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Tuning the coordination environment of single-atom catalyst M-N-C towards selective hydrogenation of functionalized nitroarenes

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Abstract

Fine-tuning of the coordination environment of single-atom catalysts (SACs) is effective to optimize their catalytic performances, yet it remains challenging due to the vulnerability of SACs. Herein, we report a new approach to engineering the coordination environment of M-N-C (M = Fe, Co, and Ni) SACs by using glutamic acid as the N/C source and pyrolysis atmosphere as a regulator. Compared with that in N2, NH3 was able to promote the do** of N at T < 700 °C yet etch the N-species at higher temperatures, by which the M-N coordination number (CN) and the electronic structure were delicately tuned. It was found that the electron density of Ni single atoms increased with the decrease of Ni-N CN. As a consequence, the capability of Ni-N-C to dissociate H2 was greatly enhanced and a higher catalytic activity in chemoselective hydrogenation of functionalized nitroarenes was achieved. Moreover, this modulation method could be applied to other transition metals including Fe and Co. In particular, the as-synthesized Co-N-C SAC afforded a turnover frequency of 152.3 h−1 with 99% selectivity to 3-vinylaniline in the hydrogenation of 3-nitrostyrene, which was the highest ever reported thus far and was at least one order of magnitude more active than state-of-the-art noble-metal-free M-N-C catalysts, demonstrating the great potential of engineering the coordination environment of SACs.

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Acknowledgements

This work was supported by the National Key Technology R&D Program of China (No. 2020YFA0710202), the National Natural Science Foundation of China (Nos. U1662130, 21690080, 21690084, and 21721004), and the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB17020100). We also thank the BL 14W beamline at the Shanghai Synchrotron Radiation Facility (SSRF).

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Authors and Affiliations

  1. School of Chemical Engineering, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China

    Dan Zhou

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

    Dan Zhou, Leilei Zhang, **aoyan Liu, Haifeng Qi, Qinggang Liu, Ji Yang, Yang Su, Jianzhong Yin & Aiqin Wang

  3. Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory (SSRF, ZJLab), Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, China

    **gyuan Ma

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Tuning the coordination environment of single-atom catalyst M-N-C towards selective hydrogenation of functionalized nitroarenes

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Zhou, D., Zhang, L., Liu, X. et al. Tuning the coordination environment of single-atom catalyst M-N-C towards selective hydrogenation of functionalized nitroarenes. Nano Res. 15, 519–527 (2022). https://doi.org/10.1007/s12274-021-3511-z

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