摘要
碳酸二苯酯(DPC)是非光气法合成聚碳酸酯的基本原料。近年来,聚碳酸酯以其良好的机械、光学和电子性能得到了广泛应用,从而使得DPC的研究与开发逐步成为人们关注的热点。以苯酚和草酸二甲酯(DMO)酯交换合成DPC是一条具有广泛发展前景的绿色合成工艺路线。本论文研究以DMO和苯酚为原料,通过酯交换反应合成用于制备DPC的甲基苯基草酸酯(MPO)和草酸二苯酯(DPO),重点研究了钼钛固体酸催化剂在该酯交换反应中的催化性能。
对钼钛双金属氧化物的活性考察表明,溶胶凝胶法制备的复合型MoO_3-TiO_2催化剂对酯交换反应的催化性能优于浸渍法制备的负载型MoO_3/TiO_2催化剂。催化剂的BET、XRD、XPS、FT-IR表征显示复合型催化剂中MoO_3与TiO_2分散均匀,并形成Mo-O-Ti键,具有良好的异质组分相容性。MoO_3在TiO_2载体表面的分散符合单层分散理论,在单层分散阈值附近MoO_3-TiO_2催化剂的催化活性最好,尤其有利于MPO歧化反应生成DPO,提高了DPO选择性。晶相MoO_3出现后,催化剂活性和DPO选择性均降低。
考察了固体超强酸SO_4~(2-)/TiO_2对苯酚和DMO酯交换反应的催化活性。BET、XRD、XPS、FT-IR等测试表明通过SO_4~(2-)的改性抑制了TiO_2在焙烧过程中的结晶化程度,并提供了良好的孔隙结构,提高了催化剂的比表面积。SO_4~(2-)与Ti~(4+)配位存在,由于S=O的强吸电子能力而产生强的电子诱导效应,从而产生超强酸中心。
SO_4~(2-)/MoO_3-TiO_2固体酸催化剂对苯酚和DMO酯交换反应表现出优良的催化性能。BET、XRD、NH3-TPD表征显示,SO_4~(2-)对复合氧化物MoO_3-TiO_2表面有修饰作用,负载SO_4~(2-)后催化剂比表面积显著提高,酸量增大。MoO_3含量为1%的SO_4~(2-)/MoO_3-TiO_2催化活性最佳,DMO转化率达64.16%,DPO和MPO的收率分别达到14.31%和43.38%。
Diphenyl carbonate (DPC) is an important organic material for non-phosgene production of polycarbonates (PCs), which has been extensively applied with good performance in mechanics, optics and electronics. Much attention has been paid to the synthesis of DPC. And the transesterification of dimethyl oxalate (DMO) with phenol to diphenyl oxalate (DPO) followed by decarbonylation of DPO to DPC is a promising route. This paper disscused the process of methyl phenyl oxalate (MPO) and DPO synthesis from the transesterification of DMO with phenol, and focused on the catalytic activities of the molybdenum-titanium solid acid catalysts in the transesterification reactions.
It was indicated that the catalytic activity of MoO_3-TiO_2 compound catalyst prepared by sol-gel method was better than the MoO_3/TiO_2 supported catalyst. The results of BET, XRD, XPS, FT-IR showed that the compound catalyst had a fine compatibility of heterogeneous components, in which MoO_3 and TiO_2 dispersed evenly with the Mo-O-Ti bond formed. The dispersion of MoO_3 on the surface of TiO_2 accorded with the theory of monolayer. The MoO_3-TiO_2 catalyst performed the best activity near the threshold of dispersed MoO_3 corresponds to a saturated monolayer. Especially, the disproportionation of MPO into DPO was accelerated and the selectivity to DPO was improved. When the crystal MoO_3 was formed, the activity of catalysts and the selectivity to DPO were both decreased.
The catalytic activity of solid superacid SO_4~(2-)/TiO_2 was inspected. The characterization of XRD, XPS, FT-IR, NH3-TPD indicated that the modification of SO_4~(2-) could inhibit the crystallization of TiO_2 during calcinations and provide a fine pore structure. As a result, the specific surface area of catalyst was highly increased. SO_4~(2-) coordinated with Ti4 + and the super acid centre created owing to the strong electronic induced effects caused by S=O.
By means of BET, XRD, NH3-TPD, the excellent performance of SO_4~(2-)/MoO_3-TiO_2 during the transesterification of DMO with phenol was related with the modification of SO_4~(2-). Supported with SO_4~(2-), the specific surface area of MoO_3-TiO_2 catalyst was increased evidently, and the quantity of acid site was also increased. The catalyst of SO_4~(2-)/MoO_3-TiO_2 with 1% MoO_3 performed best, giving 64.16% conversion of DMO, 14.31% and 43.38% yield of DPO and MPO respectively.
引文
[1]欧阳光,中国化工产品大全,北京:化学工业出版社,1998,1145~1147
[2]钱伯章,聚碳酸酯的技术发展及国内外市场分析,国外塑料,2007,25(6):44~57
[3] Ono Y, Dimethyl carbonate for environmentally benign reactions, Pure Appl. Chem., 1996, 68(2): 367~375
[4]于春梅,国内外聚碳酸酯的生产与消费,化工技术经济,2007,25(1):39~43
[5] Sikdar S K, The world of polycarbonates, Chemtech., 1987, 2, 112~118
[6]徐克勋,精细有机化工原料及中间体手册,北京:化学工业出版社,1998,381
[7] Beranek J, Hlavackova J, Preparation of diaryl carbonates, Nucleic Acid Chem., 1978, (2): 999~1001
[8] Yoshinori H, Hideki K, Michio H, Catalyst for manufacturation of diaryl carbonate, JP 0900923, 1997-04-05
[9] Chalk A J, Aromatic carbonates and polycarbonates, US 2738520, 1978-04-13
[10] Hallgen J E, Mathews R O, The reactions of carbon monoxide and phenols promoted by palladium complexes, J. Organomet. Chem., 1979, 175(1): 135~142
[11] Hallgen J E, Mathews R O, The reactions of carbon monoxide and phenols promoted by palladium complexes,US 4349485,1982-05-16
[12] Hiroshi I, Sadao D, Carbonic and esters, JP 7924827, 1979-02-24
[13] General Electric Company. Process for the preparation of diarylcarbonates, US 4533504, 1985-08-06
[14] General Electric Company. Phosphine ligand promoted synthesis of tetraaryloxyalkane, US 5973183, 1999-10-26
[15] General Electric Company. Process for making a tetraaryloxymethane using a cupric alkoxide, US 6063952, 2000-05-16
[16] Vavasori A, Toniolo L, Multistep electron transfer catalytic syetem for the oxidative carbonylation of phenyl to diphenyl carbonate, J. Mol. Catal. A: Chem., 1999, 139(2-3): 109~ 119
[17] Ishii H, Goyal M, Takeuchi K, et al., Oxidative carbonylation of phenyl to diphenyl carbonate catalyzed by Pd-Sn heterotrinuclear complex along with Mn redox catalyst without addition of ammonium halide, J. Mol. Catal. A: Chem., 1999, 144(2): 369~372
[18] Ishiii H, Goyal M, Takeuchi K, et al., Oxidative carbonylation of phenyl to diphenyl carbonate catalyzed by Pd complex with dimine ligands, Catal. Lett., 2000, 65(1-3): 57~60
[19] Ishii H, Goyal M, Ueda M, et al., Oxidative carbonylation of phenyl to diphenyl carbonate catalyzed by Pd complex with 2, 2′-bipyridyl ligands, Appl. Catal. A: Gen., 2000, 201: 101~105
[20] Vavasori A, Toniolo L, The promoting effect of chelating ligands in the oxidative carbonylation of phenyl to diphenyl carbonate catalyzed by Pd-Co-benzoquinone system, J. Mol. Catal. A: Chem., 2000, 151(1-2): 37~45
[21] Yin G, Jia C, Kitamura T, et al., A new efficient Pd-catalyzed synthesis of diphenyl carbonate with heteropolyacid as a cocatalyst, J. Organomet. Chem., 2001, 630(1): 11~16
[22]梅付名,李光兴,徐辉碧等,PdCl2-Mn(OAc)2催化苯酚氧化羰基化合成碳酸二苯酯,应用化学,2001,9:752~754
[23]张光旭,吴元欣,马沛生等,非均相催化一步合成碳酸二苯酯的研究I.载体制备方法对催化剂性能的影响,催化学报,2002,23(2):130~132
[24] Yasuda H, Watarai K, Choi J, et al., Effects of bulky ligands and water in Pd-catalyzed oxidative carbonylation of phenol, J. Mol. Catal. A: Chem., 2005, 236: 149~155
[25] Tundo P, Trotta F, Molaglio G, et al., Continuous-flow process under gas-liquid phase-transfer catalysis (GL-PTC) conditions: the reaction of dialkyl carbonates with phenols, alcohols, and mercaptans, Ind. Eng. Chem. Res., 1988, 27(9): 1565~1571
[26] I. Gabriello, R. Ugo, T. Renato, Aromatic carbonates, Ger 2528412, 1976-01-08
[27]孙碧秀,吕耀宏,碳酸二甲酯合成碳酸二苯酯的研究,天然气化工,1992,17(4):21～24
[28] Fujii T, Ishibashi T, Yamakawa F, et al., Production of Diaryl Carbonates as M aterials for Polycarbonate Synthesis, Jpn Kokai Tokkyo Koho, JP 9169704. 1997
[29]梅付名,李光兴,莫婉玲,Ti(OC4H9)4催化酯交换合成碳酸二苯酯的研究,化学试剂,2000,23(4):193~195
[30]梅付名,李光兴,莫婉玲,n-Bu2SnO催化酯交换合成碳酸二苯酯的研究,现代化工,2000,20(4):29~31
[31]高俊杰,姚洁,王公应等,钛酸酯催化碳酸二甲酯与苯酚酯交换反应的研究,分子催化,2001,15(1):21~24
[32] Kim W B, Lee J S, A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts, Catal. Lett., 1999, 59: 83~88
[33] Kim W B, Kim Y G, Lee J S. The Role of Carbon Deposition in the Gasphase Transesterification of Dimethyl Carbonate and Phenol over TiO2 /SiO2 Catalyst. Appl. Catal. A, 2000, 194~195: 403~414
[34] Oyevaar, H. Martin., To, et al., Process for continous production of carbonate esters, US 6093842, 2000-07-25
[35] Hideaki H, Yoshuyuki O, Atusi M, et al., Process for preparing carbonate esters, EP 684221, 1995-11-29
[36] Hideaki H, Kenichi W, Yoshuyuki O, Preparation of aryl carbonates and catalysts for it, JP 08198817, 1996-08-06
[37] Tuinstra H E, Process for the preparation of Phenyl Carbonates or Polycarbonate, US 5349102, 1994-05-24
[38] Mitsubishi Gas Chemical Co. Inc. Method for Production of Aromatic Carbonate, EP 760359, 1997
[39] Nishihira, Keigo, Tanabe et al, Process for producing diaryl carbonate, US 5834615, 1998-11-10
[40] Keigo N, Shinichi Y, Shuji T, Manufacturing method of diphenyl carbonate, JP 11246489, 1999-09-14
[41] Keigo N, Shinichi Y, Shuji T, Manufacturing method of diphenyl carbonate, JP 11246488, 1999-09-14
[42] Biradar A V, Umbarkar S B, Dongare M K, Transesterification of diethyl oxalate with phenol using MoO3/SiO2 catalyst. Appl. Catal. A, 2005, 285: 190~195
[43] Ito M, Preparation of aromatic carbonate diesters, JP 0892167, 1996-04-09
[44] King S, Method of producing diphenyl carbonate, US 5663406, 1997-01-11
[45] Rodney R L, Stagno J L, Beckman E J, et al., Enzymatic synthesis of carbonate monomers and polycarbonates, Biotechnology and Bioengineering, 1999, 62(3): 259~266
[46] Kongen K, Arihito C, kashun S, et al., Preparation of carbonate compounds by esterification of urea derivatives in high yield and high selectivity. JP 08198815, 1996-06-06
[47] Deborah A H, Marsha M G, Kathryn L L, Phosphine Ligand Promoted Synthesis of Tetraaryloxyalkane, US 5973183, 1999-10-26
[48] Robert M G, Kathryn L L, Process and catalysts for making diaryl carbonate tetraaryl orthocarbonates, US 5504238, 1996-04-02
[49] Kazuyoshi S, Fusashi T, Manufacture of diaryl or alkyl aryl carbonates, JP 04187661, 1992-07-06
[50] Rodney R L, Stagno J L, Beckman E J, et al., Enzymatic synthesis of carbonate monomers and polycarbonates, Biotechnology and Bioengineering, 1999, 62(3): 259~266
[51] Masashi I, Kohei S, Tatsuro T, Continuous of preparation of aromatic carbonates, JP 08188558, 1996-07-23
[52] Akinobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates, JP 09241218, 1997-09-16
[53] Terunobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates by using Lanthanide oxides, JP 0959223, 1997-03-04
[54] Nisso Petrochemical Industries Co. Ltd., Aromatic carbonic acid esters, JP 8125138, 1981-7-21
[55] Yoshifumi Y, Tsunemi S, Toshio K, Prepration of diaryl carbonates from diaryl oxalates, JP 09255628, 1997-09-30
[56] Katsumasa H, Ryoji S, Yoichi I, et al., Prepration of diaryl carbonates by dacarbonylation of diaryl oxalates, JP 0977722, 1997-03-25
[57] Katsumasa H, Ryoji S, Yoichi I, et al., Preparation of diaryl carbonates by decarbonylation of diaryl oxalates, JP 10114717, 1998-05-06
[58] Katsumasa H, Ryoji S, Yoichi I, et al., Preparation of diaryl carbonates by decarbonylation of diaryl oxalates, JP 10101618, 1998-04-21
[59] Katsumasa H, Ryoji S, Yoichi I, et al., Preparation of diaryl carbonates by decarbonylation of diaryl oxalates, JP 10109961, 1998-11-03
[60] Gabriello I, Ugo R, Renato T, Aromatic carbonates, US 2528412, 1976-01-08
[61] Asahi Chemical Industry Co. Ltd., Carbonic acid esters, JP 57183745,1982-05-04
[62] Asahi Chemical Industry Co. Ltd., Preparation of diaryl carbonates, JP 03200746, 1991-05-04
[63] Keigo N, Shuji T, Katsumasa H, et al., Process for producing diaryl carbonate, US 5922827, 1999-07-13
[64] Reisinger C P, Fischer P, Hansen S M, Process for the production of a diaryl carbonate, US 791587, 2004-03-02
[65] Nippon Catalytic Chem. Ind., Continuous preparation of aryl carbonates, JP 07304713, 1995-11-07
[66] Martin H O, Bill W T, Michael F D, et al., Process for Continous Production of Carbonate Esters, US 6093842, 2000-07-25
[67] Idemitsu Petrolchemical Co., Preparation of diphenyl carbonate from dimethyl carbonate, JP 07330687, 1995-12-19
[68] Masamichi M, Hidefumi H, Preparation of aromatic carbonates as materials for polycarbonate synthesis, JP 09241219, 1997-09-16
[69]梅付名,李光兴,酯交换法合成碳酸二苯酯的反应工艺,现代化工,2001,21(3):45~48
[70]高俊杰,朱永强,胡长伟等,二丁基二月桂酸锡催化碳酸二甲酯和苯酚酯交换反应研究,合成化学,2000,8(6):528~530
[71]姚洁,高俊杰,曾毅等,催化剂对碳酸二甲酯与苯酚酯交换反应的影响,应用化学,2003,20(9):898~902
[72] Akinobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates, JP 09241217, 1997-09-16
[73] Akinobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates, JP 09241218, 1997-09-16
[74] Terunobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates, JP 0959209, 1997-03-04
[75] Terunobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates by using Lanthanide oxides, JP 0959223, 1997-03-04
[76] Takeshi O, Kazuo T, Yoshinori H, Ester exchange of carbonate esters, JP 79125617, 1979-09-29
[77] Fu Z H, Yoshio O, Two-step synthesis of diphenyl carbonate from dimethyl carbonate and phenol using MoO3/SiO2 catalysts, J. Mol. Catal. A: Chem., 1997, 118(3): 293~299
[78] Kim W B, Lee J S, Gas phase transesterification of dimethyl carbonate and phenol over supported titanium dioxide, J. Catal., 1999, 185(2): 307~313
[79] Kim W B, Lee J S, A new process for the synthesis of dipenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts, Catal. Lett, 1999, 59(1): 83~88
[80] Enichi W, Yoshiyuki O, Hideaki T, Preparation of aryl esters and heterogeneous microporous catalysts for the method, JP 11279126, 1999-10-12
[81]周炜清,赵新强,王淑芳等,负载型n-Bu2SnO催化剂上合成碳酸二苯酯的研究,四川大学学报(工程科学版),2002,34(5):39~41
[82] Akinobu Y, Takoshi Y, Preparation of diaryl carbonates and/or alkyl aryl carbonates, JP 09241218, 1997
[83] Akinobu Y, Takoshi Y, Preparation of diaryl carbonates and/or Alkyl aryl carbonates, JP 09241217, 1997
[84]周炜清,赵新强,王延吉,酯交换法合成碳酸二苯酯用氧化铅-氧化锌催化剂的研究,催化学报,2003,24(10):760~764
[85] Zhou W Q, Zhao X Q, Wang Y J, et al., Synthesis of diphenyl carbonate by transesterification over lead and zinc double oxide catalyst, Appl. Catal. A: Gen., 2004, 260: 19~21
[86]高濂,郑珊,张青红,纳米氧化钛光催化材料及应用,北京:化学工业出版社,2002
[87]陈朝华,刘长河,钛白粉生产及应用技术,北京:化学工业出版社,2005
[88] Tauster S J, Fung S C, Strong metal-support interactions: Occurrence among the binary oxides of groups IIA-VB, J. Catal., 1978, 55(1): 29~35
[89] SoPyan I, Watanabe M, Murasawa S, et al., Effieient TiO2 powder and film phaoeatalysts with rutile crystal structure, Chem. Lett., 1996, 289(1): 69~70
[90] Bersani D,Antonioli G, Lottiei P P, et al., Raman study of nanosized titania prepared by sol-gel route, J Non-Cryst Solids, 1998, 232-234: 175~181
[91] Sun Qi, Zhang Yulong, Deng Jingfa, et al., A novel preparatlon process for thermall stable ultrafine tetragonal zonia aerogel, Appl Catal A, 1977, 152(2): 165~171
[92]吴迪,王鼎聪,赵德智,纳米二氧化钛制备工艺研究进展,钛工业进展,2005,22(3):32~36
[93]江禄森,沈燕君,TPD法对TiO2载体表面酸性的研究,浙江化工,2000,31(3):21~23
[94]刘平,周廷云,林华香, TiO2-SnO2复合光催化剂的耦合效应,物理化学学报,2001,17(3):265~69
[95]余新武,陶惠娟,方涛,纳米MoO3-TiO2的制备及对甲基红的催化降解,功能材料,2005,36(7):1053~1055
[96]田部浩三等著,郑禄彬等译,新固体酸和碱及其催化作用,北京:化学工业出版社,1992
[97] Yamaguchi T, Recent Progress in Solid Superacid, Appl. Catal., 1990, 61: 1~25
[98]张术华,毛友安,SO42-/MxOy型固体超强酸及其催化酯化,化学研究与应用,1997,9(4):327~331
[99] Hino M, Reactions of Butane and Isobutane Catalysed by Titanium Oxide Treated with Sulphate Ion, Solid Superacid Catalyst, J. Chem. Soc. Chem. Comm., 1979, 1148
[100]唐新硕,王新平,金松寿,固体超强酸SO42-/ZrO2催化正烷烃异构化和裂解反应机理的研究,浙江大学学报,1994,21(3):298~305
[101] Ramis G, Busca G, In: morterra C, Zecchina A, Costa G(Editors), Structure and Reactivity of Surfaces, Amsterdam: Elsevier Science Publishers B. V., 1989,777
[102] Hino M, Arata K, Synthesis of Solid Superacid Catalyst with Acid Strength of H0≤-16.04, J. Chem. Soc. Chem. Comm., 1980, 18: 851
[103] Corma A, Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions, Chem. Rev., 1995, 95(3): 597~607
[104]杜长海,刘蕴天,贺岩峰,SO42-/MxOy型固体超强酸催化剂的发展与应用,长春工业大学学报,2002,23(2):32~34
[105]曾健青,罗庆云,王琴等,SO42-/MnOm型固体超强酸催化剂的研究进展,石油化工,1994,23(3):191~197
[106]苏文悦,付贤智,魏可镁,SO42-表面修饰对TiO2表面结构及其光催化性能的影响,物理化学学报,2001,17(1):28~31
[107]田部浩三等著,郑禄彬等译,新固体酸和碱及其催化作用,北京:化学工业出版社,1992,182
[108]姚胜,MxOy-SO42-型固体超强酸催化剂,化学通报,1992,2:23~28
[109]高滋,陈建民,SO42-/TiO2和SO42-/Fe2O3固体超强酸研究,高等学校化学学报,1994,15(6):873~877
[110]王胜平,苯酚和草酸二甲酯酯交换反应合成碳酸二苯酯:[博士学位论文],天津;天津大学,2003
[111]郭宏利,TS-1分子筛催化苯酚和草酸二甲酯酯交换反应合成草酸二苯酯:[硕士学位论文],天津;天津大学,2003
[112]巩金龙,负载型MoO3催化草酸二甲酯和苯酚酯交换反应合成草酸二苯酯的研究:[硕士学位论文],天津;天津大学,2004
[113]杨霞,负载型TiO2催化草酸二甲酯和苯酚酯交换反应合成草酸二苯酯的研究:[硕士学位论文],天津;天津大学,2005
[114]刘悦,MoO3/TiO2-SiO2催化苯酚和草酸二甲酯酯交换合成草酸二苯酯研究:[硕士学位论文],天津;天津大学,2007
[115]王胜平,李振花,马新宾等,苯酚和草酸二甲酯酯交换合成碳酸二苯酯反应产物的气相色谱-质谱分析,分析化学,2002,30(7):829~832
[116]王胜平,马新宾,李振花等,苯酚和草酸二甲酯酯交换反应产物的气相色谱分析,分析化学,2002,30(9):1085~1087
[117]廖东亮,肖新颜,张会平等,溶胶-凝胶法制备二氧化钛的工艺研究,化学工业与工程,2003,20(5):256~260
[118] Xie Y C, Tang Y Q, Spontaneous monolayer dispersion of oxides and salts onto surface of supports: Applications to heterogeneous catalysis, Adv. Catal., 1990, 37: 1~43
[119] Joccono M L, Schiavello M, Cimino A, Structure, magnetic, and optical properties of nickel oxide supported onη– andγ– aluminasl, J. Phys. Chem., 1971, 75: 1044~1050
[120] Weigold H, The nature of molybdenum oxide species mounted on alumina: An oligomer model, J. Catal., 1983, 83: 85~98
[121]汪跃民,臧雅茹,缪方明等,NiO在NaY分子筛上的分散研究,催化学报,1995,16(6):482~486
[122]汪跃民,臧雅茹,缪方明等,ZnO在NaY沸石表面的分散研究,化学研究与应用,1997,9(1):20~24
[123] Wang X Y, Zhao B Y, Jiang D E, et al., Monolayer dispersion of MoO3, NiO and their precursors onγ–Al2O3, Appl. Catal. A: Gen., 1999, 188: 201~209
[124] Yoshinaka S, Segawa K, Hydrodesulfurization of dibenzothiophenes over molybdenum cataslyst supported on TiO2-Al2O3, Catal. Today, 1998, 45: 293~298
[125] Wang J, Dong L, Hu Y H, et al., Dispersion of NiO supported onγ–Al2O3 and TiO2/γ–Al2O3 supports, J. Solid State Chem., 2001, 157: 274~282
[126] Wang X Y, Zhao B Y, Jiang D E, et al., Monolayer dispersion of MoO3, NiO and their precursors onγ–Al2O3, Appl. Catal. A: Gen., 1999, 188: 201~209
[127] Xiao F S, Zheng S, Sun J M, et al., Dispersion of inorganic salts into zeolites and their pore modification, J. Catal., 1998, 176(2): 474~487
[128] Li X T, Shao C L, Qiu S L, et al., Light-emitting boron nitride nanoparticles encapsulated in zeolite ZSM-5, Micropor. Mesopor. Mater., 2000, 40(1~3): 263~269
[129] Menon P G, Diagnosis of industrial catalyst deactivation by surface characterization techniques, Chem. Rev., 1994, 94(4): 1021~1046
[130] HillerováE, Morishige H, Inamura K, et al., Formation of monolayer of molybdena over alumina by unconventional slurry impregnation or solvent assisted spreading method, Appl. Catal. A: Gen., 1997, 156: 1~17
[131]刘英骏,谢有畅,解刚等,MoO3与不同载体的相互作用及其单层分散量的测定,催化学报,1985,6(2):101~107
[132] Kerkhof F B, Moulijn J A, Quantitative analysis of XPS intensities for supported catalysts, J. Phys. Chem., 1979, 83: 612~618
[133] Lónyi F, Valyon J, On the interpretation of the NH3-TPD patterns of H-ZSM-5 and H-mordenite, Micropor. Mesopor. Mat., 2001, 47: 293~301
[134] Sawa M, Niwa M, Murakami Y, et al., Relationship between Acid Amount and Framework Aluminum Content in Mordenite, Zeolites, 1990, 10: 532
[135]蔡炳新,詹拥共,杨莹莹等,MoO3/TiO2纳米复合催化剂的合成及催化脱氢性能,化工学报,2007,58(6):1451~1456
[136]韩维屏,尹喜林,李永战,MoO3与TiO2界面化学分散的研究,催化学报,1992,13(1):19~24
[137] Sang L X, Zhong S H, Xiao X F, et al., Photo stimulated surface catalytic syntheses of methanol and hydrogen from methane and water over MoO3-TiO2/SiO2, Chem. J. Chinese Universities, 2004, 25(6): 1115~1119
[138] Maity S K, Rana M S, et al., Studies on physico-chemical characterization and catalysis on high surface area titania supported molybdenum hydrotreating catalyst, Applied Catalysis A: General, 2001, 205: 215~225
[139]苏文悦,付贤智,魏可镁等,SO42-/TiO2固体酸的红外和拉曼光谱研究,光谱学与光谱分析,2000,20(6):840~841
[140]苏文悦,陈亦琳,付贤智等, SO42-/TiO2固体超强酸催化剂的酸强度及光催化性能,催化学报,2001,22(2):175~176
[141]郭锡坤,孙长勇,林绮纯等,固体超强酸SO42-/TiO2负载Tm改性的研究,分子催化,2002,16(3):195~198
[142] Nakamoto K, Infrared spectra of inorganic and coordination compounds (3rd ed), New York: Wiley– interscience, 1978
[143] Bellamy L J, The Infrared spectra of complex molecules (3rd ed ), London: Methuen press, 1970
