沸石合成与转晶的拓扑学研究
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摘要
本文从拓扑学的角度研究沸石的合成与转晶。依照国际沸石协会(IZA)提供的各种结构方面与合成方面的数据，建立沸石信息库。数据库由沸石结构信息表、沸石合成信息表和沸石三维结构模型库三部分组成，通过对数据库中各种信息的统计分析，我们找到了沸石结构和沸石合成中的一些规律。基于建好的模型库，我们提出了一个用于研究沸石转晶的新方法——定向拓扑转变法，并将其应用于丝光沸石(MOR)到方沸石(ANA)的转晶过程，得到以下结论：在丝光沸石转晶过程中不涉及五元环的键比较稳定，在转变过程中不易发生断裂；在转晶开始阶段丝光沸石的骨架结构先形成许多小的二级单元，这些二级单元溶解脱离骨架，随后在一定的条件下，它们之间按照一定的方式连接，慢慢组装成方沸石的骨架结构。同时通过对所有沸石结构的观察，我们还发现每种沸石结构中都含有一个最小的结构单元，它的几何构型与沸石的三维结构有某种联系，据此，我们提出了一个理论模型——5-T模型，它由五个(四面体原子(T原子)组成，是具有沸石宏观结构特征的最小微观单元。5-T模型可以将沸石的合成条件与沸石结构联系起来，因此可以用于计算机模拟沸石的水热合成，设计新型的沸石材料。
The article is focused on the synthesis and transformation of zeolites via a topological approach. A zeolites information database, which consists of zeolites structure information table, zeolites synthesis information table and zeolites 3-D structure model database, is built up according to the data offered by IZA(International Zeolite Association). Some laws of the zeolites structure and synthesis are revealed by extensive statistics and analysis of the zeolites information database. Based on the zeolites 3-D structure model database, a novel method called Objective-Oriented Topological Transformation(OOTT) is developed to study the transformation of zeolites. Moreover, a new theoretical model, namely 5-T model, is carried out and discussed in detail. The configuration of the 5-T model has special relationship with the zeolites structure and synthesis conditions, thus it can be used to the simulation of hydrothermal synthesis and design of new zeolites materials.
The article is focused on the synthesis and transformation of zeolites via a topological approach. A zeolites information database, which consists of zeolites structure information table, zeolites synthesis information table and zeolites 3-D structure model database, is built up according to the data offered by IZA(International Zeolite Association). Some laws of the zeolites structure and synthesis are revealed by extensive statistics and analysis of the zeolites information database. Based on the zeolites 3-D structure model database, a novel method called Objective-Oriented Topological Transformation(OOTT) is developed to study the transformation of zeolites. Moreover, a new theoretical model, namely 5-T model, is carried out and discussed in detail. The configuration of the 5-T model has special relationship with the zeolites structure and synthesis conditions, thus it can be used to the simulation of hydrothermal synthesis and design of new zeolites materials.
引文
[1] Robert W. Thompson, Recent Advances in the Understanding of Zeolite Synthesis,Molecular Sieves,Vol. 1,Springer-Verlag Berlin Heidelberg ,1998 pp 4-6
[2] H. van Bekkum, E.M. Flanigen, J.C. Jansen et al. Introduction to Zeolite Science and Practice, 2nd edition, Elsevier 2001
[3] S.Mintova, N.Petkov, K.Karaghiosoff et al. Transformation of amorphous silica colloids to nanosized MEL zeolite. Mocroporous and Mesoporous Materials,2001,50 (2-3) :121-128
[4] Svetlana Mintova, Norman H.Olson, Jürgen Senker et al. Mechanism of the Transformation of Silica Precursor Solutions into Si-MFI Zeolite. Angew.Chem.,2002,114(14): 2670-2673
[5] Svetlana Mintova, Norman H. Olson, Thomas Bein .Electron Microscopy Reveals the Nucleation Mechanism of Zeolite Y from Precursor Colloids.Angew.Chem. 1999.38(21):3201-3204
[6] 赵永记，王敬中，项寿鹤等．VPI-5分子筛转晶过程的~(31)P MAS NMR和XRD研究．南开大学学报(自然科学)，1994，(3)：1-5
[7] 董维阳，孙尧俊，贺鹤勇，龙英才，高滋．B-AI-ZSM-5沸石的固相结晶过程和机理的研究．中国科学-B辑，1998，28(3)：258-266
[8] 王仰东，傅乐峰，金大明，董家禄，须沁华．NaA，MAP和MAX高铝沸石的结构定向及其转晶．无机化学学报，2002，(8)：787-791
[9] 彭建彪，谢素娟，王清遐，徐龙伢．几种分子筛转晶和混晶的控制及单一晶体的优化合成．催化学报，2002，23(4)：363-366
[10] M.M.J. Treacy & J.B. Higgins. Collection of Simulated XRD Powder Patterns for Zeolites. 4th edition, Amsterdam: Elsevier, 2001.
[11] http://www.iza-online.org
[12] http://www.zeolites.ethz.ch/Zeolites/Explanations.htm
[13] R.M. Barter, Chemical Nomenclature and Formulation of Compositions of Synthetic and Natural Zeolites. Pure Appl. Chem. 1979(51): 1091-1100
[14] http://www.iza-structure.org/databases/ Atlas/FTC_Rules.html
[15] http://www.iza-structure.org/databases/Atlas/Type_material.html
[16] http://www.iza-structure.org/databases/Atlas/Zeolite_names.html
[17] Ch. Baerlocher, A. Hepp. and W.M Meier. DLS-76, a program for the simulation of crystal structures by geometric refinement. Lab. f. Kristallographie, ETH, Zürich. 1978
[18] http://www.iza-structure.org/databases/Atlas/FD.html
[19] G.O. Grunner and F. Laves, Wiss. Z. Techn. Univers. Dresden 1971(20), 387 H.2.
[20] W. M. Meier and H. J. Moeck, The topology of three-dimensional 4-connected nets: classification of zeolite framework types using coordination sequences, J. Solid State Chem., 1979 (27):349-355
[21] M.O'Keeffe,S.T.Hyde. Vertex symbols for zeolite nets. Zeolites, 1997(19):370-374,
[22] http://www.iza-structure.org/databases/Atlas/LC.html
[23] http://www.iza-structure.org/databases/Atlas/SBU.html
[24] Barrer RM. Synthesis ofa zeolitic mineral with chabazitelike sorptive properties .J. Chem. Soc. 1948:127-132
[25] Barrer RM, Denny PJ. J. Chem.Soc. 1961:971-982
[26] Harry Robson .Verified syntheses of zeolitic materials, second Revised Edition,ELSEVIER
2001 Amsterdam
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[28] Eric G. Derouane, Francisco Lemos, Claude Naccache Fernando Rama Ribeiro. Zeolite Microporous Solids: Synthesis, Structure, and Reactivity. Proceedings of the NATO Advanced Study Institute, Sintra-Estoril, Portugal, 1991
[29] 赵修松，王清遐，李宏愿．沸石合成进展．化工进展，1994，5：32-36
[30] Randolph AD Introduction to the theory of crystallization processes,2nd ed.Academic, London, Larson MA (1988)
[31] Xu Wenyang, Li Jianquan, Li Wenyuan, Zhang Huiming, Liang Bingchang. Nonaqueous synthesis of ZSM-35 and ZSM-5.Zeolite, 1989,(9): 468-473
[32] Xu W Y, Dong J X, Li J P. Anovel method for the preparation of zeolite ZSM-5. J. Chem Soc.Chem Commun 1990 (10):755-756
[33] R. Van Grieken, J.L. Sotelo, J.M. Men_endez, J.A. Melero. Anomalous crystallization mechanism in the synthesis ofnanocrystalline ZSM-5. Microporous and Mesoporous Materials 2000 (39): 135-147
[34] Serrano, D.P.; Van Grieken, R.; Sàchez, P.; Sanz, R.; Rodriguez, L.Crystallization mechanism of all-silica zeolite beta in fluoride medium,Microporous and Mesoporous Materials 2001,46 (1): 35-46
[35] Serrano, D.P.; Uguina, M.A.; Sanz, R.; Castillo, E.; Rodriguez, A.; Sànchez, P. Synthesis and crystallization mechanism of zeolite TS-2 by microwave and conventional heating, Microporous and Mesoporous Materials 2004,69(3): 197-208
[36] 刘中清，王一萌，傅军，何鸣元．静态水热晶化法高效合成MCM 22分子筛．催化学报 2002．23(5)：439-442
[37] Berend Smit, R. Krishna, Monte Carlo simulations in zeolites. Current Opinion in Solid State and Materials Science. 2001 (5): 455-461
[38] Michael D. Macedonia, Darrin D. Moore, and Edward J. Magirnn, Michael M. Olken. Adsorption Studies of Methane, Ethane, and Argon in the Zeolite Mordenite: Molecular Simulations and Experiments, Langmuir 2000, 16, 3823-3834
[39] David Nicholson,U Roland J.-M. Pellenq Adsorption in zeolites: intermolecular interactions and computer simulation, Advances in Colloid and Interface Science, 1998(76-77): 179-202
[40] Marco Antonio Chaer Nascimento ,Computer simulations of the adsorption process of light alkanes in high-silica zeolites, Journal of Molecular Structure (Theochem).1999 (464) :239-247
[41] Konstantin S. Smirnov and Fre'de'ric Thibault-Starzyk,Confinement of Acetonitrile Molecules in Mordenite:A Computer Modeling Study, J. Phys. Chem. B 1999(103): 8595-8601
[42] E.de Vos Burchart,V.A. Verheij, H.van Bekkum, and B. van de Graaf. A consistent molecular mechanics force field for all-silica zeolites.Zeolites, 1992 (12): 183-189
[43] E.de Vos Burchart, H.van Bekkum, and B. van de Graaf. Molecular mechanics studies on MFI-type zeolites:Part3.The monoclinic-orthorhombic phase transition. Zeolites,1993 (13):212-215
[44] 李宝宗，周斌，徐文国，裘式纶，庞文琴，徐如人．高硅沸石计算晶格能与骨架拓扑结构相关．化学研究与应用．1998，10(1)：43-48
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[48] 郭敏，李乙，李激扬，于吉红，徐如人．具有特定孔道结构的分子筛骨架的设计．复旦学报(自然科学版)．2003，42(6)：861-866
[49] Yi Li, Jihong Yu, Donghan Liu, Wenfu Yan, Ruren Xu, and Ying Xu. Design of Zeolite Frameworks with Defined Pore Geometry through Constrained Assembly of Atoms. Chem. Mater. 2003(15): 2780-2785
[50] 李宝会，孙平川，王利军，金庆华，郭振亚，丁大同．系列新型大孔径分子筛骨架结构设计．无机化学学报．200016(1)：21-26
[51] Baohui Li,Pingchuan Sun,Qinghua Jin,Datong Ding.Studies on the design of a novel topological structure of molecular sieve with extra-large open pores, Zeolite, 1996(17):424-427
[52] 林德昌 周伟正 郭娟 龙英才．四氢呋喃与全硅FER，MTN，MOR和MFI沸石骨架相互作用的计算机模拟．化学学报．2003，6(6)：835～839
[53] 王利军，李宝会，金庆华，朱水平，郭振亚，王敬中，丁大同．模板剂在沸石合成过程中的作用机理研究．化学物理学报2000，13(3)：344-348
[54] 于吉红，李激扬，徐如人．用分子动力学模拟方法研究层孔与微孔磷酸铝化合物中有机胺的模板作用—指导定向合成的有效途径．化学学报．2000，58(7)：790-794
[55] 李激扬，于吉红，徐如人．微孔化合物生成中的结构导向与模板作用．无机化学学报 2004，20(1)-1-16
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[58] D. W. Lewis, G. Sankar, J. Wyles, J. M. Thomas, C. R. A. Catlow, D. J. Willock, 'Synthesis of a Small-Pore Microporous Material Using a Computationally Designed Template', Angew. Chemie, 1997, 36, 2675.
[59] C. Richard A. Catlow, David S. Coombes and Dewi W. Lewis. Computer Modeling of Nucleation, Growth, and Templating in Hydrothermal Synthesis. Chem. Mater. 1998, 10:3249-3265
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[2] H. van Bekkum, E.M. Flanigen, J.C. Jansen et al. Introduction to Zeolite Science and Practice, 2nd edition, Elsevier 2001
[3] S.Mintova, N.Petkov, K.Karaghiosoff et al. Transformation of amorphous silica colloids to nanosized MEL zeolite. Mocroporous and Mesoporous Materials,2001,50 (2-3) :121-128
[4] Svetlana Mintova, Norman H.Olson, Jürgen Senker et al. Mechanism of the Transformation of Silica Precursor Solutions into Si-MFI Zeolite. Angew.Chem.,2002,114(14): 2670-2673
[5] Svetlana Mintova, Norman H. Olson, Thomas Bein .Electron Microscopy Reveals the Nucleation Mechanism of Zeolite Y from Precursor Colloids.Angew.Chem. 1999.38(21):3201-3204
[6] 赵永记，王敬中，项寿鹤等．VPI-5分子筛转晶过程的~(31)P MAS NMR和XRD研究．南开大学学报(自然科学)，1994，(3)：1-5
[7] 董维阳，孙尧俊，贺鹤勇，龙英才，高滋．B-AI-ZSM-5沸石的固相结晶过程和机理的研究．中国科学-B辑，1998，28(3)：258-266
[8] 王仰东，傅乐峰，金大明，董家禄，须沁华．NaA，MAP和MAX高铝沸石的结构定向及其转晶．无机化学学报，2002，(8)：787-791
[9] 彭建彪，谢素娟，王清遐，徐龙伢．几种分子筛转晶和混晶的控制及单一晶体的优化合成．催化学报，2002，23(4)：363-366
[10] M.M.J. Treacy & J.B. Higgins. Collection of Simulated XRD Powder Patterns for Zeolites. 4th edition, Amsterdam: Elsevier, 2001.
[11] http://www.iza-online.org
[12] http://www.zeolites.ethz.ch/Zeolites/Explanations.htm
[13] R.M. Barter, Chemical Nomenclature and Formulation of Compositions of Synthetic and Natural Zeolites. Pure Appl. Chem. 1979(51): 1091-1100
[14] http://www.iza-structure.org/databases/ Atlas/FTC_Rules.html
[15] http://www.iza-structure.org/databases/Atlas/Type_material.html
[16] http://www.iza-structure.org/databases/Atlas/Zeolite_names.html
[17] Ch. Baerlocher, A. Hepp. and W.M Meier. DLS-76, a program for the simulation of crystal structures by geometric refinement. Lab. f. Kristallographie, ETH, Zürich. 1978
[18] http://www.iza-structure.org/databases/Atlas/FD.html
[19] G.O. Grunner and F. Laves, Wiss. Z. Techn. Univers. Dresden 1971(20), 387 H.2.
[20] W. M. Meier and H. J. Moeck, The topology of three-dimensional 4-connected nets: classification of zeolite framework types using coordination sequences, J. Solid State Chem., 1979 (27):349-355
[21] M.O'Keeffe,S.T.Hyde. Vertex symbols for zeolite nets. Zeolites, 1997(19):370-374,
[22] http://www.iza-structure.org/databases/Atlas/LC.html
[23] http://www.iza-structure.org/databases/Atlas/SBU.html
[24] Barrer RM. Synthesis ofa zeolitic mineral with chabazitelike sorptive properties .J. Chem. Soc. 1948:127-132
[25] Barrer RM, Denny PJ. J. Chem.Soc. 1961:971-982
[26] Harry Robson .Verified syntheses of zeolitic materials, second Revised Edition,ELSEVIER
2001 Amsterdam
[27] Robert W. Thompson. Recent Advances in the Understanding of Zeolite Synthesis.Molecular Sieves,Vol. 1. Springer-Verlag Berlin Heidelberg 1998:2-3
[28] Eric G. Derouane, Francisco Lemos, Claude Naccache Fernando Rama Ribeiro. Zeolite Microporous Solids: Synthesis, Structure, and Reactivity. Proceedings of the NATO Advanced Study Institute, Sintra-Estoril, Portugal, 1991
[29] 赵修松，王清遐，李宏愿．沸石合成进展．化工进展，1994，5：32-36
[30] Randolph AD Introduction to the theory of crystallization processes,2nd ed.Academic, London, Larson MA (1988)
[31] Xu Wenyang, Li Jianquan, Li Wenyuan, Zhang Huiming, Liang Bingchang. Nonaqueous synthesis of ZSM-35 and ZSM-5.Zeolite, 1989,(9): 468-473
[32] Xu W Y, Dong J X, Li J P. Anovel method for the preparation of zeolite ZSM-5. J. Chem Soc.Chem Commun 1990 (10):755-756
[33] R. Van Grieken, J.L. Sotelo, J.M. Men_endez, J.A. Melero. Anomalous crystallization mechanism in the synthesis ofnanocrystalline ZSM-5. Microporous and Mesoporous Materials 2000 (39): 135-147
[34] Serrano, D.P.; Van Grieken, R.; Sàchez, P.; Sanz, R.; Rodriguez, L.Crystallization mechanism of all-silica zeolite beta in fluoride medium,Microporous and Mesoporous Materials 2001,46 (1): 35-46
[35] Serrano, D.P.; Uguina, M.A.; Sanz, R.; Castillo, E.; Rodriguez, A.; Sànchez, P. Synthesis and crystallization mechanism of zeolite TS-2 by microwave and conventional heating, Microporous and Mesoporous Materials 2004,69(3): 197-208
[36] 刘中清，王一萌，傅军，何鸣元．静态水热晶化法高效合成MCM 22分子筛．催化学报 2002．23(5)：439-442
[37] Berend Smit, R. Krishna, Monte Carlo simulations in zeolites. Current Opinion in Solid State and Materials Science. 2001 (5): 455-461
[38] Michael D. Macedonia, Darrin D. Moore, and Edward J. Magirnn, Michael M. Olken. Adsorption Studies of Methane, Ethane, and Argon in the Zeolite Mordenite: Molecular Simulations and Experiments, Langmuir 2000, 16, 3823-3834
[39] David Nicholson,U Roland J.-M. Pellenq Adsorption in zeolites: intermolecular interactions and computer simulation, Advances in Colloid and Interface Science, 1998(76-77): 179-202
[40] Marco Antonio Chaer Nascimento ,Computer simulations of the adsorption process of light alkanes in high-silica zeolites, Journal of Molecular Structure (Theochem).1999 (464) :239-247
[41] Konstantin S. Smirnov and Fre'de'ric Thibault-Starzyk,Confinement of Acetonitrile Molecules in Mordenite:A Computer Modeling Study, J. Phys. Chem. B 1999(103): 8595-8601
[42] E.de Vos Burchart,V.A. Verheij, H.van Bekkum, and B. van de Graaf. A consistent molecular mechanics force field for all-silica zeolites.Zeolites, 1992 (12): 183-189
[43] E.de Vos Burchart, H.van Bekkum, and B. van de Graaf. Molecular mechanics studies on MFI-type zeolites:Part3.The monoclinic-orthorhombic phase transition. Zeolites,1993 (13):212-215
[44] 李宝宗，周斌，徐文国，裘式纶，庞文琴，徐如人．高硅沸石计算晶格能与骨架拓扑结构相关．化学研究与应用．1998，10(1)：43-48
[45] 李宝宗，国永敏，庞文琴，徐如人．低硅沸石骨架结构及其稳定性的模拟计算．无机材料学报．2000，15(2)：315-323
[46] 李宝宗，徐文国，裘式纶，庞文琴，徐如人．高硅沸石骨架结构及其稳定性的模拟计算(Ⅰ)．物理化学学报．1998，14(1)：45-50
[47] 李宝宗，徐文国，裘式纶，庞文琴，徐如人．高硅沸石骨架结构及其稳定性的模拟计算(Ⅱ)．催化学报．1998，19(2)：154-158
[48] 郭敏，李乙，李激扬，于吉红，徐如人．具有特定孔道结构的分子筛骨架的设计．复旦学报(自然科学版)．2003，42(6)：861-866
[49] Yi Li, Jihong Yu, Donghan Liu, Wenfu Yan, Ruren Xu, and Ying Xu. Design of Zeolite Frameworks with Defined Pore Geometry through Constrained Assembly of Atoms. Chem. Mater. 2003(15): 2780-2785
[50] 李宝会，孙平川，王利军，金庆华，郭振亚，丁大同．系列新型大孔径分子筛骨架结构设计．无机化学学报．200016(1)：21-26
[51] Baohui Li,Pingchuan Sun,Qinghua Jin,Datong Ding.Studies on the design of a novel topological structure of molecular sieve with extra-large open pores, Zeolite, 1996(17):424-427
[52] 林德昌 周伟正 郭娟 龙英才．四氢呋喃与全硅FER，MTN，MOR和MFI沸石骨架相互作用的计算机模拟．化学学报．2003，6(6)：835～839
[53] 王利军，李宝会，金庆华，朱水平，郭振亚，王敬中，丁大同．模板剂在沸石合成过程中的作用机理研究．化学物理学报2000，13(3)：344-348
[54] 于吉红，李激扬，徐如人．用分子动力学模拟方法研究层孔与微孔磷酸铝化合物中有机胺的模板作用—指导定向合成的有效途径．化学学报．2000，58(7)：790-794
[55] 李激扬，于吉红，徐如人．微孔化合物生成中的结构导向与模板作用．无机化学学报 2004，20(1)-1-16
[56] D. W. Lewis, C. M. Freeman, C. R. A. Catlow, 'Predicting The Templating Ability Of Organic Additives For The Synthesis Of Microporous Materials', J. Phys. Chem., 1995, 99, 11194.
[57] D. W. Lewis, D. J. Willock, C. R. A. Catlow, J. M. Thomas, G. J. Hutchings, 'De Novo Design of Structure-Directing Agents for the Synthesis of Microporous Solids', Nature, 1996, 382, 604.
[58] D. W. Lewis, G. Sankar, J. Wyles, J. M. Thomas, C. R. A. Catlow, D. J. Willock, 'Synthesis of a Small-Pore Microporous Material Using a Computationally Designed Template', Angew. Chemie, 1997, 36, 2675.
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