采用浸渍法制备了Si-MCM-41和Al-MCM-41 (Si/Al=50)介孔分子筛,SiO2,γ-Al2O3及MgO等负载的ZrO2催化剂,考察了其在以异丙醇为氢源苯甲醛Meerwein-Ponndorf-Verley(MPV)还原反应中的催化活性,并与纯ZrO2的催化活性进行对比.同时,采用X射线衍射、N2吸脱附法、X射线光电子能谱、紫外-可见漫反射光谱和吡啶原位吸附红外光谱等手段表征了催化剂.结果表明,ZrO2负载于Si-MCM-41,Al-MCM-41和SiO2后,催化活性明显提高,这归因于ZrO2与载体间存在强相互作用形成Zr-O-Si 键,使催化剂表面Zr-OH数量显著增多,Lewis酸中心强度增强,并出现Br(o)nsted酸中心,三种催化剂的活性高低次序是5%ZrO2/Si-MCM-41> 5%ZrO2/Al-MCM-41> 5%ZrO2/SiO2.而5%ZrO2/Al2O3和5%ZrO2/MgO基本无催化活性,可归因为ZrO2与γ-Al2O3的弱相互作用使5%ZrO2/Al2O3的酸性与γ-Al2O3类似,ZrO2与MgO的强相互作用使5%ZrO2/MgO基本无酸性.
A series of zirconia catalysts supported on Si-MCM-41 and Al-doped MCM-41 (Si/Al =50) mesoporous molecular sieves,silica,γ-Al2O3,and MgO were prepared by the wet impregnation method.The catalytic activities of these materials in the Meerwein-Ponndorf-Verley reduction (MPV) of benzaldehyde with 2-propanol as reducing agent were investigated,and compared to that of hydrous zireonia.The materials were characterized by X-ray diffraction,nitrogen adsorption-desorption,X-ray photoelectron spectroscopy,UV-Vis diffuse reflectance spectroscopy,and Fourier transform infrared and thermal desorption of pyridine.Loading zirconia on Si-MCM-41,Al-MCM-41,and SiO2 gave improved catalytic activity.This is attributed to a strong interaction of zirconia with the support to form Si--O-Zr bonds,which gave a significant increase in the amount of exposed Zr-OH groups and stronger Lewis acidity as well as an appearance of Br(o)nsted acid sites.The activity of 5%ZrO2/Si-MCM-41 was the highest,followed by those of 5%ZrO2/Al-MCM-41 and 5%ZrO2/SiO2.However,5%ZrO2/Al2O3 and 5%ZrO2/MgO gave very low catalytic activities.This is ascribed to that the acidities of 5%ZrO2/Al2O3 and the γ-Al2O3 support were similar due to the weak interaction of zirconia with γ-Al2O3,and 5%ZrO2MgO had no acidity because of the strong interaction between zirconia and MgO.
参考文献
[1] | Ruiz JR;Jimenez-Sanchidrian C .Heterogeneous catalysis in the Meerwein-Ponndorf-Verley reduction of carbonyl compounds[J].Current organic chemistry,2007(13):1113-1125. |
[2] | Gli(n)ski M .[J].Applied Catalysis A:General,2008,349:133. |
[3] | Zhu Y Z;Liu S H;Jaenicke S;Chuah G .[J].Catalysis Today,2004,97:249. |
[4] | Liu SH.;Jaenicke S.;Chuah GK. .Hydrous zirconia as a selective catalyst for the Meerwein-Ponndorf-Verley reduction of cinnamaldehyde[J].Journal of Catalysis,2002(2):321-330. |
[5] | 石能富,张波,徐春雷,张新波,陈银飞,葛忠华.MgZrAlO复合氧化物催化酮氢转移还原反应[J].高校化学工程学报,2011(01):61-66. |
[6] | Zhu Y Z;Chuah G K;Jaenicke S .[J].Journal of Catalysis,2006,241:25. |
[7] | Samuel P P;Shylesh S;Singh A P .[J].J Mol CatalA,2007,266:11. |
[8] | Zhu YZ.;Jaenicke S.;Chuah GK. .Supported zirconium propoxide - A versatile heterogeneous catalyst for the Meerwein-Ponndorf-Verley reduction[J].Journal of Catalysis,2003(2):396-404. |
[9] | 徐春雷,张波,袁剑,卢晗锋,陈银飞,葛忠华.负载型MgO催化苯乙酮Meerwein-Ponndorf-Verley反应中的载体效应[J].化学学报,2011(04):368-374. |
[10] | Busto M;Lovato M E;Vera C R;Shimizu K Grau J M .[J].Applied Catalysis A:General,2009,355:123. |
[11] | 胡胜华,薛明伟,陈慧,孙寅璐,沈俭一.高载量、高活性Ni/Al2O3催化剂的制备及其芳环加氢催化反应[J].催化学报,2011(06):917-925. |
[12] | Ciuparu D;Ensuque A;Bozon-Verduraz F .[J].Applied Catalysis A:General,2007,326:130. |
[13] | Liu D P;Quek X Y;Cheo W N E;Lau R Borgna A Yang Y H .[J].Journal of Catalysis,2009,266:380. |
[14] | Chen C-L;Cheng S F;Lin H-P;Wong S-T Mou C-Y .[J].Applied Catalysis A:General,2001,215:21. |
[15] | Damyanova S;Petrov L;Centeeno M A;Grange P .[J].Applied Catalysis A:General,2002,224:271. |
[16] | Reddy B M;Chowdhury B;Smirniotis P G .[J].Applied Catalysis A:General,2001,211:19. |
[17] | Reddy B M;Sreekanth P M;Yamada Y;Kobayashi T .[J].Journal of Molecular Catalysis A:Chemical,2005,227:81. |
[18] | Wakiya N;Kuroyanagi K;Xuan Y;Shinozaki K Mizutani N .[J].Thin Solid Films,2000,372:156. |
[19] | López E F;Escribano V S;Panizza M;Carnasciali M M Busca G .[J].Journal of Materials Chemistry,2001,11:1891. |
[20] | Zhao J;Yue Y H;Hua W M;He H Y Gao Z .[J].Applied Catalysis A:General,2008,336:133. |
[21] | Chary K V R;Ramesh K;Naresh D;Ramana Rao P V Ramachandra Rao A Venkat Rao V .[J].Catalysis Today,2009,141:187. |
[22] | Wang J-H;Mou C-Y .[J].Microporous and Mesoporous Materials,2008,110:260. |
[23] | Ordomsky V V;Sushkevich V L;Ivanova I I .[J].Journal of Molecular Catalysis A:Chemical,2010,333:85. |
[24] | Ahmed MA .[J].FuelProcess Technol,2011,92:1121. |
[25] | Flego C;Carluccio L;Rizzo C;Perego C .[J].Catalysis Communications,2001,2:43. |
[26] | Garg S;Soni K;Muthu Kumaran G;Bal R,Gora-Marek K,Gupta J K,Sharma L D,Murali Dhar G .[J].Catalysis Today,2009,14:125. |
[27] | Zhang W;Tay H L;Lim S S;Wang Y S Zhong Z Y Xu R .[J].Applied Catalysis B:Environmental,2010,95:93. |
[28] | Zhao Y B;Li W;Zhang M H;Tao K Y .[J].Catalysis Communications,2002,3:239. |
[29] | Rodríguez Avenda(n)o R G;De Los Reyes J A;Viveros T;Montoya De La Fuente J A .[J].Catalysis Today,2009,148:12. |
[30] | Gervasini A;Messi C;Flahaut D;Guimon C .[J].Applied Catalysis A:General,2009,367:113. |
[31] | Li J C;Xiang L;Xu F;Wang Z W Wei F .[J].Applied Surface Science,2006,253:766. |
[32] | Scirè S;Crisafulli C;Maggiore R;Minicò S Gavagno S .[J].Applied Surface Science,1998,136:311. |
[33] | García V;Fernández J J;Ruíz W;Mondragón F Moreno A .[J].Catalysis Communications,2009,11:240. |
[34] | Urbano, F.J.;Aramendía, M.A.;Marinas, A.;Marinas, J.M. .An insight into the Meerwein-Ponndorf-Verley reduction of α,β-unsaturated carbonyl compounds: Tuning the acid-base properties of modified zirconia catalysts[J].Journal of Catalysis,2009(1):79-88. |
- 下载量()
- 访问量()
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%