,M.D.,Allendorf.Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal-Organic Frameworks.,J.Am.Chem.Soc.129(2007)7136.,12.H.Furukawa,M.A.Miller,and O.M.Yaghi,Independent verification of the saturation hydrogen uptake in MOF-177 and establishment of a benchmark for hydrogen adsorption in metal-organic frameworks,.J.Materi.Chem.,2007,17,3197-3204,13.S.Hermes,F.Schrder,R.Chelmowski et al.,Selective Nucleation and Growth of Metal-Organic Open Framework Thin Films on Patterned COOH/CF3-Terminated Self-Assembled Monolayers on Au(111),.J.Am.Chem.Soc.2005,127,13744-13745,19,谢谢！,20,21,附图,21,Wang,C.et al.J.Am.Chem.Soc.2011,133,13445-13454,附图,22,Wang,C.et al.J.Am.Chem.Soc.2011,133,13445-13454,22,