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Rational construction of multiple hollow silicalite-1 zeolite with enhanced quasi acidity for robust vapor-phase Beckmann rearrangement

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Abstract

Develo** efficient and stable zeolites for vapor-phase Beckmann rearrangement of cyclohexanone oxime is still a great challenge to realize ε-caprolactam (CPL) green production. In this work, the hierarchical porous silicalite-1 zeolites with multiple hollow structure (S-1-M) are explored by in-situ desilication—recrystallization post-treatment of spongy highway-like zeolites (S-1-S), which are synthesized through silanization synthesis of conventional bulky silicalite-1 (S-1). Compared to S-1, S-1-M achieves superior catalytic performance, with improving the CPL selectivity from 85.7% to 94.1% and prolonging the catalyst lifetime from 74 to 126 h at a weight hourly space velocity (WHSV) of 6 h−1. Comprehensive physiochemical studies demonstrate that the highly dispersed intracrystalline cavities within S-1-M endow greater mass diffusion and better quasi acidity inducing by the enhanced H-bonds among abundant H-bonded silanols, which is cooperatively responsible for its superior catalytic performance.

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Acknowledgements

This work was supported by the National Key Basic Research Development Plan “973” Project (No. 2006CB202508), the National Key R&D Program of China (No. 2021YFA1502600), State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC) (No. 33600000-20-ZC0607-0024), the SINOPEC Project (Nos. 411058 and 413025), and the National Natural Science Foundation (Nos. 21808244, 22178347, and 22072182).

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  1. Peng Zhang and **anfeng Yi contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Bei**g, 100083, China

    Peng Zhang, Changjiu **a, **nxin Peng, **aoxin Zhang, Yibin Luo & **ngtian Shu

  2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, 430071, China

    **anfeng Yi & Anmin Zheng

  3. Shandong Hualu-Hengsheng Chemical Co., Ltd., Dezhou, 253024, China

    Shuai Zhang, Lifeng Cui & Fuhong Yu

  4. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Bei**g, 100190, China

    Chengxiang Li

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  1. Peng Zhang
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Correspondence to Changjiu **a, Anmin Zheng or **aoxin Zhang.

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Rational construction of multiple hollow silicalite-1 zeolite with enhanced quasi acidity for robust vapor-phase Beckmann rearrangement

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Zhang, P., Yi, X., **a, C. et al. Rational construction of multiple hollow silicalite-1 zeolite with enhanced quasi acidity for robust vapor-phase Beckmann rearrangement. Nano Res. 16, 7958–7966 (2023). https://doi.org/10.1007/s12274-022-5305-3

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