A novel MOFs-induced strategy for preparing anatase-free hierarchical TS-1 zeolite:synthesis routes, growth mechanisms and enhanced catalytic performance

Guoqing An; Chang'an Wang; Hongyi Gao; Ge Wang; Yibin Luo; Zhiyuan Liu; Changjiu Xia; Siqi Liu; Xinxin Peng; Zhixiang Cheng; Xingtian Shu

doi:10.1016/j.jcis.2022.10.113

A novel MOFs-induced strategy for preparing anatase-free hierarchical TS-1 zeolite:synthesis routes, growth mechanisms and enhanced catalytic performance

J Colloid Interface Sci. 2023 Mar:633:291-302. doi: 10.1016/j.jcis.2022.10.113. Epub 2022 Nov 12.

Authors

Guoqing An¹, Chang'an Wang², Hongyi Gao³, Ge Wang⁴, Yibin Luo⁵, Zhiyuan Liu¹, Changjiu Xia⁵, Siqi Liu¹, Xinxin Peng⁵, Zhixiang Cheng¹, Xingtian Shu⁶

Affiliations

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China.
² Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China; Shunde Graduate School, University of Science and Technology Beijing, Shunde 528399, P. R. China.
³ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China; SINOPEC Changling Branch Company, Yueyang 414012, P. R. China.
⁴ Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China. Electronic address: gewang@ustb.edu.cn.
⁵ Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China.
⁶ Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, P. R. China. Electronic address: shuxingtian.ripp@sinopec.com.

PMID: 36459934
DOI: 10.1016/j.jcis.2022.10.113

Abstract

Titanosilicate-1 zeolites (TS-1) as one of the most commonly used catalysts for alkene epoxidation, construction of hierarchical pores as well as elimination of anatase to promote mass transportation and avoid invalid decomposition of hydrogen peroxide are always desirable yet challenging goals. Here, a novel and unique Ti-based metal organic frameworks (MOFs)-induced synthetic strategy for fabricating anatase-free hierarchical TS-1 was first proposed. All the components of MOFs perform different functions: the uniformly distributed Ti nodes replace conventional tetrabutyl titanate (TBOT) to serve as sole Ti source for constructing zeolite crystal; the separated ligands can be embedded in the zeolite framework and act as template to in situ build hierarchical pore structure; the coordination interaction between Ti nodes and ligands can efficiently avoid the anatase generation by balancing the forming rates of Ti-OH and Si-OH. This synthetic strategy is of general applicability, and two different synthetic routes including traditional hydrothermal process and steam assisted crystallization (SAC) procedure are successfully adopted. The obtained hydrothermal TS-1 and SAC anatase-free samples all possess abundant intercrystalline mesopores of 20-50 nm and even macropores between 50 and 150 nm, improving the conversion over 25 % for 1‑hexene epoxidation than TS-1 sample prepared by conventional route. The influences of the amount of Ti MOFs precursor and the crystallization process are studied in detail, and possible synthesis mechanisms are proposed. This MOFs-induced strategy might open up an avenue for the rational design of ideal and hierarchical zeolite to boost the catalytic efficiency.

Keywords: Anatase-free; Catalytic performance; Crystal growth mechanisms; Hierarchical TS-1; MOFs-induced; Synthetic strategy.