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通过用酸性HTiF简单处理ERB-P沸石合成的MWW型钛硅酸盐及其在1-己烯与HO的液相环氧化反应中的催化性能

MWW-Type Titanosilicate Synthesized by Simply Treating ERB-P Zeolite with Acidic HTiF and Its Catalytic Performance in a Liquid Epoxidation of 1-Hexene with HO.

作者信息

Guo Shujuan, Zhang Yanjie, Ye Yuansong, Song Jinzhe, Li Mengru

机构信息

Ocean College, Minjiang University, Fuzhou 350108, Fujian, P. R. China.

School of Chemical Engineering, Fuzhou University, Fuzhou 350116, Fujian, P. R. China.

出版信息

ACS Omega. 2020 Apr 23;5(17):9912-9919. doi: 10.1021/acsomega.0c00184. eCollection 2020 May 5.

Abstract

Synthesis of a Ti-incorporated zeolite using a simple and economical method has recently become a focus of attention. The direct hydrothermal synthesis of Ti-MWW is most commonly applied; however, it is challenging to perform and exhibits low titanium utilization. An innovative strategy of synthesizing Ti-MWW is proposed in the present study by simply treating the ERB-1 precursor of an MWW-type boron silicate with a HTiF/HNO solution. This significantly shortens the Ti grafting process from 5 days to only a few hours and reduces the use of the structure-directing agent hexamethyleneimine (HMI); furthermore, no extraframework Ti is observed in the precursor, indicating good atomic economy. Typically, a piperidine (PI)-treated sample Ti-MWW exhibits a higher conversion (76.6%) than the original Ti-MWW (44.8%) in the epoxidation of 1-hexene. X-ray diffraction (XRD), inductively coupled plasma (ICP), and transmission electron microscopy (TEM) techniques are used to explain in detail the probable mechanism underlying the incorporation of Ti species into the MWW framework. X-ray photoelectron spectroscopy (XPS) is employed to study the coordinate state of the Ti and F species in the samples after treatment with a piperidine solution. This method can be applied to synthesize other kinds of lamellar-structured zeolites with heteroatoms.

摘要

最近,使用简单且经济的方法合成含钛沸石已成为关注焦点。Ti-MWW的直接水热合成是最常用的方法;然而,该方法实施具有挑战性且钛利用率低。本研究提出了一种合成Ti-MWW的创新策略,即通过用HTiF/HNO溶液简单处理MWW型硼硅酸盐的ERB-1前体。这显著缩短了Ti接枝过程,从5天缩短至仅数小时,并减少了结构导向剂六亚甲基亚胺(HMI)的使用;此外,在前体中未观察到额外的骨架钛,表明具有良好的原子经济性。通常,在1-己烯环氧化反应中,用哌啶(PI)处理的样品Ti-MWW比原始Ti-MWW表现出更高的转化率(76.6%对比44.8%)。使用X射线衍射(XRD)、电感耦合等离子体(ICP)和透射电子显微镜(TEM)技术详细解释了Ti物种掺入MWW骨架的可能机制。采用X射线光电子能谱(XPS)研究用哌啶溶液处理后样品中Ti和F物种的配位状态。该方法可用于合成其他种类的含杂原子层状结构沸石。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0131/7203989/1cc75284801c/ao0c00184_0001.jpg

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