中文摘要：

TS-1分子筛具有MFI拓扑结构,因其独特的择形选择性和优异的催化氧化能力而广受关注.最早报道的TS-1合成方法采用大量四丙基氢氧化铵（TPAOH）作为有机结构导向剂,TPAOH价格昂贵,制约着TS-1分子筛大规模应用.开发廉价、环境友好的合成工艺是TS-1分子筛合成领域的重要课题.以价格相对较低的四丙基溴化铵（TPABr）代替TPAOH做有机结构导向剂,以氨水为碱源可合成TS-1分子筛,但产物晶粒尺寸远远大于以TPAOH做模板的合成结果,影响TS-1分子筛的传质和催化性能.因此,人们对该法进行了改进,选用有机胺作为碱源,TPABr为结构导向剂合成TS-1分子筛,但始终未能将其晶粒尺寸降至1μm以下.在合成体系中引入预先合成的TS-1分子筛或TS-1胶态前驱体作为晶种可以促进成核,缩短成核诱导期,有利于获得小晶粒尺寸的TS-1分子筛.此类方法往往需要辅助以大量有机胺等结构导向剂;胶态TS-1前驱体的制备需要特别小心以保证晶种中Ti的四配位状态,通常需要经历低温水解钛酸四丁酯（TBOT）和高温加热除醇等繁琐步骤.而胶态纯硅silicalite-1制备则相对简单,且已广泛用于导向合成同样具有MFI结构的ZSM-5沸石,但目前鲜有以silicalite-1做晶种合成TS-1分子筛的报道.基于此,本文以纯硅胶态silicalite-1为晶种,以氨水做碱源,辅助以少量TPABr做导向剂,合成了小晶粒TS-1分子筛,并以正己烯环氧化和环己酮氨肟化做探针反应考察了所得TS-1分子筛的催化氧化性能.X射线衍射结果表明,当晶种中SiO2占合成体系中SiO2的10 wt%（晶种引入TPAOH,TPAOH/SiO2=0.35）,加入TPABr（TPABr/Si O2=0.03）做辅助结构导向剂,即合成体系中总（TPAOH＋TPABr）/Si O2摩尔比低至0.07时,所得样品依然具有良好的结晶度.扫描电镜照片观察不到无定形物存在;晶种中SiO2占合成体系中SiO2的10 wt%时,所得TS-1晶粒尺寸约为250 nm×150 nm×50 nm;其他条件不

英文摘要：

Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.