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Nano Research 2022, 15(5): 3980-3990 https://doi.org/10.1007/s12274-022-4091-2
Research Article | Issue | Published: 18 January 2022

Biomass-assisted approach for large-scale construction of multi-functional isolated single-atom site catalysts

Show Author's Information Tao Wu1,2,3,§,  Sha Li4,§,  Shoujie Liu4,§,  Weng-Chon Cheong5,  Cheng Peng1,  Kai Yao1,  Yingping Li1,  Jieyue Wang1,  Binbin Jiang6( ),  Zheng Chen3( ),  Zhiming Chen2,  Xianwen Wei1,  Konglin Wu1,2( )
Key Laboratory of Metallurgical Emission Reduction & Resources Recycling, Ministry of Education, Institute of Clean Energy and Advanced Nanocatalysis (iClean), School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, China
Anhui Laboratory of Clean Catalytic Engineering, School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China
Center of Single-Atom, Clusters, and Nanomaterials (CAN), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
Chemistry and Chemical Engineering of Guangdong Laboratory, Shantou 515063, China
Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macao, China
School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials, Anqing Normal University, Anqing 246011, China

§ Tao Wu, Sha Li, and Shoujie Liu contributed equally to this work.

Keywords:
hydrogenation, single-atom site, multifunctional catalyst, heteroatomic coordination, oxydehydrogenation
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Catalysts
Cite this article:
Wu T, Li S, Liu S, et al. Biomass-assisted approach for large-scale construction of multi-functional isolated single-atom site catalysts. Nano Research, 2022, 15(5): 3980-3990. https://doi.org/10.1007/s12274-022-4091-2
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Abstract Full text Electronic supplementary material About this article

In recent years, the isolated single-atom site (ISAS) catalysts have attracted much attention as they are cost-effective, can achieve 100% atom-utilization efficiency, and often display superior catalytic performance. Here, we developed a biomass-assisted pyrolysis-etching-activation (PEA) strategy to construct ISAS metal decorated on N and B co-doped porous carbon (ISAS M/NBPC, M = Co, Fe, or Ni) catalysts. This PEA strategy can be applied in the universal and large-scale preparation of ISAS catalysts. Interestingly, the ISAS M/NBPC (M = Co, Fe, or Ni) catalysts show multi-functional features and excellent catalytic activities. They can be used to conduct different types of catalytic reactions, such as O-silylation (OSI), oxidative dehydrogenation (ODH), and transfer hydrogenation (THG). In addition, we used the transfer hydrogenation of nitrobenzene as a typical reaction and revealed the difference between ISAS Co/NBPC and ISAS Co/NPC (N-doped porous carbon) catalysts by density functional theory (DFT) calculations, and which showed that the decreased barrier of the rate-determining step and the low-lying potential energy diagram indicate that the catalytic activity is higher when ISAS Co/NBPC is used than that when ISAS Co/NPC is used. These results demonstrate that the catalytic performance can be effectively improved by adjusting the coordination environment around the ISAS.


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Electronic supplementary material
About this article

Biomass-assisted approach for large-scale construction of multi-functional isolated single-atom site catalysts

Show Author's information Tao Wu1,2,3,§, Sha Li4,§, Shoujie Liu4,§, Weng-Chon Cheong5, Cheng Peng1, Kai Yao1, Yingping Li1, Jieyue Wang1, Binbin Jiang6( ), Zheng Chen3( ), Zhiming Chen2, Xianwen Wei1, Konglin Wu1,2( )
Key Laboratory of Metallurgical Emission Reduction & Resources Recycling, Ministry of Education, Institute of Clean Energy and Advanced Nanocatalysis (iClean), School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, China
Anhui Laboratory of Clean Catalytic Engineering, School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China
Center of Single-Atom, Clusters, and Nanomaterials (CAN), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, China
Chemistry and Chemical Engineering of Guangdong Laboratory, Shantou 515063, China
Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macao, China
School of Chemistry and Chemical Engineering, Anhui Key Laboratory of Photoelectric-Magnetic Functional Materials, Anqing Normal University, Anqing 246011, China

§ Tao Wu, Sha Li, and Shoujie Liu contributed equally to this work.

Abstract

In recent years, the isolated single-atom site (ISAS) catalysts have attracted much attention as they are cost-effective, can achieve 100% atom-utilization efficiency, and often display superior catalytic performance. Here, we developed a biomass-assisted pyrolysis-etching-activation (PEA) strategy to construct ISAS metal decorated on N and B co-doped porous carbon (ISAS M/NBPC, M = Co, Fe, or Ni) catalysts. This PEA strategy can be applied in the universal and large-scale preparation of ISAS catalysts. Interestingly, the ISAS M/NBPC (M = Co, Fe, or Ni) catalysts show multi-functional features and excellent catalytic activities. They can be used to conduct different types of catalytic reactions, such as O-silylation (OSI), oxidative dehydrogenation (ODH), and transfer hydrogenation (THG). In addition, we used the transfer hydrogenation of nitrobenzene as a typical reaction and revealed the difference between ISAS Co/NBPC and ISAS Co/NPC (N-doped porous carbon) catalysts by density functional theory (DFT) calculations, and which showed that the decreased barrier of the rate-determining step and the low-lying potential energy diagram indicate that the catalytic activity is higher when ISAS Co/NBPC is used than that when ISAS Co/NPC is used. These results demonstrate that the catalytic performance can be effectively improved by adjusting the coordination environment around the ISAS.

Keywords: hydrogenation, single-atom site, multifunctional catalyst, heteroatomic coordination, oxydehydrogenation

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Publication history
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Acknowledgements

Publication history

Received: 10 November 2021
Revised: 20 December 2021
Accepted: 21 December 2021
Published: 18 January 2022
Issue date: May 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21771003, 51902003, 21901007, 22002085, and 21501004), the University Synergy Innovation Program of Anhui Province (No. GXXT-2021-020), the Anhui Province Natural Science Foundation (Nos. 2008085QB53 and 2008085QB83), the Natural Science Research Project of Anhui Province Education Department (No. KJ2019A0581), the Open Project of Key Laboratory of Metallurgical Emission Reduction & Resources Recycling of Ministry of Education (No. JKF21-03), and the Open Foundation of Anhui Laboratory of Clean Catalytic Engineering (No. LCCE-01). We acknowledge the 1W1B beamline station of Beijing Synchrotron Radiation Facility (BSRF), and the Institute of Physics of Chinese Academy of Sciences. We acknowledge the National Synchrotron Radiation Laboratory (NSRL) of Hefei. We also thank Prof. Lirong Zheng, Prof. Wensheng Yan, Prof. Qinghua Zhang, and Prof. Jun Luo for their help in catalyst characterizations. Thanks to Prof. Chen Chen of Tsinghua University and Prof. Junjie Mao of Anhui Normal University for their help in materials characterizations and catalytic testing. We thank LetPub (www.letpub.com) for its linguistic assistance during the preparation of this manuscript.

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