桥联有机硅烷组装多级孔TS-1聚集体及其催化性能研究

doi:10.1016/S1872-2067(18)63026-8

催化学报 ›› 2018, Vol. 39 ›› Issue (2): 275-282.DOI: 10.1016/S1872-2067(18)63026-8

桥联有机硅烷组装多级孔TS-1聚集体及其催化性能研究

陈丽, 薛腾, 丁键, 吴海虹, 张坤, 吴鹏, 何鸣元

华东师范大学化学与分子工程学院, 上海 200062

收稿日期:2017-10-08 修回日期:2018-01-18 出版日期:2018-02-18 发布日期:2018-02-10
通讯作者: 吴海虹
基金资助:
国家自然科学基金（21503081，21503073，21403070，21707093）；国家重点基础研究发展计划（2017YFA0403102）.

Hydrothermal synthesis and catalytic performance of bulky titanium silicalite-1 aggregates assembled by bridged organosilane

Li Chen, Teng Xue, Jian Ding, Hai Hong Wu, Kun Zhang, Peng Wu, Ming, Yuan He

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemical and Molecular Engineering, East China Normal University, Shanghai 200062, China

Received:2017-10-08 Revised:2018-01-18 Online:2018-02-18 Published:2018-02-10
Contact: 10.1016/S1872-2067(18)63026-8
Supported by:
This work was supported by the National Natural Science Foundation of China (21503081, 21503073, 21403070, 21707093), and the National Key Research and Development Program of China (2017YFA0403102).

摘要/Abstract

摘要：

TS-1分子筛在H₂O₂参与的有机物分子选择氧化及环氧化反应中具有优异的催化性能，一直广受关注.目前，随着精细化工反应中大分子及液相反应的增多，目前工业上使用的微米级尺寸的沸石晶粒催化材料因其狭窄的孔道和较大的扩散阻力而越来越不能满足工业的实际生产需求与应用.小晶粒纳米沸石由于具有较大的外比表面积和较高的晶内扩散速率，因而在提高催化剂的利用率、增强大分子转化能力、减小深度反应、提高选择性以及降低结焦失活等方面均表现出优越的性能.然而，尺寸低于100 nm的沸石又存在着分离问题.因此，具有高催化活性、又能一步实现分离与回收的纳米沸石聚集体的合成，引起了人们的研究兴趣.目前可以通过使用聚苯乙烯球，球型阴离子交换树脂，硅烷化聚合物，聚合诱导胶体聚集（PICA）等实现纳米沸石聚集体材料的合成.其中采用有机硅烷化试剂来制备多级孔纳米沸石聚集体材料提供了一种新的路线.在沸石晶体表面修饰上有机硅烷化试剂，含Si-C键的有机硅烷化物种可以有效地阻止沸石颗粒的晶体生长，抑制形成大的沸石晶体，从而得到纳米粒子聚集体；同时有机硅烷化物种也对纳米沸石进行了表面改性，提高了其疏水性.特别是在有机相中硅烷化沸石可以形成小的、均匀的、聚集的疏水性的纳米沸石.同时，硅烷化试剂的本质和分子大小是沸石聚集体中多级孔大小的决定性因素.具有可调结构的多级孔沸石晶体可以通过在常规的碱性沸石合成混合物溶液中添加一个两性有机硅表面活性剂而合成.研究发现，固定在沸石纳米晶表面的机硅烷物种Si-C键能部分抑制纳米颗粒进一步聚集成较大的晶体，使用硅烷化晶种的方法可以合成具有高比表面的多级孔ZSM-5等沸石.然而，目前已报道的通过硅烷化晶种方法中得到的多级孔TS-1沸石材料的尺寸仅有100-150 nm，仍不利于分离和回收.近来桥联有机硅烷试剂进入人们的视野——通过干胶法合成多级孔β沸石，然而它们的尺寸也只有300-500 nm，反应分离和回收仍然非常困难.
本文采用有机桥联硅烷化合物作为硅烷化试剂，将TS-1纳米沸石晶种或者晶体组装聚集成大的沸石聚集体.TEM和SEM结果表明，桥联有机硅烷在沸石晶体的聚集和后续的晶体生长中起到了非常有效的作用，成功地将100 nm左右的纳米沸石晶种或晶体桥联/组装成宏观大尺寸（5-40 μm）的沸石聚集体.这些TS-1聚集体具有较好的机械强度，即使连续超声1 h也不会毁坏其结构，表明所得到的沸石材料可以在制备上解决分离困难并且在催化应用上容易回收.XRD，BET以及UV-Vis分析结果表明，引入在TS-1沸石晶种或者晶体溶液中有机硅烷试剂不会影响沸石的晶体结构、微孔体积以及Ti的配位状态.将H₂O₂作为氧化剂评价TS-1沸石聚集体和传统的纳米TS-1在烯烃环氧化反应中的催化性能，结果表明，硅烷化步骤对小分子己烯氧化的活性和选择性的影响不大，在环己烯大分子的氧化反应里表现出了较高的活性和选择性.

关键词: 桥联有机硅烷, TS-1沸石晶种, TS-1沸石晶体, 沸石聚集体, 烯烃环氧化反应

Abstract:

A facile and effective method to synthesize TS-1 zeolite aggregates has been presented. The crystallization of silanized seeds and nanocrystallites led to large and irregular TS-1 zeolite aggregates ranging from 5 to 40 μm in size, based on the special sol-gel chemistry of bridged organosilane. Epoxidation of 1-hexene and cyclohexene was used as a probe reaction to investigate the catalytic performance of the resulting materials. These TS-1 zeolite aggregates possessed both the conventional nanoparticle properties of TS-1 zeolites and variable surface hydrophilic/hydrophobic features, which enhanced the catalytic properties of hydroperoxides for alkene epoxidation. Moreover, the large aggregates effectively simplified the separation procedure during preparation and catalytic reactions.

Key words: Bridged organosilane, TS-1 seeds, TS-1 nanocrystallites, Zeolite aggregation, Alkene epoxidation

陈丽, 薛腾, 丁键, 吴海虹, 张坤, 吴鹏, 何鸣元. 桥联有机硅烷组装多级孔TS-1聚集体及其催化性能研究[J]. 催化学报, 2018, 39(2): 275-282.

Li Chen, Teng Xue, Jian Ding, Hai Hong Wu, Kun Zhang, Peng Wu, Ming, Yuan He. Hydrothermal synthesis and catalytic performance of bulky titanium silicalite-1 aggregates assembled by bridged organosilane[J]. Chinese Journal of Catalysis, 2018, 39(2): 275-282.

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桥联有机硅烷组装多级孔TS-1聚集体及其催化性能研究

Hydrothermal synthesis and catalytic performance of bulky titanium silicalite-1 aggregates assembled by bridged organosilane

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