1、分子筛发展简史姜久兴1微孔材料介孔材料大孔材料无机材料金属-有机骨架材料有机聚合物孔径分布孔径分布骨架组成骨架组成能源、环境、材料等领域具有重要的应用能源、环境、材料等领域具有重要的应用催化、吸附与分离等性能催化、吸附与分离等性能分分子子水水平平超超分分子子水水平平宏宏观观颗颗粒粒2 nm50 nmIUPAC 多孔材料分类2同素异形体(Allotropes)Etc.-C:CarbonSiO2:Silicon DioxideEtc.-AllotropesIsotopeIsomer3Play with Parameters水热，溶剂热，离子热模板剂，阳离子 无机到有机 季铵盐到季膦盐，膦铵，配合物
2、 换成阴离子？单分子模板剂，高分子，超分子模板剂OH-，F-，OHSi-Al，PO-S，NSi-M，O-Ligand电荷匹配-电荷不匹配等等水水热热配比配比模板剂模板剂矿化剂溶胶浓溶胶浓度度SiO24天然1756低硅铝水水热热8,12R碱金属碱金属OH-稀溶胶稀溶胶低硅铝低硅铝NaA,NaX,MOR194050sNaY水水热热12R季铵盐季铵盐OH-稀溶胶稀溶胶高高硅铝硅铝1960s BetaBarrer&DennyULKerr and Kokotailo Mobil水水热热10R季铵盐季铵盐OH-稀溶胶稀溶胶高高纯纯硅硅1970s ZSM-5Silicalite-1Mobil vsUnion
3、CarbideWilson&FlanigenUC水水热热8,12RF-稀溶胶稀溶胶高硅铝高硅铝1978季铵盐季铵盐水水热热8,12RpH 6-9,F-稀溶胶稀溶胶磷酸铝磷酸铝 1982,AlPO4-n有机胺有机胺水水热热18RpH 6-9,F-稀溶胶稀溶胶磷酸铝磷酸铝 1988,VPI-5有机胺有机胺Milton&BarrerFlanigenUCMark DavisMCM-48MCM-411992水体系水体系碱体系碱体系阳离子阳离子氧化硅氧化硅Jeffrey A.Lawton Mobil1992,Mobil MCM-41Mesoporous沸石分子筛沸石分子筛合成大事记合成大事记MOFCF5水
4、水热热14R稀溶胶稀溶胶高硅铝高硅铝1996,UTD-1二茂钴二茂钴OH-水水热热14R浓溶胶浓溶胶纯硅纯硅1996,Pure Silica Beta F-or OH-有机胺有机胺水水热热UP to 30R浓溶胶浓溶胶硅锗硅锗2000,GeSi ITQ-nF-or OH-季铵盐季铵盐离子离子热热12R浓溶胶浓溶胶磷酸铝磷酸铝2004,SIZ-nF-or OH-离子液离子液体体R.MorrisU St A12R浓溶胶浓溶胶2006,Green Beta低硅铝低硅铝水水热热碱金属碱金属OH-肖肖丰收丰收浙江大学浙江大学12RNone2012,Inverse Sigma2D-3D-2DNoneNon
5、e高硅锗高硅锗NoneNone2016,Free Radical2D-3D-2DNoneOHNoneC.E.A.KirschhockCSCCFreyhardtUT于吉红于吉红吉林大学吉林大学Miguel CamblorICMM-CSICCorma,M.J.Daz-Cabaas,V.Forns,Angew.Chem.Int.Ed.2000,39,2346;A.CormaITQ水水热热12R稀溶胶稀溶胶高硅铝高硅铝1994,MCM-22有机胺有机胺OH-低硅铝离子离子热热12R2003,CDMOH-低硅铝季铵盐季铵盐稀溶胶稀溶胶6G.J.Lewis UOP从天然沸石到合成沸石 玄武岩（岩浆岩，高温
6、高压，地下热水或温泉）的孔洞中（陆成沉积物）。含有火山玻璃质的沉积物与富钠的海水反应，也可以生成沸石（海成沉积物）。火山沉积物与碱性的湖水的作用而生成沸石（碱性盐湖沉积物）。到十九世纪末，发现在沉积岩中也存在沸石。7天然沸石891940s 50s:从天然沸石到合成沸石 1862，Claire Deville，Levynite（高温水热）1940s,Richard Barrer (中低温水热170-270C)zeolite P and Q(ZK-5,KFI)(U of London,Aberdeen)1949,Robert Milton(Linde corporation div,U.C.),使
7、用更温和的条件合成 Na-A,B(Na-P),C(Sodalite),X.10The Founding FathersRichard Barrer(1910-1996)R.M.Milton(1920-2000)111960s.从低硅到高硅沸石 1964 年Breck 成功的合成与开发出了Y 型分子筛（Si/Al=1.53.0）Barrer and Danny Kerr and Kokotailo(mobil)1967,high silica Beta(5Si/Al 100H2O/SiO2 OH-56参考文献分子筛与多孔材料化学第二版，徐如人，霍启升，庞文琴等著,科学出版社，2014 Edite
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