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Single-atom Fe with Fe1N3 structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene

Fe1N3结构单原子Fe催化剂在硝基苯加氢和转移 加氢中的优异性能

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Abstract

The design of non-noble metal heterogeneous catalyst with superior performance for selective hydrogenation or transfer hydrogenation of nitroarenes to amines is significant but challenging. Herein, a single-atom Fe supported by nitrogen-doped carbon (Fe1/N-C) catalyst is reported. The Fe1/N-C sample shows superior performances for the selective hydrogenation and transfer hydrogenation of nitrobenzene to aniline at different temperatures. Density functional theory (DFT) calculations show that the superior catalytic activity for the selective hydrogenation at lower temperatures could be attributed to the effective activation of the reactant and intermediates by the Fe1/N-C. Moreover, the excellent performance of Fe1/N-C for the selective transfer hydrogenation could be attributed to that the reaction energy barrier for dehydrogenation of isopropanol can be overcome by elevated temperatures.

摘要

设计性能优异的硝基化合物选择性加氢或转移加氢生成胺 类的非贵金属多相催化剂具有重要的意义, 但又具有很大的挑战 性. 本文报道了氮掺杂碳负载的单原子Fe催化剂(Fe1/N-C). 通过调 控温度, Fe1/N-C催化剂对硝基苯的选择性加氢和转移加氢均具有 良好的催化性能. DFT计算表明, Fe1/N-C在较低温度下能够很好 地活化反应物和中间体, 因此具有较高的选择性加氢活性. 此外, Fe1/N-C在较高温度下可以克服异丙醇脱氢反应的能量障碍, 因此 具有很好的转移加氢性能.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0702003), the National Natural Science Foundation of China (21890383, 21671117, 21871159 and 21901135), and the Science and Technology Key Project of Guangdong Province of China (2020B010188002). We thank the 1W1B station in Bei**g Synchrotron Radiation Facility.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Bei**g, 100084, China

    Shubo Tian  (田书博), Qi Xu  (徐琪), Jiarui Yang  (杨嘉睿), Qiang Liu  (刘**), Dingsheng Wang  (王定胜) & Yadong Li  (**亚栋)

  2. Tian** Key Laboratory of Advanced Functional Porous Materials; Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tian** University of Technology, Tian**, 300384, China

    Min Hu  (胡敏) & Jia He  (何佳)

  3. Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, 230031, China

    Wanbing Gong  (龚万兵), Chun Chen  (陈春) & Huijun Zhao  (赵惠军)

  4. Bei**g Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Bei**g Institute of Technology, Bei**g, 100081, China

    Wenxing Chen  (陈文星) & Youqi Zhu  (朱有奇)

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  1. Shubo Tian  (田书博)
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  2. Min Hu  (胡敏)
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Contributions

Tian S designed and performed the experiments, and analyzed the data; Hu M and He J conducted the density functional theory calculations; Xu Q and Zhu Y assisted to carry out the experiments; Gong W, Chen C, and Zhao H designed and performed the catalytic experiment; Chen W and Yang J helped with XAFS characterization and the corresponding data analysis; Liu Q assisted to analyze the data; Wang D and Li Y conceived the research project, and analyzed the results. All authors contributed to the general discussion and writing the paper.

Corresponding author

Correspondence to Dingsheng Wang  (王定胜).

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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.

Shubo Tian received his BSc (2013), MSc (2016), and PhD (2019) degrees from Hebei Normal University, University of the Chinese Academy of Sciences, and Tsinghua University, respectively. He is currently a postdoctor in the National University of Singapore. His research interests are focused on the syntheses and applications of isolated single-atom-site and cluster catalysts.

Min Hu received her BSc (2018) degree from Ludong University. She is currently studying for a master’s degree at the Institute for New Energy Materials and Low-Carbon Technology, Tian** University of Technology. Her main research directions are first-principles and molecular dynamics simulations.

Qi Xu received his BSc degree from the University of Science and Technology of China in 2017. Now, he is a PhD student under the supervision of Prof. Dingsheng Wang at Tsinghua University. His research interests mainly focus on the design and fabrication of single-atomic catalysts for heterogeneous catalysis.

Dingsheng Wang received his BSc degree from the Department of Chemistry and Physics, University of Science and Technology of China in 2004, and his PhD degree from the Department of Chemistry, Tsinghua University in 2009, under the supervision of Prof. Yadong Li. He did his postdoctoral research at the Department of Physics, Tsinghua University, with Prof. Shoushan Fan. He joined the faculty of the Department of Chemistry, Tsinghua University in 2012.

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40843_2020_1443_MOESM1_ESM.pdf

Single-atom Fe with Fe1N3 structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene

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Tian, S., Hu, M., Xu, Q. et al. Single-atom Fe with Fe1N3 structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene. Sci. China Mater. 64, 642–650 (2021). https://doi.org/10.1007/s40843-020-1443-8

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