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Research Article

Dynamically modulated synthesis of hollow metal-organic frameworks for selective hydrogenation reactions

Liyun Xiao1Chuanqi Cheng2Zhixi Li1Chaoyang Zheng1Jing Du1Meina Song1Yue Wan1Shaopeng Li1Guo Jun3Meiting Zhao1( )
Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin 300072, China
Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
State Key Laboratory of Separation Membranes and Membrane Processes, School of Chemistry, Tiangong University, Tianjin 300387, China
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Graphical Abstract

A thioether-modified UiO-67 hollow metal-organic framework (MOF) (H-UiO-67-S) was prepared by dynamically modulated synthesis method. After supporting Pd nanoparticles, the Pd@H-UiO-67-S can selectively reduce 4-chloronitrobenzene to 4-chloroaniline, due to the interaction between thioether and Pd in the confined pores of H-UiO-67-S, which not only selectively adsorbs nitro groups on reactants but also limits the adsorption of amino groups on products.

Abstract

Hollow metal-organic frameworks (MOFs) have attracted increasing attention in the field of catalysis in recent years due to their unique cavity structure with fast mass-diffusion rates and easily accessible active sites. Here, we report the use of dynamic modulators, which are formed by the in-situ imine condensation reaction of 4-aminobenzoic acid and 4-formylbenzoic acid, to regulate the growth of MOFs to synthesize well-defined hollow thioether functionalized UiO-67 (denoted as H-UiO-67-S) single crystals. After supporting Pd nanoparticles, the designed catalysts Pd@H-UiO-67-S show excellent conversion (> 99.9%), selectivity (> 99.9%), and stability (10 cycles) in the selective hydrogenation of nitrobenzenes with other reducible groups. Density functional theory calculations and the experimental results reveal that Pd nanoparticles not only selectively adsorb the nitro-groups on nitrobenzene, but also restrict the adsorption of the aniline product, due to the interaction of thioether with Pd in the confined pores of H-UiO-67-S, finally result in a significant increase in selectivity of nitro-hydrogenation.

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Nano Research
Pages 11334-11341
Cite this article:
Xiao L, Cheng C, Li Z, et al. Dynamically modulated synthesis of hollow metal-organic frameworks for selective hydrogenation reactions. Nano Research, 2023, 16(8): 11334-11341. https://doi.org/10.1007/s12274-023-5750-7
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Received: 03 March 2023
Revised: 09 April 2023
Accepted: 16 April 2023
Published: 20 May 2023
© Tsinghua University Press 2023
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