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Solvent-free synthesis of Co@NC catalyst with Co—N species as active sites for chemoselective hydrogenation of nitro compounds

无溶剂合成以Co—N物种为活性位点的Co@NC催化 剂用于芳香硝基化合物选择加氢

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Abstract

Metal-organic frameworks (MOFs) derived Co-based catalysts have received extensive attention in the chemoselective hydrogenation of nitroarenes, while they usually require a lot of solvent during the synthesis and identification of active species. This study explores a solid-phase synthesis strategy to obtain MOF precursors without using any solvent, which is then foamed and pyrolyzed to synthesize the Co@NC-X catalyst. It was found that a nitrogen-doped graphene shell can well encapsulate the Co nanoparticles. The resulting catalyst, which was pyrolyzed at 800°C, exhibited ~100% conversion for the hydrogenation of 3-nitrostyrene and >99% selectivity to 3-vinylaniline. This catalyst also showed excellent stability and good substrate universality for the hydrogenation of extensive substituted nitroarenes. Various characterizations revealed a positive relationship between the catalytic performance and the content of Co—N species tuned by pyrolysis temperature. This work provides a novel and green strategy to design an efficient Co-based catalyst for chemoselective hydrogenation.

摘要

金属有机骨架(MOFs)衍生的Co基催化剂用于芳香硝基化合物 选择加氢引起了广泛的关注, 但催化剂合成过程中使用大量溶剂, 且对 催化剂中活性中心的认识存在争议. 本文开发了一种固相合成策略, 在 不使用任何溶剂的情况下获得MOF前体材料, 经发泡和热解处理获得 Co@NC催化剂. 研究发现, 800°C热解所得的催化剂中Co纳米颗粒被 氮掺杂石墨烯壳层包裹, 在3-硝基苯乙烯的加氢过程中表现出~100% 的转化率, 3-乙烯基苯胺的选择性大于99%, 同时, 该催化剂具有良好 的循环稳定性和底物普适性. 表征和实验结果证明该催化剂中Co—N物 种为活性中心, 其含量可通过热解温度进行调变, 且催化性能与Co—N 物种的含量存在正相关关系. 本工作为设计用于选择加氢反应的高效 Co基催化剂提供了一种新的绿色合成策略.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21808193, 21878283, 22022814, and 22002118), China Postdoctoral Science Foundation (2020TQ0245), the Science and Technology Innovation Development Plan of Yantai (2021XDHZ069), the Youth Innovation Promotion Association CAS (Y2021057), Dalian Science Foundation for Distinguished Young Scholars (2021RJ10), and Taishan Scholars Program of Shandong province (tsqn202103051).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, China

    Haisheng Wei  (魏海生), Huaxing Song  (宋华兴), Xiaorui Yan  (颜晓瑞), Wenhua Wang  (王文华), Wanzhong Ren  (任万忠) & Mingyuan Zhu  (朱明远)

  2. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Geqian Fang  (方葛钱) & Jian Lin  (林坚)

  3. Interdisciplinary Research Center of Biology & Catalysis, School of Life Sciences, Northwestern Polytechnical University, Xi’an, 710072, China

    Yujing Ren  (任煜京)

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  1. Haisheng Wei  (魏海生)
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Contributions

Wei H, Song H and Ren Y participated in the design of this study, conducted the experiments, performed data analysis and drafted the manuscript. Yan X and Fang G conducted the experiments. Wang W, Ren W and Zhu M provided assistance for the data acquisition and analysis. Lin J proposed the idea, supervised the research and revised the manuscript. All authors read and approved the content of the manuscript.

Corresponding author

Correspondence to Jian Lin  (林坚).

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The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Haisheng Wei received his PhD degree from Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS) under the supervision of Prof. Aiqin Wang and Prof. Tao Zhang in 2015. His research interests focus on the design, synthesis and characterization of highly dispersed supported metal catalysts for the synthesis of fine chemicals.

Huaxing Song is currently a master student at the College of Chemistry and Chemical Engineering, Yantai University. His research interest focuses on the development of MOFs-derived materials and their corresponding performances in selective hydrogenation reactions.

Yujing Ren is currently an associate professor at the School of Life Sciences, Northwestern Polytechnical University (NWPU). He received his PhD degree from DICP, CAS under the supervision of Prof. Dangsheng Su, Prof. Aiqin Wang and Prof. Tao Zhang in 2020, and then joined the NWPU. His research interests include single-atom catalysis, selective hydrogenation/hydrogenolysis reactions and nanozyme.

Jian Lin received his PhD degree from the DICP, CAS in 2011. He is now a professor at the DICP. His research interests include controlled syntheses and characterizations of highly dispersed metal catalysts, and their applications in heterogeneous oxidation and hydrogenation catalysis.

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40843_2022_2108_MOESM1_ESM.pdf

Solvent-free synthesis of Co@NC catalyst with Co—N species as active sites for chemoselective hydrogenation of nitro compounds

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Wei, H., Song, H., Ren, Y. et al. Solvent-free synthesis of Co@NC catalyst with Co—N species as active sites for chemoselective hydrogenation of nitro compounds. Sci. China Mater. 66, 169–178 (2023). https://doi.org/10.1007/s40843-022-2108-4

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