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Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes

负载于超薄氮掺杂碳纳米片上的钴单原子催化芳香硝基化合物氢转移反应

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Abstract

Selective transfer hydrogenation of nitroarenes to amines with transition metal nanocatalysts is appealing due to its low-cost, moderate reaction conditions, good activity and excellent selectivity. Single-atom catalysts (SACs) possessing advantages of maximum atom efficiency and particular electronic structure are expected to be more effective for this reaction, yet no report about it. Herein, cobalt single atoms anchored on N-doped ultrathin carbon nanosheets (denoted as CoSAs/NCNS) were produced and demonstrated as an outstanding SAC for selective transfer hydrogenation of nitroarenes to amines with formic acid as hydrogen donor. The turnover frequency (TOF) reached 110.6 h−1, which was 20 times higher than the best results of cobalt nanoparticles reported in literatures under similar reaction conditions. Moreover, CoSAs/NCNS exhibited excellent selectivity for a variety of nitroarenes bearing other reducible functionalities, such as iodo, cyano, keto, vinyl, alkynyl and ester groups. The findings further highlight the ability and advantages of SACs in heterogeneous catalysis.

摘要

过渡金属催化芳香硝基化合物氢转移反应制备胺类化合物, 具有成本低廉、 反应条件温和、 高活性、 高选择性等优点. 单原子催化剂具有最大的原子利用率和独特的电子结构, 有望进一步提升其催化反应性能, 但目前还没有关于单原子催化剂应用于该反应的文献报道. 本文制备了负载于氮掺杂超薄碳纳米片上的钴单原子催化剂(简写为CoSAs/NCNS), 并将其应用于芳香硝基化合物氢转移反应中, 在与文献报道类似的反应条件下, 该催化剂的 TOF达110.6 h−1, 是已报道结果的20倍; 且该催化剂对一系列具有其他不饱和官能团(如: 卤素, 氰基, 醛基, 乙烯基和乙炔基等)的硝基化合物具有优异的选择性.

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Acknowledgements

The authors acknowledge the financial support from the National Key R&D Program of China (2018YFA0208504), the National Natural Science Foundation of China (21573244 and 21573245), and the Youth Innovation Promotion Association of CAS (2017049).

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Authors and Affiliations

  1. Bei**g National Laboratory for Molecular Sciences Laboratory of Molecular Nanostructures and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Bei**g, 100190, China

    Huining Li  (**会宁), Changyan Cao  (曹昌燕), Jian Liu  (刘剑), Yang Shi  (施杨) & Weiguo Song  (宋卫国)

  2. University of Chinese Academy of Sciences, Bei**g, 100049, China

    Huining Li  (**会宁), Changyan Cao  (曹昌燕), Jian Liu  (刘剑), Yang Shi  (施杨) & Weiguo Song  (宋卫国)

  3. Shanghai Synchroton Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China

    Rui Si  (司锐)

  4. Bei**g National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Bei**g, 100190, China

    Lin Gu  (谷林)

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  1. Huining Li  (**会宁)
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  6. Lin Gu  (谷林)
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Corresponding authors

Correspondence to Changyan Cao  (曹昌燕) or Weiguo Song  (宋卫国).

Additional information

Huining Li received her BSc degree from Hebei Normal University in 2014. Now, she is a PhD student under the supervision of Prof. Weiguo Song at the Institute of Chemistry, Chinese Academy of Sciences, China. Her research interests mainly focus on the design and fabrication of single-atom catalysts for heterogeneous catalysis.

Changyan Cao obtained his PhD degree from Harbin Institute of Technology in 2011. Since then he did postdoctoral research under the supervision of Prof. Weiguo Song at the Institute of Chemistry, Chinese Academy of Sciences. Currently, he is an associate professor in Prof. Weiguo Song’s group. His current research interest mainly focuses on the design and controllable synthesis of nanocatalysts with high-performance.

Weiguo Song obtained his BSc degree from Peking University in 1992 and his PhD degree from the University of Southern California in 2001. Now, he is a full professor in the Institute of Chemistry, Chinese Academy of Sciences. His current research interest mainly focuses on the synthesis of nanostructured materials and their applications in heavy metal ions adsorption and nanocatalysis.

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Li, H., Cao, C., Liu, J. et al. Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes. Sci. China Mater. 62, 1306–1314 (2019). https://doi.org/10.1007/s40843-019-9426-x

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