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Nano Research 2022, 15(6): 5024-5031 https://doi.org/10.1007/s12274-022-4235-4
Research Article | Issue | Published: 22 March 2022

Breaking the activity limitation of iridium single-atom catalyst in hydrogenation of quinoline with synergistic nanoparticles catalysis

Show Author's Information Qikai Shen1,2,  Hongqiang Jin1,2,  Peipei Li1,2,  Xiaohu Yu3,  Lirong Zheng4,  Weiguo Song1,2( ),  Changyan Cao1,2( )
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Sciences, Shaanxi University of Technology, Hanzhong 723000, China
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
Keywords:
heterogeneous catalysis, hydrogenation, single atom, synergistic, quinoline
Topics:
Catalytic
Cite this article:
Shen Q, Jin H, Li P, et al. Breaking the activity limitation of iridium single-atom catalyst in hydrogenation of quinoline with synergistic nanoparticles catalysis. Nano Research, 2022, 15(6): 5024-5031. https://doi.org/10.1007/s12274-022-4235-4
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Abstract Full text Electronic supplementary material About this article

Single-atom catalysts (SACs) with the advantages of homogeneous and heterogeneous catalysts have become a hot-spot in catalysis field. However, for lack of metal–metal bond in SACs, H2 has to go through heterolytic dissociation pathway, which has higher barrier than homolytic dissociation pathway, and thus limits the hydrogenation activity of SACs. Herein, we propose and demonstrate through constructing synergistic iridium single atoms and nanoparticles co-existed catalyst (denoted as Ir1+NPs/CMK) to boost the catalytic activity of quinoline hydrogenation. Both experimental and density functional theory calculation results confirm that Ir1 single sites activate quinoline, while Ir nanoparticles boost hydrogen dissociation. H atoms generated at Ir nanoparticles migrate to the quinoline bounded Ir1 single sites to complete hydrogenation. The Ir1+NPs/CMK catalyst exhibits much higher reactivity with turnover frequency of 7,800 h−1 than those counterpart Ir1/CMK and IrNPs/CMK catalysts, and is 20,000 times higher activity of commercial Ir/C benchmark catalyst for hydrogenation of quinoline under the same reaction conditions. This synergistic catalysis strategy between single atoms and nanoparticles provides a solution to further improve the performance of SACs for hydrogenation.


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Electronic supplementary material
About this article

Breaking the activity limitation of iridium single-atom catalyst in hydrogenation of quinoline with synergistic nanoparticles catalysis

Show Author's information Qikai Shen1,2, Hongqiang Jin1,2, Peipei Li1,2, Xiaohu Yu3, Lirong Zheng4, Weiguo Song1,2( ), Changyan Cao1,2( )
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China
Institute of Theoretical and Computational Chemistry, Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Sciences, Shaanxi University of Technology, Hanzhong 723000, China
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

Abstract

Single-atom catalysts (SACs) with the advantages of homogeneous and heterogeneous catalysts have become a hot-spot in catalysis field. However, for lack of metal–metal bond in SACs, H2 has to go through heterolytic dissociation pathway, which has higher barrier than homolytic dissociation pathway, and thus limits the hydrogenation activity of SACs. Herein, we propose and demonstrate through constructing synergistic iridium single atoms and nanoparticles co-existed catalyst (denoted as Ir1+NPs/CMK) to boost the catalytic activity of quinoline hydrogenation. Both experimental and density functional theory calculation results confirm that Ir1 single sites activate quinoline, while Ir nanoparticles boost hydrogen dissociation. H atoms generated at Ir nanoparticles migrate to the quinoline bounded Ir1 single sites to complete hydrogenation. The Ir1+NPs/CMK catalyst exhibits much higher reactivity with turnover frequency of 7,800 h−1 than those counterpart Ir1/CMK and IrNPs/CMK catalysts, and is 20,000 times higher activity of commercial Ir/C benchmark catalyst for hydrogenation of quinoline under the same reaction conditions. This synergistic catalysis strategy between single atoms and nanoparticles provides a solution to further improve the performance of SACs for hydrogenation.

Keywords: heterogeneous catalysis, hydrogenation, single atom, synergistic, quinoline

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Publication history
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Acknowledgements

Publication history

Received: 20 January 2022
Revised: 11 February 2022
Accepted: 13 February 2022
Published: 22 March 2022
Issue date: April 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

The authors thank the National Natural Science Foundation of China (Nos. 92161112 and 21932006), the National Key Research and Development Program of China (Nos. 2018YFA0208504 and 2018YFA0703503), the Youth Innovation Promotion Association of CAS (No. 2017049), and the National Science Basic Program of Shaanxi (No. S2020-JC-WT-0001).

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