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

作　　者：Peng Zhang Xianfeng Yi Changjiu Xia Xinxin Peng Shuai Zhang Chengxiang Li Anmin Zheng Xiaoxin Zhang Yibin Luo Lifeng Cui Fuhong Yu Xingtian Shu 

机构地区：[1]State Key Laboratory of Catalytic Materials and Reaction Engineering,Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China [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 [3]Shandong Hualu-Hengsheng Chemical Co.,Ltd.,Dezhou 253024,China [4]State Key Laboratory of Multiphase Complex Systems,Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China

出　　处：《Nano Research》2023年第5期7958-7966,共9页纳米研究（英文版）

基　　金：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);the National Natural Science Foundation(Nos.21808244,22178347,and 22072182).

摘　　要：Developing efficient and stable zeolites for vapor-phase Beckmann rearrangement of cyclohexanone oxime is still a great challenge to realizeε-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.

关 键 词：hollow silicalite-1 H-bonded silanols quasi acidity vapor-phase Beckmann rearrangement 

分 类 号：O64[理学—物理化学]