Precisely Tailoring the Second Coordination Sphere of a Cobalt Single‐Atom Catalyst for Selective Hydrogenation of Halogenated Nitroarenes
The development of highly efficient and cost-effective nonprecious metal catalysts for the selective hydrogenation of halogenated nitroarenes is very appealing yet challenging. Here, we demonstrate that the hydrogenation activity and selectivity of Co single-atom catalyst (SAC) can be tuned by tailoring the structure of second coordination sphere via P doping. As revealed by synchrotron radiation-based X-ray absorption spectroscopy characterizations, such a P doping on N-coordinated Co SAC results in the unsymmetric Co-N<sub>4</sub>P<sub>1</sub> coordination structure. With a combination of experimental characterizations and theoretical simulations, we find that tailoring the second coordination sphere can greatly improve H<sub>2</sub> dissociation and product desorption. As a result, the Co-N<sub>4</sub>P<sub>1</sub> SAC exhibits superior activity, selectivity and stability for the hydrogenation of halogenated nitroarenes to corresponding amines (20 examples, >99 % yields) at 80 °C under 0.5 MPa H<sub>2</sub> pressure, significantly outperforming most heterogeneous catalysts reported in the literature. We expect that this work opens a new avenue for the design of highly efficient nonprecious metal SACs for important hydrogenation reactions.
Authors
- Wanbing Gong (ORCID: https://orcid.org/0009-0005-9196-3666)
- Ran Long (ORCID: https://orcid.org/0000-0003-4845-9120)
- Huijun Zhao (ORCID: https://orcid.org/0000-0002-3028-0459)
- Juwen Gu (ORCID: https://orcid.org/0000-0002-5372-6740)
- Yujie Xiong (ORCID: https://orcid.org/0000-0002-1995-8257)
- Songbai Qiu (ORCID: https://orcid.org/0000-0002-1732-8884)
- Jiayi Li (ORCID: https://orcid.org/0000-0002-0179-1348)
- Guangyu Chen (ORCID: https://orcid.org/0009-0003-3051-5259)
- Jiawei Li (ORCID: https://orcid.org/0000-0002-9069-7002)
Institutions
- Griffith University (AU)
- University of Science and Technology of China (CN)
- Guangdong University of Technology (CN)
- Suzhou University of Science and Technology (CN)
- National Synchrotron Radiation Laboratory (CN)
- Anhui Normal University (CN)
Publication Details
- Journal
- Angewandte Chemie International Edition
- Published
- 2024-11-26
- DOI
- https://doi.org/10.1002/anie.202421277
- Citations
- 11
- Primary Topic
- Nanomaterials for catalytic reactions
- Type
- article
- Field-Weighted Citation Impact
- 2.75
Funders
- Salt Science Research Foundation
- National Key Laboratory of Human Factors Engineering
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- University of Science and Technology of China
- National Synchrotron Radiation Laboratory
- West Light Foundation of the Chinese Academy of Sciences
- Natural Science Foundation of Anhui Province
- Fundamental Research Funds for the Central Universities
- Youth Innovation Promotion Association