含钛多孔材料的合成、表征及催化性能研究
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摘要
1983年钛硅分子筛被首次合成,由于其在以H_2O_2为氧化剂、温和条件下进行的有机物分子的选择氧化中具有优异的催化性能,引起了国内外学者的广泛关注。传统的钛硅沸石催化剂具有较高的活性和稳定性,但是狭窄的孔道使得它们不能有效催化大分子的反应。中孔钛硅分子筛的出现在一定程度上解决了这个问题,由于其具有2.0nm以上的宽阔孔道和巨大的比表面积,在大分子的催化转化以及吸附分离等领域中展示出良好的应用前景。然而,与沸石晶体材料不同,中孔钛硅分子筛的孔壁呈无定形,这使得它们的固有催化活性较低,严重限制了它们在工业上的广泛应用。本论文以克服现有钛硅催化材料的缺陷为出发点,在开发新型含钛多孔材料上进行了较为深入的研究。论文的主要内容如下:
对Ti-HMS中孔分子筛的合成过程、样品的结构及催化性能进行了研究。研究发现常规的Ti-HMS分子筛的合成体系呈弱碱性,合成Ti-HM9-carboxylicS较为适宜的n(HCl)/n(DDA)为0.07,对应合成体系的pH值为10.72。在合成过程中增加钛源的用量,所得Ti-HMS分子筛中的骨架钛和非骨架钛含量均增加。较高的晶化温度对Ti-HMS分子筛的合成不利。Ti-HMS晶化过程中母液pH值的变化不大。Ti-HMS分子筛具有无序的蠕虫状结构。Ti-HMS分子筛能够满足大分子硫化物氧化反应的要求,而对于受扩散限制不明显的小分子氧化反应,其催化活性不及TS-1分子筛。以水溶性硅酸钠为硅源也可以合成出含钛中孔分子筛Ti-HMS。
以TS-1分子筛前驱体溶液为硅源和钛源,长链烷基胺为模板剂,在室温条件下合成出一种新型的具有蠕虫状结构的中孔分子筛Ti-WMS。与常规的Ti-HMS相比,Ti-WMS分子筛的有序度较低,孔壁较厚,骨架中包含TS-1沸石的基本结构单元,并可能具有类似于沸石晶体环境中的骨架钛物种。除了均一的中孔,Ti-WMS分子筛中还含有一定量的微孔。Ti-WMS分子筛具有比Ti-HMS分子筛更强的氧化能力,在小分子硫化物噻吩的氧化脱除反应中表现出更高的活性,而在其它大分子硫化物的氧化反应中Ti-WMS分子筛表现出与Ti-HMS分子筛相当的活性。
利用部分晶化的TS-1胶液与十二胺自组装,在室温下制备出一种既包含中孔结构,又含有TS-1沸石相的中孔—微孔复合含钛分子筛Ti-HMS/TS-1。通过对所得样品进行表征和催化性能的考察,发现Ti-HMS/TS-1分子筛中的中孔相与沸石相并非独立存在,沸石的晶粒被包裹或镶嵌于中孔相的团聚体中。Ti-HMS/TS-1分子筛中的中孔相不同于常规的Ti-HMS中孔材料,其孔壁更厚,有序度较低。Ti-HMS/TS-1结合了Ti-HMS和TS-1分子筛的优势,对于噻吩、苯并噻吩和二苯并噻吩的氧化脱除均具有较高的活性。
Since titanium silicalite was synthesized first in 1983,it has attracted much attention for its excellent catalytic performance in the selective oxidation of organic molecules with H_2O_2. Though traditional Ti-containing zeolites possess high activity and stability,the narrow channel make thern inacitive in the reactions of bulky molecules.Ti-containing mesoporous silicas have capacious framework pores(＞2.0nm) and large surface area and exhibit high activity in some large molecular reactions.However,the relative lower oxidation ability and stability of these mesoporous materials,arising from the amorphous nature of their pore walls prevent their wide uses in the industrial process.The purpose of this paper is synthesizing novel materials with multiporous and highly active sites,in order to overcome the shortcoming of existing catalytic materials.
The paper has the following main contents.
The synthesis,characterization and catalytic performance of Ti-HMS mesoporous molecular sieve are studied.It has been shown that traditional Ti-HMS is synthesized under slightly alkaline condition.When the n(HCl)/n(DDA) is 0.07 and the corresponding pH value is 10.72,the obtained Ti-HMS has high quality.With the increase of the amount of titanium source,the contents of both framework and extra-framework titanium species in the products are increased and the optimal n(SiO_2)/n(TiO_2) is 50.Higher crystallization temperature is adverse to the synthesis of Ti-HMS and the pH value of mother liquid change little during the crystallization process.Traditional Ti-HMS possesses wormlike structure.Ti-HMS exhibits excellent performance in oxidation of bulky sulfides.For the reaction of small molecules, however,the activities of Ti-HMS are not as good as TS-1.Ti-containing mesoporous silicas Ti-HMS can also be synthesized with soluble sodium silicate as silica source.
A novel Ti-containing mesoporous material with wormlike structure(Ti-WMS) is assembled from the preformed TS-1 precursors with long-chain alkylamine under ambient temperature.The structural and catalytic performances of obtained Ti-WMS have been researched.The results show that comparing with conventional Ti-HMS,Ti-WMS has a lower order degree and a larger wall thickness.Ti-WMS contains the structural units of TS-1 and the zeolite-like active sites.Besides the uniform mesopores,there are some micropores in the Ti-WMS.Ti-WMS possesses highly oxidation ability and exhibits much higher activity than Ti-HMS in thiophene oxidation.In oxidation of some bulky sulfides,Ti-WMS is also active,with similar activities to Ti-HMS.
A novel Ti-containing meso-microporous material Ti-HMS/TS-1 is synthesized by assembly of TS-1 gel with partial crystallization with dodecylamine at ambient temperature. The material is characterized by a series of techniques and its catalytic performance is investigated by means of sulfides oxidation.It has been shown that Ti-HMS/TS-1 possesses simultaneously a mesoporous phase and a crystalline zeolitic phase and two phases are composite rather than the physical mixture.In addition,relative to conventional Ti-HMS,the mesoporous phase in the Ti-HMS/TS-1 has lower order degree and larger pore wall thickness and may contain the zeolitic structural units.Ti-HMS/TS-1 combines the advantage of single Ti-HMS and TS-1 and exhibits high activity in oxidation of both bulky and small molecular sulfides.
对Ti-HMS中孔分子筛的合成过程、样品的结构及催化性能进行了研究。研究发现常规的Ti-HMS分子筛的合成体系呈弱碱性,合成Ti-HM9-carboxylicS较为适宜的n(HCl)/n(DDA)为0.07,对应合成体系的pH值为10.72。在合成过程中增加钛源的用量,所得Ti-HMS分子筛中的骨架钛和非骨架钛含量均增加。较高的晶化温度对Ti-HMS分子筛的合成不利。Ti-HMS晶化过程中母液pH值的变化不大。Ti-HMS分子筛具有无序的蠕虫状结构。Ti-HMS分子筛能够满足大分子硫化物氧化反应的要求,而对于受扩散限制不明显的小分子氧化反应,其催化活性不及TS-1分子筛。以水溶性硅酸钠为硅源也可以合成出含钛中孔分子筛Ti-HMS。
以TS-1分子筛前驱体溶液为硅源和钛源,长链烷基胺为模板剂,在室温条件下合成出一种新型的具有蠕虫状结构的中孔分子筛Ti-WMS。与常规的Ti-HMS相比,Ti-WMS分子筛的有序度较低,孔壁较厚,骨架中包含TS-1沸石的基本结构单元,并可能具有类似于沸石晶体环境中的骨架钛物种。除了均一的中孔,Ti-WMS分子筛中还含有一定量的微孔。Ti-WMS分子筛具有比Ti-HMS分子筛更强的氧化能力,在小分子硫化物噻吩的氧化脱除反应中表现出更高的活性,而在其它大分子硫化物的氧化反应中Ti-WMS分子筛表现出与Ti-HMS分子筛相当的活性。
利用部分晶化的TS-1胶液与十二胺自组装,在室温下制备出一种既包含中孔结构,又含有TS-1沸石相的中孔—微孔复合含钛分子筛Ti-HMS/TS-1。通过对所得样品进行表征和催化性能的考察,发现Ti-HMS/TS-1分子筛中的中孔相与沸石相并非独立存在,沸石的晶粒被包裹或镶嵌于中孔相的团聚体中。Ti-HMS/TS-1分子筛中的中孔相不同于常规的Ti-HMS中孔材料,其孔壁更厚,有序度较低。Ti-HMS/TS-1结合了Ti-HMS和TS-1分子筛的优势,对于噻吩、苯并噻吩和二苯并噻吩的氧化脱除均具有较高的活性。
Since titanium silicalite was synthesized first in 1983,it has attracted much attention for its excellent catalytic performance in the selective oxidation of organic molecules with H_2O_2. Though traditional Ti-containing zeolites possess high activity and stability,the narrow channel make thern inacitive in the reactions of bulky molecules.Ti-containing mesoporous silicas have capacious framework pores(＞2.0nm) and large surface area and exhibit high activity in some large molecular reactions.However,the relative lower oxidation ability and stability of these mesoporous materials,arising from the amorphous nature of their pore walls prevent their wide uses in the industrial process.The purpose of this paper is synthesizing novel materials with multiporous and highly active sites,in order to overcome the shortcoming of existing catalytic materials.
The paper has the following main contents.
The synthesis,characterization and catalytic performance of Ti-HMS mesoporous molecular sieve are studied.It has been shown that traditional Ti-HMS is synthesized under slightly alkaline condition.When the n(HCl)/n(DDA) is 0.07 and the corresponding pH value is 10.72,the obtained Ti-HMS has high quality.With the increase of the amount of titanium source,the contents of both framework and extra-framework titanium species in the products are increased and the optimal n(SiO_2)/n(TiO_2) is 50.Higher crystallization temperature is adverse to the synthesis of Ti-HMS and the pH value of mother liquid change little during the crystallization process.Traditional Ti-HMS possesses wormlike structure.Ti-HMS exhibits excellent performance in oxidation of bulky sulfides.For the reaction of small molecules, however,the activities of Ti-HMS are not as good as TS-1.Ti-containing mesoporous silicas Ti-HMS can also be synthesized with soluble sodium silicate as silica source.
A novel Ti-containing mesoporous material with wormlike structure(Ti-WMS) is assembled from the preformed TS-1 precursors with long-chain alkylamine under ambient temperature.The structural and catalytic performances of obtained Ti-WMS have been researched.The results show that comparing with conventional Ti-HMS,Ti-WMS has a lower order degree and a larger wall thickness.Ti-WMS contains the structural units of TS-1 and the zeolite-like active sites.Besides the uniform mesopores,there are some micropores in the Ti-WMS.Ti-WMS possesses highly oxidation ability and exhibits much higher activity than Ti-HMS in thiophene oxidation.In oxidation of some bulky sulfides,Ti-WMS is also active,with similar activities to Ti-HMS.
A novel Ti-containing meso-microporous material Ti-HMS/TS-1 is synthesized by assembly of TS-1 gel with partial crystallization with dodecylamine at ambient temperature. The material is characterized by a series of techniques and its catalytic performance is investigated by means of sulfides oxidation.It has been shown that Ti-HMS/TS-1 possesses simultaneously a mesoporous phase and a crystalline zeolitic phase and two phases are composite rather than the physical mixture.In addition,relative to conventional Ti-HMS,the mesoporous phase in the Ti-HMS/TS-1 has lower order degree and larger pore wall thickness and may contain the zeolitic structural units.Ti-HMS/TS-1 combines the advantage of single Ti-HMS and TS-1 and exhibits high activity in oxidation of both bulky and small molecular sulfides.
引文
[1]Everett D H.In IUPAC mannul of symbols and terminology,Pure Appl.Chem.,1972,31(4),578-638.
[2]陈连璋.沸石分子筛催化.大连:大连理工大学出版社.1990.
[3]Wilson S T,Lok B M,Messina C A et al.Aluminophosphate molecular sieves:a new class of microporous crystalline inorganic solids.J.Am.Chem.Soc.,1982,104(4):i146-1147.
[4]Kresge C T,Leonowicz M E,Roth W J et al.Ordered mesoporous molecular sieve synthesized by a liquid-crystal template mechanism.Nature,1992,359(6397):710-712.
[5]Beck J S,Vartuli J C,Zresage C T et al.A new family of mesoporous molecular sieves prepared with liquid crystal templates.J.Am.Chem.Soc.,1992,114(27):10834-10843.
[6]Yanagisawa T,Shimizu T,Zuroda K et al.The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials.Bull.Chem.Soc.Jpn.,1990,63(4):988-992.
[7]Inagaki S,Fukushima Y,Kuroda K.Synthesis of highly ordered mesoporous materials from a layered polysilicate.J.Chem.Soc.Chem.Commun.,1993,(8):680-682.
[8]Tanev P T,Pinnavaia T J.A neutral templating route to mesoporous molecular sieves.Science,1995,267(5199):865-867.
[9]Bagshaw S A,Prouzet E,Pinnavaia T J.Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants.Science,1995,269(5228):1242-1244.
[10]Ryoo R,Kim J M,Ko C H et al.Disordered molecular sieve with branched mesoporous channel network.J.Phys.Chem.1996,100(45):17718-17721.
[11]Huo Q S,Leon R,Petroff P M et al.Mesostructure design with Gemini surfactants:supercage formation in a three dimensional hexagonal array.Science,1995,268(5215):1324-1327.
[12]Huo Q S,Margolese,D I,Stucky G D.Surfactant control of phases in the synthesis of mesoporous silica-based materials.Chem.Mater.,1996,8(5):1147-I160.
[13]Sakamoto Y,Kaneda M,Terasaki O,et al.Direct imaging of the pores and cages of three-dimensional mesoporous materials.Nature,2000,408(6811):449-453.
[14]Zhao D Y,Huo Q S,Feng J L et al.Novel mesoporous silicates with two-dimensional mesostructure direction using rigid bolaform surfactants.Chem.Mater.,1999,11(10):2668-2672.
[15]Zhao D Y,Feng J L,Huo Q S et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores.Science,1998,279(5350):548-552.
[16]Zhao D Y,Huo Q S,Feng J L et al.Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered,hydrothermally stable,mesoporous silica structures.J.Am.Chem.Soc.,1998,120(24):6024-6036.
[17]Chen C Y,Burkett S L,Li H X et al.Studies on mesoporous materials Ⅱ.synthesis mechanism of MCM-41.Micropor.Mater.,1993,2(1):27-34.
[18]Firouzi A,Kumar D,Bull L M et al.Cooperative organization of inorganic-surfactant and biomimetic assemblies.Science,1995,267(5201):1138-1143.
[19]Huo Q S,Margolese D I,Ciesla U et al.Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays.1994,6(8):1176-1191.
[20]Firouzi A,Atef F,Oertli A G et al.Alkaline lyotropic silicate-surfactant liquid crystals.J.Am.Chem.Soc.,1997,119(5):3596-3610.
[21]徐如人,庞文琴,于吉红等.分子筛与多孔材料化学.北京:科学出版社.2004.
[22]Zhang W Z,Fr(o|¨)ba M,Wang J L et al.Mesoporous titanosilicate molecular sieves prepared at ambient temperature by electrostatic(S~+I~-,S~+X~-I~+) and neutral(S°I°) assembly pathways:a comparison of physical properties and catalytic activity for peroxide oxidations.J.Am.Chem.Soc.,1996,118(38):9164-9171.
[23]Taramasso M,Perego G,Notari B.Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides.U.S.Pat.4410501,1983.
[24]Clerici M G,Bellussi G,Romano U.Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalites.J.Catal.1991,129(1):159-167.
[25]曹国英,李宏愿,夏清华等.TS分子筛催化剂上烯丙基氯的环氧化性能.催化学报,1995,16(3):217-221。
[26]高焕新,曹静,陆巍然等.丙烯氧化制环氧丙烷催化剂的合成.石油学报(石油加工),2000,16(3):79-83.
[27]李钢.钛硅分子筛的合成、表征及催化丙烯环氧化性能的研究.大连理工大学博士学位论文,2000.
[28]Notari B.Titanium silicalites.Catal.Today,1993,18(2):163-172.
[29]柯于勇,卢冠忠,王正荣.TS分子筛的催化氧化性能研究Ⅲ.苯酚氧化制苯二酚.华东理工大学学报,1998,24(1):116-121.
[30]Thangaraj A,Kumar R,Ratnasamy P.Direct catalytic hydroxylation of benzene with hydrogen peroxide over titanium-silicate zeolites.Appl.Catal.,1990,57(1):L1-L3.
[31]戴延凤,刘希尧,萨学理.TS-1分子筛催化苯的羟基化性能.分子催化,1998,12(1):48-52.
[32]Tatsumi T,Jappar N.Ammoximation of cyclic ketones on TS-1 and amorphous SiO_2-TiO_2.J.Catal.,1996,161(2):570-576.
[33]Thangaraj A,Sivasanker S,Ratnasamy P.Catalytic properties of crystalline titanium silicalites Ⅲ.ammoximation of cyclohexanone.J.Catal.,1991,131(2):394-400.
[34]高焕新,舒祖斌,曹静等.钛硅分子筛TS-1催化环己酮氨氧化制环己酮肟.催化学报,1998,19(4):329-333
[35]Neri C,Buonomo F.Process for oxidizing alcohols to aldehydes and/or ketones.Eur.Pat.0102655,1984.
[36]Maspero F,Romano U.Oxidation of alcohol with H2O2 catalyzed by titanium silicalite-1.J.Catal.,1994,146(2):476-482.
[37]Clerici M G.Oxidation of saturated hydrocarbons with hydrogen peroxide,catalyzed by titanium silicates.Appl.Catal.,1991,68(1):249-261.
[38]柯于勇,卢冠忠,沈丹风等.TS分子筛的催化氧化性能研究Ⅰ.戊烷的氧化.石油化工,1997,26(2):82-87.
[39]Hulea V,Fajula F,Bousquet J.Mild oxidation with H_2O_2 over Ti-containing molecular sieves-a very efficient method for removing aromatic sulfur compounds from fuels.J.Catal.,2001,198(2):179-186.
[40]Shiraishi Y,Hara H,Komosawa I.Oxidative desulfurization process for light oil using titanium silicate molecular sieve catalysts.J.Chem.Eng.Jpn.,2002,35(12):1305-1311.
[41]Kong L Y,Li G,Wang X S.Kinetics and mechanism of liquid-phase oxidation of thiophene over TS-1 using H_2O_2 under mild conditions.Catal.Lett.,2004,92(3-4):163-167.
[42]Kong L Y,Li G,Wang X S.Mild oxidation of thiophene over TS-1/H_2O_2.Catal.Today.2004,93-95:341-345.
[43]Sheldon R A,Downing R S.Heterogeneous catalytic transformations for environmentally friendly production.Appl.Catal.A:General,1999,189(2):163-183.
[44]Padovan M,Leofanti G,Roffia P et al.Method for the preparation of titanium silicates.Eur.Pat.311983,1989.
[45]Uguina M A,Ovejero G,Grieken R V et al.Synthesis of titanium silicalite-1 from an SiO_2-TiO_2 cogel using a wetness impregnation method.J.Chem.5oc.,Chem.Commun.,1994,(1):27-28.
[46]Li G,Guo XW,Wang XS et al.Synthesis of titanium silicalites in different template systems and their catalytic performance,Appl.Catal.A:General,1999,185(1):11-18.
[47]张义华,王祥生,郭新闻等.钛硅分子筛TS-1的合成、表征及催化性能.催化学报,2001,22(1):92-94.
[48]Gao H X,Suo J S,Li S B.A easy way to prepare TS-1.J.Chem.Soc.,Chem.Commun.,1995,(8):835-843.
[49]高焕新,索继栓,吕功煊等.钛硅分子筛(TS-1)的合成、结构表征及催化性能研究.分子催化,1996,10(1):25-32.
[50]Zhang G Y,Sterte J,Schoeman B.Discrete colloidal crystals of titanium silicalite-1.J.Chem.Soc.,Chem.Commun.,1995.(22):2259-2260.
[51]Tuel A.Crystallization of titanium silicalite-1(TS-1) from gels containing hexanediamine and tetrapropylammounium bromide.Zeolites,1996,16(2-3):108-117.
[52]张雄福,王桂茹,刘海鸥等.在己二胺体系中Ti-SiZSM-5沸石的合成因素研究.石油学报(石油加工),1997,13(3):21-26.
[53]Shibata M,Gabekuca Z.Synthesis of MFI titanosilicates from methylamine-TPABr media.Zeolites,1997,19(4):246-252.
[54]李钢,郭新闻,王祥生等.TPABr-正丁胺体系中的合成与表征.大连理工大学学报,1998,38(3):363-367.
[55]李钢,郭新闻,王祥生.钛硅分子筛结构表征及催化性能研究.燃料化学学报.1998,26(2):119-124.
[56]张义华.钛基催化材料的合成、表征和选择氧化性能研究.大连理工大学博士学位论文,2001.
[57]李钢,王祥生,王丽琴等.两种钛硅分子筛合成体系的比较.石油学报(石油加工),2003,19(4):76-81.
[58]郭新闻,王桂茹,王祥生.Ti-Si Pentasil型杂原子分子筛的气固相痛经取代法制备及其羟基化性能Ⅰ.母体Na~+含量的影响.催化学报,1994,15(3):309-313.
[59]郭新闻,王桂茹,王祥生.Ti-Si Pentasil型杂原子分子筛的气固相痛经取代法制备及其羟基化性能Ⅱ.制备条件及母体对钛进入骨架的影响.催化学报,1995,16(4):420-424.
[60]张法智,郭新闻,王祥生.气固相同晶取代法Ti-ZSM-5沸石的表征及催化性能.大连理工大学学报,1998,38(3):368-371.
[61]Wang X S,Guo X W.Synthesis,characterization and catalytic properties of low cost titanium silicalite.Catal.Today,1999,51(1):177-186.
[62]李明丰,郭新闻,于桂燕等.以de-[B]ZSM-5为母体的钛硅沸石Ti-ZSM-5合成.石油化工,1998,27(5):319-323.
[63]刘民.Ti-ZSM-5沸石的气固相合成、表征和催化性能研究.大连理工大学博士学位论文,2005.
[64]Reddy J S,Kumar R,Ratnasamy P.Titanium silicate-2:synthesis,characterization and catalytic properties.Appl.Catal.,1990,58(2):L1-L4.
[65]Tuel A.Synthesis,characterization,and catalytic properties of the new TiZSM-12zeolite.Zeolites,1995,15(3):236-242.
[66]Serrano D P,Li H X,Davis M E.Synthesis of titanium-containing ZSM-48.J.Chem.Soc.,Chem.Commun.,1992,(10):745-747.
[67]Camblor M A,Corma A,Perez-Pariente J.Synthesis of titanoaluminosilicates isomorphous to zeolite Beta,active as oxidation catalysts.Zeolites,1993,13(2):82-87.
[68]Camblor,M A,Constantini A,Corma A et al.Synthesis and catalytic activity of aluminium-free zeolite Ti-β oxidation catalysts.Chem.Commun.1996,(11):1339-1440.
[69]Blasco T,Camblor M A,Corma A et al.The state of Ti in titanoaluminosilicates isomorohous with zeolite.beta.J.Am.Chem.Soc.,1993,115(25):11806-11813.
[70]Corma A,Esteve P,Martinez A et al.Oxidation of olefins with hydrogen peroxide and tert-butyl hydroperoxide on Ti-Beta catalyst.J.Catal.1995,152(1):18-24.
[71]Leonowiez M E,Lawton J A,Lawton S Let al.MCM-22:A molecular sieve with two independent multidimensional channel systems.Science,1994,264(5167):1910-1913.
[72]Sasidharan M,Wu P,Tatsumi T.Direct fomation of pinacols from olefins over various titano- silicates.J.Catal.2002,209(1):260-265.
[73]Corma A,Navarro M T,Perez-Pariente J.Synthesis of an ultralarge pore titanium silicate isomorphous to MCM-41 and its application as a catalyst for selective oxidation of hydrocarbons.J.Chem.Soc.,Chem.Commun.,1994,(2):147-148.
[74]Blasco T,Corma A,Navarro M T et al.Synthesis,characterization,and catalytic activity of Ti-MCM-41 structures.J.Catal.1995,156(1):65-74.
[75]Alba M D,Luan Z,Klinowski J.Titanosilicate mesoporous molecular sieve MCM-41:synthesis and characterization.J.Phys.Chem.,1996,100(6):2178-2182.
[76]Yu J Q,Feng Z C,Xu Let al.Ti-MCM-41 synthesized from colloidal silica and titanium trichloride:synthesis,characterization,and catalysis.Chem.Mater.2001,13(3):994-998.
[77]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅰ.Ti-MCM-41分子筛的合成.催化学报,2001,22(3):267-270.
[78]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅱ.Ti-MCM-41分子筛的表征.催化学报,2001,22(4):331-334.
[79]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅲ.Ti-MCM-41分子筛的催化活性.催化学报,2001,22(4):335-338.
[80]Zhang W Z,Pinnavaia T J.Transition metal substituted derivatives of cubic MCM-48mesoporous molecular sieves.Catal.Lett.,1996,38(3-4):261-265.
[81]Morey M,Davidson A,Stucky G.A new step toward transition metal incorporation in cubic mesoporous materials:preparation and characterization of Ti-MCM-48.Micropor.Mater.,1996,6(2):99-104.
[82]Koyano K A,Tatsumi T.Synthesis of titanium-containing mesoporous molecular sieves with a cubic structure.J.Chem.Soc.,Chem.Commun.,1996,(2):145-146.
[83]Corma A,Kan Q.Synthesis of Si and Ti-Si-MCM-48 mesoporous materials with controlled pore sizes in the absence of polar organic additives and alkali metal ions.Chem.Commun.,1998,(5):579-580.
[84]Tanev P T,Chibwe M,Pinnavaia T J.Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds.Nature,1994,368(6469):321-323.
[85]Zhang W Z,Wang J L,Tanev P T et al.Catalytic hydroxylation of benzene over transition-metal substituted hexagonal mesoporous siIicas.Chem.Commun.,1996,(8):979-980.
[86]Gontier S,Tuel A.Synthesis and characterization of Ti-containing mesoporous silicas.Zeolites,1995,15(7):601-610.
[87]金长子,李钢,王祥生等.Ti-HMS分子筛的合成、表征及催化性能研究.石油学报(石油加工),2005,21(6):51-56.
[88]金长子,李钢,王祥生等.Ti-HMS和TS-1分子筛结构和催化性能的对比研究.催化学报,2007,28(2):170-174.
[89]王云,李钢,王祥生等.Ti-HMS催化氧化脱除模拟燃料中的硫化物.催化学报,2005,26(7):567-570.
[90]罗勇,卢冠忠,黄家桢等.用无机钛源合成Ti-HMS中孔分子筛.华东理工大学学报,2002,28(5):529-532.
[91]Bagshaw S A,Di Renzo F,Fajula F.Preparation of metal-incorporated MSU mesoporous silica molecular sieves.Ti incorporation via a totally non-ionic route.Chem.Commun.,1996,(18):2209-2210.
[92]朱金华,沈伟,徐华龙等.水热一步法合成Ti-SBA-15分子筛及其催化性能研究.化学学报,2003,61(2):202-207.
[93]Chen Y Y,Huang Y L,Xiu J H et al.Direct synthesis,characterization and catalytic activity of titanium-substituted SBA-I5 mesoporous molecular sieves.Appl.Catal A:General,2004,273(1-2):185-191.
[94]Luan Z H,Kevan L.Characterization of titanium-containing mesoporous silica molecular sieve SBA-15 and generation of paramagnetic hole and electron centers.Micropor.Mesopor.Mater.,2001,44-45:337-344.
[95]Newalkar B L,Olanrewaju J,Komarneni S.Direct synthesis of titanium-substituted mesoporous SBA-15 molecular sieve under microwave-hydrothermal conditions.Chem.Mater.2001,13(2):552-557.
[96]Wu S,Han Y,Zou Y C et al.Synthesis of heteroatom substituted SBA-15 by the "pH-Adjusting" method.Chem.Mater.2004,16(3):486-492.
[97]吴硕.高水热稳定的介孔杂原子分子筛的合成与表征.吉林大学硕士学位论文,2004
[98]Xiao F S,Han Y,Yu Y et al.Hydrothermally stable ordered mesoporous titanosilicates with highly active catalytic sites.J.Am.Chem.Soc.,2002,124(6):B88-889.
[99]Meng X J,Li D F,Yang X Y et al.Synthesis,characterization,and catalytic activity of mesostructured titanosilicates assembled from polymer surfactants with preformed titanosilicate precursors in strongly acidic media.J.Phys.Chem.B 2003,107(34):8972-8980.
[100]Meng X J,Fan W B,Kubota Y et al.Improvement in thermal stability and catalytic activity of titanium species in mesoporous titanosilicates by addition of ammonium salts.J.Catal.,2006,244(2):192-198.
[101]Yang X Y,Han Y,Lin K F et al.Ordered mesoporous titanosilicates with catalytically stable and active four-coordinated titanium sites.Chem.Commun.,2004,(19):2612-2613.
[102]Han Y,Li D F,Zhao Let al.High-temperature generalized synthesis of stable ordered mesoporous silica-based materials by using fluorocarbon-hydrocarbon surfactant mixtures.Angew.Chem.Int.Ed.,2003,42(31):3633-3637.
[103]Lin K F,Sun Z H,Lin S et al.Ordered mesoporous titanosilicates with better catalytically active titanium sites assembled from Preformed titanosilicate precursors with zeolite building units in alkaline media.Micropor.Mesopor.Mater.,2004,72(1-3):193-201.
[104]Jin C Z,Li G,Wang X Set al.Synthesis,characterization and catalytic performance of Ti-containing mesoporous molecular sieves assembled from titanosilicate precursors.Chem.Mater.2007,19(7):1664-1670.
[105]Poladi R H P R,Landry C C.Oxidation of octane and cyclohexane using a new porous substrate,Ti-MMM-1.Micropor.Mesopor.Mater.,2002,52(1):11-18.
[106]On D T,Lutic D,Kaliaguine S.An example of mesostructured zeolitic material:UL-TS-1.Micropor.Mesopor.Mater.,2001,44-45:435-444.
[107]Jin C Z,Li G,Wang X Set al.A titanium containing micro/mesoporous.composite and its catalytic performance in oxidative desulfurization.Micropor.Mesopor.Mater.,2008,111(1-3):236-242.
[108]Tao Y,Kanoh H,Abrams L et al.Mesopore-modified zeolites:preparation,characterization,and applications.Chem.Rev.,2006,106(3):896-910.
[109]李鹏.有机碱改性TS-1的表征及其甲乙酮氨氧化性能的研究.大连理工大学硕士学位论文,2006.
[110]赵丽霞,李钢,金长子等.四丙基氢氧化铵改性TS-1催化氧化脱除2-甲基噻吩.石油学报(石油加工),2007,23(4):95-99.
[111]Schmidt I,Krogh A,Wienberg K et al.Catalytic epoxidation of alkenes with hydrogen peroxide over first mesoporous titanium-containing zeolite.Chem.Commun.,2000,(21):2157-2158.
[112]林凯峰.具有高氧化活性的介孔催化材料的合成及其结构与催化性能表征.吉林大学博士学位论文,2005.
[113]Fang Y M,Hu H Q.Mesoporous TS-1:Nanocasting synthesis with CMK-3 as template and its performance in catalytic oxidation of aromatic thiophene.Catal.Commun.,2007,8(5):817-820.
[114]Wang L Q,Wang X S,Guo X W et al.Quick synthesis of titanium silicalite-1.Chin.J.Catal.,2001,22(6):513-514.
[115]李钢,王祥生,金长子等.Ti-HMS分子筛的合成与表征.催化学报,2004,25(4):315-318.
[116]Blasco T,Camlor M A,Corma A et al.The state of Ti in titanoaluminosilicates isomorphous with zeolite beta.J.Am.Chem.Soc.,1993,i15(25):11806-11813.
[117]王丽琴,王祥生,郭新闻等。合成TS-1分子筛的结晶动力学及催化性能研究。催化学报,200324(2):132-136.
[118]Zhang W Zh,Pauly T R,Pinnavaia T J.Tailoring the framework and textural mesopores of HMS molecular Sieves through an electrically neutral(S~0I~0) assembly pathway.Chem.Mater.,1997,9(11):2491-2498.
[119]Yayssilov G N.Structural and physicochemical features of titanium silicalites.Catal.Rev-Sci.Eng.,1997,39(3):209-251.
[120]de Man A J M,Sauer J.Coordination,structure,and vibrational spectra of titanium in silicates and zeolites in comparison with related molecules.An ab initio study.J.Phys.Chem.,1996,100(12):5025-5034.
[121]Camblor M A,Corma A,Perez-Pariente J.Infrared spectroscopic investigation of titanium in zeolites.A new assignment of the 960 cm~(-1) band..l.Chem.Soc.,Chem.Commun.,1993,(6):557-559.
[122]Reddy R S,Reddy J S,Kumar R et al.Sulfoxidation of thioethers using titanium silicate molecular sieve catalysts.J.Chem.Soc.,Chem.Commun.,1992,(2):84-85.
[123]Chica,A.;Corma,A.;Domine,M.E.Catalytic oxidative desulfurization(ODS) of diesel fuel on a continuous fix-bed reactor.J.Catal.,2006,242(2):299-308.
[124]Pinnavaia T J,Pauly T R,Kim S S.Process for the preparation of hybrid mesoporous molecular sieve silicas from amine surfactants.U.S.Pat.6800266,2004.
[125]van der Pol A J H P,van Hooff J H C.Parameters affecting the synthesis of titanium silicate 1.Appl.Catal.A:General,1992,92(2):93-111.
[126]Li G,Wang X S,Yan H S et al.Effect of sodium ions on propylene epoxidation catalyzed by titanium silicalite.Appl.Catal.A:General,2001,218(1-2):31-38.
[127]韩宇.高水热稳定的介孔分子筛的合成与表征.吉林大学博士学位论文,2003.
[128]Miyazawa K,Inagaki S.Control of the microporosity within the pore walls of ordered mesoporous silica SBA-15.Chem.Commun.,2000,(21):2121-2122.
[129]Bonardet J L,Fraissard J,Gedeon A et al.Nuclear magnetic resonance of physisorbed ~(129)Xe used as a probe to investigate porous solids.Catal.Rev-Sci.Eng.,1999,41(2):115-225.
[130]Zhang W P,Han X W,Liu X C et al.Xenon probe for detecting the microporous structure of nanosized HZSM-5 zeolite.Chem.Commun.,2001,(3):293-294.
[131]Haake M,Pines A,Reimer J A et al.Surface-enhanced NMR using continuous-flow laser-polarized xenon.J.Am.Chem.Soc.,1997,119(48):11711-11712.
[132]Zhang W,Ratcliffe C I,Moudrakovski I et al.Distribution of gallium nanocrystals in Ga/MCM-41 mesocomposites by continuous-flow hyperpolarized 129Xe NMR spectroscopy.Anal.Chem.,2005,77(10):3379-3392.
[133]Sakthivel A,Huang S J,Chen W H et al.Replication of mesoporous aluminosilicate molecular sieves(RMMs) with zeolite framework from mesoporous carbons(CMKs).Chem.Mater.,2004,16(16):3168-3175.
[134]赵丽霞.钛硅分子筛催化氧化脱除硫化物研究.大连理工大学硕士学位论文,2007.
[135]Xia Y D,Mokaya R.Are mesoporous silicas and aluminosilicas assembled from zeolite seeds inherently hydrothermally stable? Comparative evaluation of MCM-48 materials assembled from zeolite seeds.J.Mater.Chem.,2004,14(23):3427-3435.
[136]Han Y,Li N,Zhao L et al.Understanding of the high hydrothermal stability of the mesoporous materials prepared by the assembly of triblock copolymer with preformed zeolite precursors in acidic media.J.Phys.Chem.B,2003,107(31):7551-7556.
[137]Liu Y,Pinnavaia T J.Assembly of wormhole aluminosilicate mesostructures from zeolite seeds.J.Mater.Chem.,2004,14(7):1099-1103.
[138]Tarter P T,Pinnavaia T J.Mesoporous silica molecular sieves prepared by ionic and neutral surfactant templating:a comparison of physical properties.Chem.Mater.,1996,8(8):2068-2079.
[139]Guo W P,Huang L M,Deng Pet al.Characterization of Beta/MCM-41 composite molecular sieve compared with the mechanical mixture.Micropor.Mesopor.Mater.,2001,44-45:427-434.
[140]De Filippis P,Scarsella M.Oxidative desulfurization:oxidation reactivity of sulfur compounds in different organic matrixes.Energ.Fuel.,2003,17(6):1452-1455.
[1]Xiao F S,Han Y,Yu Yet al.Hydrothermally stable ordered mesoporous titanosilicates with highly active catalytic sites.J.Am.Chem.Soc.,2002,124(6):888-889.
[2]Meng X J,Li D F,Yang X Y et al.Synthesis,characterization,and catalytic activity of mesostructured titanosilicates assembled from polymer surfactants with preformed titanosilicate precursors in strongly acidic media.J.Phys.Chem.B 2003,107(34):8972-8980.
[3]Meng X J,Fan W B,Kubota Yet al.Improvement in thermal stability and catalytic activity of titanium species in mesoporous titanosilicates by addition of ammonium salts.J.Catal.,2006,244(2):192-198.
[4]Yang X Y,Han Y,Lin K F et al.Ordered mesoporous titanosilicates with catalytically stable and active four-coordinated titanium sites.Chem.Commun.,2004,(19):2612-2613.
[5]Lin K F,Sun Z H,Lin S et al.Ordered mesoporous titanosilicates with better catalytically active titanium sites assembled from preformed titanosilicate precursors with zeolite building units in alkaline media.Micropor.Mesopor.Mater.,2004,72(1-3):193-201.
[6]Jin C Z,Li G,Wang X S et al.Synthesis,characterization and catalytic performance of Ti-containing mesoporous molecular sieves assembled from titanosilicate precursors.Chem.Mater.2007,19(7):1664-1670.
[7]Liu Y,Zhang W Z,Pinnavaia T J.Steam-stable aluminosilicate mesostructures assembled from zeolite type Y seeds.J.Am.Chem.Soc.,2000,122(36):8791-8792.
[8]Zhang Z T,Han Y,Xiao F Set al.Mesoporous aluminosilicates with ordered hexagonal structure,strong acidity,and extraordinary hydrothermal stability at high temperatures.J.Am.Chem.Soc.,2001,123(21):5014-5021.
[9]Liu Y,Zhang W Z,Pinnavaia T J.Steam-stable aluminosilicate mesostructures assembled from zeolite ZSM-5 and zeolite Beta seeds.Angew.Chem.,Int.Ed.,2001,40(7):1255-1258.
[10]Han Y,Wu S,Sun Y Y et al.Hydrothermally stable ordered hexagonal mesoporous alunminosilicates assembled from a triblock copolymer and preformed aluminosilicate precursors in strongly acidic media.Chem.Mater.,2002,14(3):1144-1148.
[11]Goto Y,Fukushima Y,Ratu P et al.Mesoporous material from zeolite.J.Porous.Mat.,2002,9(1):43-48.
[12]Inagaki S,Ogura M,Inami T et al.Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite.Micropor.Mesopor.Mater.,2004,74(1-3):163-170.
[13]Wang H,Liu Y,Pinnavaia T J.Highly acidic mesostructured aluminosilicates assembled from surfactant-mediated zeolite hydrolysis products.J.Phys.Chem.B,2006,110(10):4524-4526.
[14]李英武.含钛中孔分子筛的合成、表征及其催化性能.大连理工大学硕士学位论文,2004.
[15]王姗,窦志荣,李玉平等.强酸性和水热稳定的MCM-41分子筛的合成.太原理工大学学报,2005,36(3):273-275.
[16]Cizmek A,Subotic B,Aiello R et al.Dissolution of high-silica zeolites in alkaline solutions I.Dissolution of silicalite-1 and ZSM-5 with different aluminum content.Micropor.Mater.,1995,4(2-3):159-168.
[2]陈连璋.沸石分子筛催化.大连:大连理工大学出版社.1990.
[3]Wilson S T,Lok B M,Messina C A et al.Aluminophosphate molecular sieves:a new class of microporous crystalline inorganic solids.J.Am.Chem.Soc.,1982,104(4):i146-1147.
[4]Kresge C T,Leonowicz M E,Roth W J et al.Ordered mesoporous molecular sieve synthesized by a liquid-crystal template mechanism.Nature,1992,359(6397):710-712.
[5]Beck J S,Vartuli J C,Zresage C T et al.A new family of mesoporous molecular sieves prepared with liquid crystal templates.J.Am.Chem.Soc.,1992,114(27):10834-10843.
[6]Yanagisawa T,Shimizu T,Zuroda K et al.The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials.Bull.Chem.Soc.Jpn.,1990,63(4):988-992.
[7]Inagaki S,Fukushima Y,Kuroda K.Synthesis of highly ordered mesoporous materials from a layered polysilicate.J.Chem.Soc.Chem.Commun.,1993,(8):680-682.
[8]Tanev P T,Pinnavaia T J.A neutral templating route to mesoporous molecular sieves.Science,1995,267(5199):865-867.
[9]Bagshaw S A,Prouzet E,Pinnavaia T J.Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants.Science,1995,269(5228):1242-1244.
[10]Ryoo R,Kim J M,Ko C H et al.Disordered molecular sieve with branched mesoporous channel network.J.Phys.Chem.1996,100(45):17718-17721.
[11]Huo Q S,Leon R,Petroff P M et al.Mesostructure design with Gemini surfactants:supercage formation in a three dimensional hexagonal array.Science,1995,268(5215):1324-1327.
[12]Huo Q S,Margolese,D I,Stucky G D.Surfactant control of phases in the synthesis of mesoporous silica-based materials.Chem.Mater.,1996,8(5):1147-I160.
[13]Sakamoto Y,Kaneda M,Terasaki O,et al.Direct imaging of the pores and cages of three-dimensional mesoporous materials.Nature,2000,408(6811):449-453.
[14]Zhao D Y,Huo Q S,Feng J L et al.Novel mesoporous silicates with two-dimensional mesostructure direction using rigid bolaform surfactants.Chem.Mater.,1999,11(10):2668-2672.
[15]Zhao D Y,Feng J L,Huo Q S et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores.Science,1998,279(5350):548-552.
[16]Zhao D Y,Huo Q S,Feng J L et al.Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered,hydrothermally stable,mesoporous silica structures.J.Am.Chem.Soc.,1998,120(24):6024-6036.
[17]Chen C Y,Burkett S L,Li H X et al.Studies on mesoporous materials Ⅱ.synthesis mechanism of MCM-41.Micropor.Mater.,1993,2(1):27-34.
[18]Firouzi A,Kumar D,Bull L M et al.Cooperative organization of inorganic-surfactant and biomimetic assemblies.Science,1995,267(5201):1138-1143.
[19]Huo Q S,Margolese D I,Ciesla U et al.Organization of organic molecules with inorganic molecular species into nanocomposite biphase arrays.1994,6(8):1176-1191.
[20]Firouzi A,Atef F,Oertli A G et al.Alkaline lyotropic silicate-surfactant liquid crystals.J.Am.Chem.Soc.,1997,119(5):3596-3610.
[21]徐如人,庞文琴,于吉红等.分子筛与多孔材料化学.北京:科学出版社.2004.
[22]Zhang W Z,Fr(o|¨)ba M,Wang J L et al.Mesoporous titanosilicate molecular sieves prepared at ambient temperature by electrostatic(S~+I~-,S~+X~-I~+) and neutral(S°I°) assembly pathways:a comparison of physical properties and catalytic activity for peroxide oxidations.J.Am.Chem.Soc.,1996,118(38):9164-9171.
[23]Taramasso M,Perego G,Notari B.Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides.U.S.Pat.4410501,1983.
[24]Clerici M G,Bellussi G,Romano U.Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalites.J.Catal.1991,129(1):159-167.
[25]曹国英,李宏愿,夏清华等.TS分子筛催化剂上烯丙基氯的环氧化性能.催化学报,1995,16(3):217-221。
[26]高焕新,曹静,陆巍然等.丙烯氧化制环氧丙烷催化剂的合成.石油学报(石油加工),2000,16(3):79-83.
[27]李钢.钛硅分子筛的合成、表征及催化丙烯环氧化性能的研究.大连理工大学博士学位论文,2000.
[28]Notari B.Titanium silicalites.Catal.Today,1993,18(2):163-172.
[29]柯于勇,卢冠忠,王正荣.TS分子筛的催化氧化性能研究Ⅲ.苯酚氧化制苯二酚.华东理工大学学报,1998,24(1):116-121.
[30]Thangaraj A,Kumar R,Ratnasamy P.Direct catalytic hydroxylation of benzene with hydrogen peroxide over titanium-silicate zeolites.Appl.Catal.,1990,57(1):L1-L3.
[31]戴延凤,刘希尧,萨学理.TS-1分子筛催化苯的羟基化性能.分子催化,1998,12(1):48-52.
[32]Tatsumi T,Jappar N.Ammoximation of cyclic ketones on TS-1 and amorphous SiO_2-TiO_2.J.Catal.,1996,161(2):570-576.
[33]Thangaraj A,Sivasanker S,Ratnasamy P.Catalytic properties of crystalline titanium silicalites Ⅲ.ammoximation of cyclohexanone.J.Catal.,1991,131(2):394-400.
[34]高焕新,舒祖斌,曹静等.钛硅分子筛TS-1催化环己酮氨氧化制环己酮肟.催化学报,1998,19(4):329-333
[35]Neri C,Buonomo F.Process for oxidizing alcohols to aldehydes and/or ketones.Eur.Pat.0102655,1984.
[36]Maspero F,Romano U.Oxidation of alcohol with H2O2 catalyzed by titanium silicalite-1.J.Catal.,1994,146(2):476-482.
[37]Clerici M G.Oxidation of saturated hydrocarbons with hydrogen peroxide,catalyzed by titanium silicates.Appl.Catal.,1991,68(1):249-261.
[38]柯于勇,卢冠忠,沈丹风等.TS分子筛的催化氧化性能研究Ⅰ.戊烷的氧化.石油化工,1997,26(2):82-87.
[39]Hulea V,Fajula F,Bousquet J.Mild oxidation with H_2O_2 over Ti-containing molecular sieves-a very efficient method for removing aromatic sulfur compounds from fuels.J.Catal.,2001,198(2):179-186.
[40]Shiraishi Y,Hara H,Komosawa I.Oxidative desulfurization process for light oil using titanium silicate molecular sieve catalysts.J.Chem.Eng.Jpn.,2002,35(12):1305-1311.
[41]Kong L Y,Li G,Wang X S.Kinetics and mechanism of liquid-phase oxidation of thiophene over TS-1 using H_2O_2 under mild conditions.Catal.Lett.,2004,92(3-4):163-167.
[42]Kong L Y,Li G,Wang X S.Mild oxidation of thiophene over TS-1/H_2O_2.Catal.Today.2004,93-95:341-345.
[43]Sheldon R A,Downing R S.Heterogeneous catalytic transformations for environmentally friendly production.Appl.Catal.A:General,1999,189(2):163-183.
[44]Padovan M,Leofanti G,Roffia P et al.Method for the preparation of titanium silicates.Eur.Pat.311983,1989.
[45]Uguina M A,Ovejero G,Grieken R V et al.Synthesis of titanium silicalite-1 from an SiO_2-TiO_2 cogel using a wetness impregnation method.J.Chem.5oc.,Chem.Commun.,1994,(1):27-28.
[46]Li G,Guo XW,Wang XS et al.Synthesis of titanium silicalites in different template systems and their catalytic performance,Appl.Catal.A:General,1999,185(1):11-18.
[47]张义华,王祥生,郭新闻等.钛硅分子筛TS-1的合成、表征及催化性能.催化学报,2001,22(1):92-94.
[48]Gao H X,Suo J S,Li S B.A easy way to prepare TS-1.J.Chem.Soc.,Chem.Commun.,1995,(8):835-843.
[49]高焕新,索继栓,吕功煊等.钛硅分子筛(TS-1)的合成、结构表征及催化性能研究.分子催化,1996,10(1):25-32.
[50]Zhang G Y,Sterte J,Schoeman B.Discrete colloidal crystals of titanium silicalite-1.J.Chem.Soc.,Chem.Commun.,1995.(22):2259-2260.
[51]Tuel A.Crystallization of titanium silicalite-1(TS-1) from gels containing hexanediamine and tetrapropylammounium bromide.Zeolites,1996,16(2-3):108-117.
[52]张雄福,王桂茹,刘海鸥等.在己二胺体系中Ti-SiZSM-5沸石的合成因素研究.石油学报(石油加工),1997,13(3):21-26.
[53]Shibata M,Gabekuca Z.Synthesis of MFI titanosilicates from methylamine-TPABr media.Zeolites,1997,19(4):246-252.
[54]李钢,郭新闻,王祥生等.TPABr-正丁胺体系中的合成与表征.大连理工大学学报,1998,38(3):363-367.
[55]李钢,郭新闻,王祥生.钛硅分子筛结构表征及催化性能研究.燃料化学学报.1998,26(2):119-124.
[56]张义华.钛基催化材料的合成、表征和选择氧化性能研究.大连理工大学博士学位论文,2001.
[57]李钢,王祥生,王丽琴等.两种钛硅分子筛合成体系的比较.石油学报(石油加工),2003,19(4):76-81.
[58]郭新闻,王桂茹,王祥生.Ti-Si Pentasil型杂原子分子筛的气固相痛经取代法制备及其羟基化性能Ⅰ.母体Na~+含量的影响.催化学报,1994,15(3):309-313.
[59]郭新闻,王桂茹,王祥生.Ti-Si Pentasil型杂原子分子筛的气固相痛经取代法制备及其羟基化性能Ⅱ.制备条件及母体对钛进入骨架的影响.催化学报,1995,16(4):420-424.
[60]张法智,郭新闻,王祥生.气固相同晶取代法Ti-ZSM-5沸石的表征及催化性能.大连理工大学学报,1998,38(3):368-371.
[61]Wang X S,Guo X W.Synthesis,characterization and catalytic properties of low cost titanium silicalite.Catal.Today,1999,51(1):177-186.
[62]李明丰,郭新闻,于桂燕等.以de-[B]ZSM-5为母体的钛硅沸石Ti-ZSM-5合成.石油化工,1998,27(5):319-323.
[63]刘民.Ti-ZSM-5沸石的气固相合成、表征和催化性能研究.大连理工大学博士学位论文,2005.
[64]Reddy J S,Kumar R,Ratnasamy P.Titanium silicate-2:synthesis,characterization and catalytic properties.Appl.Catal.,1990,58(2):L1-L4.
[65]Tuel A.Synthesis,characterization,and catalytic properties of the new TiZSM-12zeolite.Zeolites,1995,15(3):236-242.
[66]Serrano D P,Li H X,Davis M E.Synthesis of titanium-containing ZSM-48.J.Chem.Soc.,Chem.Commun.,1992,(10):745-747.
[67]Camblor M A,Corma A,Perez-Pariente J.Synthesis of titanoaluminosilicates isomorphous to zeolite Beta,active as oxidation catalysts.Zeolites,1993,13(2):82-87.
[68]Camblor,M A,Constantini A,Corma A et al.Synthesis and catalytic activity of aluminium-free zeolite Ti-β oxidation catalysts.Chem.Commun.1996,(11):1339-1440.
[69]Blasco T,Camblor M A,Corma A et al.The state of Ti in titanoaluminosilicates isomorohous with zeolite.beta.J.Am.Chem.Soc.,1993,115(25):11806-11813.
[70]Corma A,Esteve P,Martinez A et al.Oxidation of olefins with hydrogen peroxide and tert-butyl hydroperoxide on Ti-Beta catalyst.J.Catal.1995,152(1):18-24.
[71]Leonowiez M E,Lawton J A,Lawton S Let al.MCM-22:A molecular sieve with two independent multidimensional channel systems.Science,1994,264(5167):1910-1913.
[72]Sasidharan M,Wu P,Tatsumi T.Direct fomation of pinacols from olefins over various titano- silicates.J.Catal.2002,209(1):260-265.
[73]Corma A,Navarro M T,Perez-Pariente J.Synthesis of an ultralarge pore titanium silicate isomorphous to MCM-41 and its application as a catalyst for selective oxidation of hydrocarbons.J.Chem.Soc.,Chem.Commun.,1994,(2):147-148.
[74]Blasco T,Corma A,Navarro M T et al.Synthesis,characterization,and catalytic activity of Ti-MCM-41 structures.J.Catal.1995,156(1):65-74.
[75]Alba M D,Luan Z,Klinowski J.Titanosilicate mesoporous molecular sieve MCM-41:synthesis and characterization.J.Phys.Chem.,1996,100(6):2178-2182.
[76]Yu J Q,Feng Z C,Xu Let al.Ti-MCM-41 synthesized from colloidal silica and titanium trichloride:synthesis,characterization,and catalysis.Chem.Mater.2001,13(3):994-998.
[77]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅰ.Ti-MCM-41分子筛的合成.催化学报,2001,22(3):267-270.
[78]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅱ.Ti-MCM-41分子筛的表征.催化学报,2001,22(4):331-334.
[79]于健强,李灿,许磊等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅲ.Ti-MCM-41分子筛的催化活性.催化学报,2001,22(4):335-338.
[80]Zhang W Z,Pinnavaia T J.Transition metal substituted derivatives of cubic MCM-48mesoporous molecular sieves.Catal.Lett.,1996,38(3-4):261-265.
[81]Morey M,Davidson A,Stucky G.A new step toward transition metal incorporation in cubic mesoporous materials:preparation and characterization of Ti-MCM-48.Micropor.Mater.,1996,6(2):99-104.
[82]Koyano K A,Tatsumi T.Synthesis of titanium-containing mesoporous molecular sieves with a cubic structure.J.Chem.Soc.,Chem.Commun.,1996,(2):145-146.
[83]Corma A,Kan Q.Synthesis of Si and Ti-Si-MCM-48 mesoporous materials with controlled pore sizes in the absence of polar organic additives and alkali metal ions.Chem.Commun.,1998,(5):579-580.
[84]Tanev P T,Chibwe M,Pinnavaia T J.Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds.Nature,1994,368(6469):321-323.
[85]Zhang W Z,Wang J L,Tanev P T et al.Catalytic hydroxylation of benzene over transition-metal substituted hexagonal mesoporous siIicas.Chem.Commun.,1996,(8):979-980.
[86]Gontier S,Tuel A.Synthesis and characterization of Ti-containing mesoporous silicas.Zeolites,1995,15(7):601-610.
[87]金长子,李钢,王祥生等.Ti-HMS分子筛的合成、表征及催化性能研究.石油学报(石油加工),2005,21(6):51-56.
[88]金长子,李钢,王祥生等.Ti-HMS和TS-1分子筛结构和催化性能的对比研究.催化学报,2007,28(2):170-174.
[89]王云,李钢,王祥生等.Ti-HMS催化氧化脱除模拟燃料中的硫化物.催化学报,2005,26(7):567-570.
[90]罗勇,卢冠忠,黄家桢等.用无机钛源合成Ti-HMS中孔分子筛.华东理工大学学报,2002,28(5):529-532.
[91]Bagshaw S A,Di Renzo F,Fajula F.Preparation of metal-incorporated MSU mesoporous silica molecular sieves.Ti incorporation via a totally non-ionic route.Chem.Commun.,1996,(18):2209-2210.
[92]朱金华,沈伟,徐华龙等.水热一步法合成Ti-SBA-15分子筛及其催化性能研究.化学学报,2003,61(2):202-207.
[93]Chen Y Y,Huang Y L,Xiu J H et al.Direct synthesis,characterization and catalytic activity of titanium-substituted SBA-I5 mesoporous molecular sieves.Appl.Catal A:General,2004,273(1-2):185-191.
[94]Luan Z H,Kevan L.Characterization of titanium-containing mesoporous silica molecular sieve SBA-15 and generation of paramagnetic hole and electron centers.Micropor.Mesopor.Mater.,2001,44-45:337-344.
[95]Newalkar B L,Olanrewaju J,Komarneni S.Direct synthesis of titanium-substituted mesoporous SBA-15 molecular sieve under microwave-hydrothermal conditions.Chem.Mater.2001,13(2):552-557.
[96]Wu S,Han Y,Zou Y C et al.Synthesis of heteroatom substituted SBA-15 by the "pH-Adjusting" method.Chem.Mater.2004,16(3):486-492.
[97]吴硕.高水热稳定的介孔杂原子分子筛的合成与表征.吉林大学硕士学位论文,2004
[98]Xiao F S,Han Y,Yu Y et al.Hydrothermally stable ordered mesoporous titanosilicates with highly active catalytic sites.J.Am.Chem.Soc.,2002,124(6):B88-889.
[99]Meng X J,Li D F,Yang X Y et al.Synthesis,characterization,and catalytic activity of mesostructured titanosilicates assembled from polymer surfactants with preformed titanosilicate precursors in strongly acidic media.J.Phys.Chem.B 2003,107(34):8972-8980.
[100]Meng X J,Fan W B,Kubota Y et al.Improvement in thermal stability and catalytic activity of titanium species in mesoporous titanosilicates by addition of ammonium salts.J.Catal.,2006,244(2):192-198.
[101]Yang X Y,Han Y,Lin K F et al.Ordered mesoporous titanosilicates with catalytically stable and active four-coordinated titanium sites.Chem.Commun.,2004,(19):2612-2613.
[102]Han Y,Li D F,Zhao Let al.High-temperature generalized synthesis of stable ordered mesoporous silica-based materials by using fluorocarbon-hydrocarbon surfactant mixtures.Angew.Chem.Int.Ed.,2003,42(31):3633-3637.
[103]Lin K F,Sun Z H,Lin S et al.Ordered mesoporous titanosilicates with better catalytically active titanium sites assembled from Preformed titanosilicate precursors with zeolite building units in alkaline media.Micropor.Mesopor.Mater.,2004,72(1-3):193-201.
[104]Jin C Z,Li G,Wang X Set al.Synthesis,characterization and catalytic performance of Ti-containing mesoporous molecular sieves assembled from titanosilicate precursors.Chem.Mater.2007,19(7):1664-1670.
[105]Poladi R H P R,Landry C C.Oxidation of octane and cyclohexane using a new porous substrate,Ti-MMM-1.Micropor.Mesopor.Mater.,2002,52(1):11-18.
[106]On D T,Lutic D,Kaliaguine S.An example of mesostructured zeolitic material:UL-TS-1.Micropor.Mesopor.Mater.,2001,44-45:435-444.
[107]Jin C Z,Li G,Wang X Set al.A titanium containing micro/mesoporous.composite and its catalytic performance in oxidative desulfurization.Micropor.Mesopor.Mater.,2008,111(1-3):236-242.
[108]Tao Y,Kanoh H,Abrams L et al.Mesopore-modified zeolites:preparation,characterization,and applications.Chem.Rev.,2006,106(3):896-910.
[109]李鹏.有机碱改性TS-1的表征及其甲乙酮氨氧化性能的研究.大连理工大学硕士学位论文,2006.
[110]赵丽霞,李钢,金长子等.四丙基氢氧化铵改性TS-1催化氧化脱除2-甲基噻吩.石油学报(石油加工),2007,23(4):95-99.
[111]Schmidt I,Krogh A,Wienberg K et al.Catalytic epoxidation of alkenes with hydrogen peroxide over first mesoporous titanium-containing zeolite.Chem.Commun.,2000,(21):2157-2158.
[112]林凯峰.具有高氧化活性的介孔催化材料的合成及其结构与催化性能表征.吉林大学博士学位论文,2005.
[113]Fang Y M,Hu H Q.Mesoporous TS-1:Nanocasting synthesis with CMK-3 as template and its performance in catalytic oxidation of aromatic thiophene.Catal.Commun.,2007,8(5):817-820.
[114]Wang L Q,Wang X S,Guo X W et al.Quick synthesis of titanium silicalite-1.Chin.J.Catal.,2001,22(6):513-514.
[115]李钢,王祥生,金长子等.Ti-HMS分子筛的合成与表征.催化学报,2004,25(4):315-318.
[116]Blasco T,Camlor M A,Corma A et al.The state of Ti in titanoaluminosilicates isomorphous with zeolite beta.J.Am.Chem.Soc.,1993,i15(25):11806-11813.
[117]王丽琴,王祥生,郭新闻等。合成TS-1分子筛的结晶动力学及催化性能研究。催化学报,200324(2):132-136.
[118]Zhang W Zh,Pauly T R,Pinnavaia T J.Tailoring the framework and textural mesopores of HMS molecular Sieves through an electrically neutral(S~0I~0) assembly pathway.Chem.Mater.,1997,9(11):2491-2498.
[119]Yayssilov G N.Structural and physicochemical features of titanium silicalites.Catal.Rev-Sci.Eng.,1997,39(3):209-251.
[120]de Man A J M,Sauer J.Coordination,structure,and vibrational spectra of titanium in silicates and zeolites in comparison with related molecules.An ab initio study.J.Phys.Chem.,1996,100(12):5025-5034.
[121]Camblor M A,Corma A,Perez-Pariente J.Infrared spectroscopic investigation of titanium in zeolites.A new assignment of the 960 cm~(-1) band..l.Chem.Soc.,Chem.Commun.,1993,(6):557-559.
[122]Reddy R S,Reddy J S,Kumar R et al.Sulfoxidation of thioethers using titanium silicate molecular sieve catalysts.J.Chem.Soc.,Chem.Commun.,1992,(2):84-85.
[123]Chica,A.;Corma,A.;Domine,M.E.Catalytic oxidative desulfurization(ODS) of diesel fuel on a continuous fix-bed reactor.J.Catal.,2006,242(2):299-308.
[124]Pinnavaia T J,Pauly T R,Kim S S.Process for the preparation of hybrid mesoporous molecular sieve silicas from amine surfactants.U.S.Pat.6800266,2004.
[125]van der Pol A J H P,van Hooff J H C.Parameters affecting the synthesis of titanium silicate 1.Appl.Catal.A:General,1992,92(2):93-111.
[126]Li G,Wang X S,Yan H S et al.Effect of sodium ions on propylene epoxidation catalyzed by titanium silicalite.Appl.Catal.A:General,2001,218(1-2):31-38.
[127]韩宇.高水热稳定的介孔分子筛的合成与表征.吉林大学博士学位论文,2003.
[128]Miyazawa K,Inagaki S.Control of the microporosity within the pore walls of ordered mesoporous silica SBA-15.Chem.Commun.,2000,(21):2121-2122.
[129]Bonardet J L,Fraissard J,Gedeon A et al.Nuclear magnetic resonance of physisorbed ~(129)Xe used as a probe to investigate porous solids.Catal.Rev-Sci.Eng.,1999,41(2):115-225.
[130]Zhang W P,Han X W,Liu X C et al.Xenon probe for detecting the microporous structure of nanosized HZSM-5 zeolite.Chem.Commun.,2001,(3):293-294.
[131]Haake M,Pines A,Reimer J A et al.Surface-enhanced NMR using continuous-flow laser-polarized xenon.J.Am.Chem.Soc.,1997,119(48):11711-11712.
[132]Zhang W,Ratcliffe C I,Moudrakovski I et al.Distribution of gallium nanocrystals in Ga/MCM-41 mesocomposites by continuous-flow hyperpolarized 129Xe NMR spectroscopy.Anal.Chem.,2005,77(10):3379-3392.
[133]Sakthivel A,Huang S J,Chen W H et al.Replication of mesoporous aluminosilicate molecular sieves(RMMs) with zeolite framework from mesoporous carbons(CMKs).Chem.Mater.,2004,16(16):3168-3175.
[134]赵丽霞.钛硅分子筛催化氧化脱除硫化物研究.大连理工大学硕士学位论文,2007.
[135]Xia Y D,Mokaya R.Are mesoporous silicas and aluminosilicas assembled from zeolite seeds inherently hydrothermally stable? Comparative evaluation of MCM-48 materials assembled from zeolite seeds.J.Mater.Chem.,2004,14(23):3427-3435.
[136]Han Y,Li N,Zhao L et al.Understanding of the high hydrothermal stability of the mesoporous materials prepared by the assembly of triblock copolymer with preformed zeolite precursors in acidic media.J.Phys.Chem.B,2003,107(31):7551-7556.
[137]Liu Y,Pinnavaia T J.Assembly of wormhole aluminosilicate mesostructures from zeolite seeds.J.Mater.Chem.,2004,14(7):1099-1103.
[138]Tarter P T,Pinnavaia T J.Mesoporous silica molecular sieves prepared by ionic and neutral surfactant templating:a comparison of physical properties.Chem.Mater.,1996,8(8):2068-2079.
[139]Guo W P,Huang L M,Deng Pet al.Characterization of Beta/MCM-41 composite molecular sieve compared with the mechanical mixture.Micropor.Mesopor.Mater.,2001,44-45:427-434.
[140]De Filippis P,Scarsella M.Oxidative desulfurization:oxidation reactivity of sulfur compounds in different organic matrixes.Energ.Fuel.,2003,17(6):1452-1455.
[1]Xiao F S,Han Y,Yu Yet al.Hydrothermally stable ordered mesoporous titanosilicates with highly active catalytic sites.J.Am.Chem.Soc.,2002,124(6):888-889.
[2]Meng X J,Li D F,Yang X Y et al.Synthesis,characterization,and catalytic activity of mesostructured titanosilicates assembled from polymer surfactants with preformed titanosilicate precursors in strongly acidic media.J.Phys.Chem.B 2003,107(34):8972-8980.
[3]Meng X J,Fan W B,Kubota Yet al.Improvement in thermal stability and catalytic activity of titanium species in mesoporous titanosilicates by addition of ammonium salts.J.Catal.,2006,244(2):192-198.
[4]Yang X Y,Han Y,Lin K F et al.Ordered mesoporous titanosilicates with catalytically stable and active four-coordinated titanium sites.Chem.Commun.,2004,(19):2612-2613.
[5]Lin K F,Sun Z H,Lin S et al.Ordered mesoporous titanosilicates with better catalytically active titanium sites assembled from preformed titanosilicate precursors with zeolite building units in alkaline media.Micropor.Mesopor.Mater.,2004,72(1-3):193-201.
[6]Jin C Z,Li G,Wang X S et al.Synthesis,characterization and catalytic performance of Ti-containing mesoporous molecular sieves assembled from titanosilicate precursors.Chem.Mater.2007,19(7):1664-1670.
[7]Liu Y,Zhang W Z,Pinnavaia T J.Steam-stable aluminosilicate mesostructures assembled from zeolite type Y seeds.J.Am.Chem.Soc.,2000,122(36):8791-8792.
[8]Zhang Z T,Han Y,Xiao F Set al.Mesoporous aluminosilicates with ordered hexagonal structure,strong acidity,and extraordinary hydrothermal stability at high temperatures.J.Am.Chem.Soc.,2001,123(21):5014-5021.
[9]Liu Y,Zhang W Z,Pinnavaia T J.Steam-stable aluminosilicate mesostructures assembled from zeolite ZSM-5 and zeolite Beta seeds.Angew.Chem.,Int.Ed.,2001,40(7):1255-1258.
[10]Han Y,Wu S,Sun Y Y et al.Hydrothermally stable ordered hexagonal mesoporous alunminosilicates assembled from a triblock copolymer and preformed aluminosilicate precursors in strongly acidic media.Chem.Mater.,2002,14(3):1144-1148.
[11]Goto Y,Fukushima Y,Ratu P et al.Mesoporous material from zeolite.J.Porous.Mat.,2002,9(1):43-48.
[12]Inagaki S,Ogura M,Inami T et al.Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite.Micropor.Mesopor.Mater.,2004,74(1-3):163-170.
[13]Wang H,Liu Y,Pinnavaia T J.Highly acidic mesostructured aluminosilicates assembled from surfactant-mediated zeolite hydrolysis products.J.Phys.Chem.B,2006,110(10):4524-4526.
[14]李英武.含钛中孔分子筛的合成、表征及其催化性能.大连理工大学硕士学位论文,2004.
[15]王姗,窦志荣,李玉平等.强酸性和水热稳定的MCM-41分子筛的合成.太原理工大学学报,2005,36(3):273-275.
[16]Cizmek A,Subotic B,Aiello R et al.Dissolution of high-silica zeolites in alkaline solutions I.Dissolution of silicalite-1 and ZSM-5 with different aluminum content.Micropor.Mater.,1995,4(2-3):159-168.