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

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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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Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (Nos. 21905195, M. T. Z. and 22103055, J. G.), Natural Science Foundation of Tianjin City (No. 20JCYBJC00800, M. T. Z.), Science and Technology Plans of Tianjin (No. 21ZYJDJC00050, J. G.), and PEIYANG Young Scholars Program of Tianjin University (No. 2020XRX-0023, M. T. Z.).

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Authors and Affiliations

  1. Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin, 300072, China

    Liyun Xiao, Zhixi Li, Chaoyang Zheng, Jing Du, Meina Song, Yue Wan, Shaopeng Li & Meiting Zhao

  2. Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China

    Chuanqi Cheng

  3. State Key Laboratory of Separation Membranes and Membrane Processes, School of Chemistry, Tiangong University, Tianjin, 300387, China

    Guo Jun

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  1. Liyun Xiao
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Xiao, L., Cheng, C., Li, Z. et al. Dynamically modulated synthesis of hollow metal-organic frameworks for selective hydrogenation reactions. Nano Res. 16, 11334–11341 (2023). https://doi.org/10.1007/s12274-023-5750-7

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