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具有 Gemini 型结构的有机硅烷作为介孔生成剂用于合成分级多孔 ZSM-5 沸石。

Organosilane with Gemini-Type Structure as the Mesoporogen for the Synthesis of the Hierarchical Porous ZSM-5 Zeolite.

作者信息

Zhu Haibo, Abou-Hamad Edy, Chen Yin, Saih Youssef, Liu Weibing, Samal Akshaya Kumar, Basset Jean-Marie

机构信息

KAUST Catalysis Center, King Abdullah University of Science and Technology , Thuwal 23955-6900, Kingdom of Saudi Arabia.

College of Chemistry and Chemical Engineering, Central South University , Changsha, Hunan 410083, P. R. China.

出版信息

Langmuir. 2016 Mar 1;32(8):2085-92. doi: 10.1021/acs.langmuir.5b04383. Epub 2016 Feb 17.

Abstract

A new kind of organosilane (1,6-bis(diethyl(3-trimethoxysilylpropyl)ammonium) hexane bromide) with a gemini-type structure was prepared and used as a mesoporogen for the synthesis of hierarchical porous ZSM-5 zeolite. There are two quaternary ammonium centers along with double-hydrolyzable -RSi(OMe)3 fragments in the organosilane, which results in a strong interaction between this mesoporogen and silica-alumina gel. The organosilane can be easily incorporated into the ZSM-5 zeolite structure during the crystallization process, and it was finally removed by calcination, leading to secondary pores in ZSM-5. The synthesized ZSM-5 has been systematically studied by XRD, nitrogen adsorption, SEM, TEM, TG, and solid-state one-dimensional (1D) and two-dimensional (2D) NMR, which reveal information on its detailed structure. It has a hierarchical porosity system, which combines the intrinsic micropores coming from the crystalline structure and irregular mesopores created by the organosilane template. Moreover, the mesoposity including pore size and volume within ZSM-5 can be systematically tuned by changing the organosilane/TEOS ratio, which confirms that this organosilane has high flexibility of use as a template for the synthesis of hierarchical porous zeolite.

摘要

制备了一种具有双子型结构的新型有机硅烷(1,6-双(二乙基(3-三甲氧基硅丙基)铵)己烷溴化物),并将其用作合成分级多孔ZSM-5沸石的介孔生成剂。该有机硅烷中有两个季铵中心以及双可水解的-RSi(OMe)3片段,这导致该介孔生成剂与硅铝凝胶之间存在强相互作用。在结晶过程中,该有机硅烷能够轻松地掺入ZSM-5沸石结构中,最终通过煅烧将其除去,从而在ZSM-5中形成二次孔。通过XRD、氮气吸附、SEM、TEM、TG以及固态一维(1D)和二维(2D)NMR对合成的ZSM-5进行了系统研究,这些研究揭示了其详细结构的信息。它具有分级孔隙系统,该系统结合了来自晶体结构的固有微孔和由有机硅烷模板产生的不规则介孔。此外,通过改变有机硅烷/TEOS比例,可以系统地调节ZSM-5中的介孔率,包括孔径和体积,这证实了这种有机硅烷作为分级多孔沸石合成模板具有很高的使用灵活性。

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