巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能

doi:10.1016/S1872-2067(12)60603-2

催化学报 ›› 2013, Vol. 34 ›› Issue (8): 1519-1526.DOI: 10.1016/S1872-2067(12)60603-2

巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能

张嘉熙^a, 黄高伟^a, 张琤^a,b, 何群华^b, 黄超^a, 杨旭^c, 宋慧宇^a, 梁振兴^a, 杜丽^a,d, 廖世军^a,d

a 华南理工大学化学与化工学院, 广东广州510640;
b 广东省环境监测中心, 广东广州510640;
c 中国科学院广州能源研究所, 中国科学院可再生能源与天然气水合物重点实验室, 广东广州510640;
d 华南理工大学化学与化工学院, 广东省燃料电池技术重点实验室, 广东广州510640

收稿日期:2013-03-24 修回日期:2013-04-18 出版日期:2013-08-16 发布日期:2013-07-30
通讯作者: 杜丽,廖世军
基金资助:
国家自然科学基金(51102099, 21003052); 广东省自然科学基金(S2011040000964); 广东省教育厅育苗工程(2011); 中央高校基本科研业务费.

Immobilization of highly active Pd nano-catalysts on functionalized mesoporous silica supports using mercapto groups as anchoring sites and their catalytic performance for phenol hydrogenation

Jiaxi Zhang^a, Gaowei Huang^a, Cheng Zhang^a,b, Qunhua He^b, Chao Huang^a, Xu Yang^c, Huiyu Song^a, Zhenxing Liang^a, Li Du^a,d, Shijun Liao^a,d

a School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China;
b Guangdong Environmental Monitoring Center, Guangzhou 510640, Guangdong, China;
c Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China;
d The Key Laboratory of Fuel Cell Technology of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China

Received:2013-03-24 Revised:2013-04-18 Online:2013-08-16 Published:2013-07-30
Supported by:
This work was supported by the National Natural Science Foundation of China (51102099, 21003052), the Natural Science Foundation of Guangdong Province (S2011040000964), the Training Project for the Outstanding and Innovative Talents in Guangdong Colleges and Universities (Yumiao Project, 2011), and the Fundamental Research Funds for the Central Universities, SCUT.

摘要/Abstract

摘要： 以含巯基官能团有机硅烷修饰的介孔材料MCM-41和SBA-15为载体, 采用浸渍-氢气还原法制备了高分散和高活性的负载型Pd催化剂. X射线衍射、N₂吸附-脱附和透射电子显微镜表征结果显示, 所制Pd催化剂Pd-SH-MCM-41和Pd-SH-SBA-15具有很好的长程有序结构、分布均匀的孔径、高比表面积及高度分散的Pd颗粒. 苯酚加氢反应结果表明, 以Pd-SH-MCM-41和Pd-SH-SBA-15为催化剂时, 在80℃, 1.0MPa反应1h, 苯酚转化率达99%以上, 环己酮选择性为98%. 它们的催化活性为商业Pd/C催化剂的5倍, Pd/MCM-41和Pd/SBA-15催化剂的3倍. 这可归因于介孔材料表面修饰的巯基官能团对Pd的锚定作用, 避免了Pd颗粒的团聚, 使其高度分散在介孔材料上.

关键词: 介孔氧化硅, 巯基修饰, 钯, 锚定, 负载型催化剂, 苯酚加氢

Abstract: Highly active and highly dispersed Pd-loaded nano-catalysts using mercapto group (-SH) functionalized mesoporous silica supports, namely, Pd-SH-MCM-41 and Pd-SH-SBA-15, were prepared using an impregnation-reduction approach. The surface -SH groups are believed to facilitate the high distribution and immobilization of the Pd nanoparticles within the silica supports through an anchoring interaction. The catalysts featured long-range ordered structures, uniform pore size, high surface area, and highly dispersed Pd nanoparticles as characterized by X-ray diffraction, N₂ adsorption-desorption, and transmission electron microscopy. The catalysts showed activity five times higher than that of commercial Pd/C catalyst and three times higher than those of Pd/MCM-41 and Pd/SBA-15 catalysts. Within 1 h of reaction at 80℃ and 1.0 MPa, the conversion of phenol attained was greater than 99%, and the selectivity for cyclohexanone was 98%.

Key words: Mesoporous silica, Mercapto group functionalization, Palladium, Anchoring, Supported catalyst, Phenol hydrogenation

张嘉熙, 黄高伟, 张琤, 何群华, 黄超, 杨旭, 宋慧宇, 梁振兴, 杜丽, 廖世军. 巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能[J]. 催化学报, 2013, 34(8): 1519-1526.

Jiaxi Zhang, Gaowei Huang, Cheng Zhang, Qunhua He, Chao Huang, Xu Yang, Huiyu Song, Zhenxing Liang, Li Du, Shijun Liao. Immobilization of highly active Pd nano-catalysts on functionalized mesoporous silica supports using mercapto groups as anchoring sites and their catalytic performance for phenol hydrogenation[J]. Chinese Journal of Catalysis, 2013, 34(8): 1519-1526.

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巯基功能化介孔材料高效锚定钯负载型催化剂的制备及其苯酚加氢催化性能

Immobilization of highly active Pd nano-catalysts on functionalized mesoporous silica supports using mercapto groups as anchoring sites and their catalytic performance for phenol hydrogenation

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