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Nano Research 2022, 15(2): 1230-1237 https://doi.org/10.1007/s12274-021-3630-6
Research Article | Issue | Published: 09 July 2021

In-situ growth of heterophase Ni nanocrystals on graphene for enhanced catalytic reduction of 4-nitrophenol

Show Author's Information Jiahao Zhuang1,2,§,  Feng He3,§,  Xianglin Liu4,  Pengchao Si1,2,  Fangna Gu2( ),  Jing Xu4,  Yu Wang2,  Guangwen Xu3,  Ziyi Zhong5,6( ),  Fabing Su2,3( )
School of Chemical Engineering University of Chinese Academy of SciencesBeijing 100049 China
State Key Laboratory of Multiphase Complex Systems Institute of Process Engineering Chinese Academy of SciencesBeijing 100190 China
Key Laboratory on Resources Chemicals and Materials of Ministry of Education Shenyang University of Chemical TechnologyShenyang 110142 China
State Key Laboratory of Chemical Engineering School of Chemical EngineeringEast China University of Science and TechnologyShanghai 200237 China
Department of Chemical Engineering Guangdong Technion-Israel Institute of Technology (GTIIT)Shantou 515063 China
Technion-Israel Institute of Technology (IIT)Haifa 32000 Israel

§ Jiahao Zhuang and Feng He contributed equally to this work.

Keywords:
graphene, catalysts, Ni nanocrystals, heterophase structure, 4-nitrophenol (4-NP) reduction
Topics:
Physicochemical properties
Cite this article:
Zhuang J, He F, Liu X, et al. In-situ growth of heterophase Ni nanocrystals on graphene for enhanced catalytic reduction of 4-nitrophenol. Nano Research, 2022, 15(2): 1230-1237. https://doi.org/10.1007/s12274-021-3630-6
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Abstract Full text Electronic supplementary material About this article

Generating heterophase structures in nanomaterials, e.g., heterophase metal nanocrystals, is an effective way to tune their physicochemical properties because of their high-energy nature and unique electronic environment of the generated interfaces. However, the direct synthesis of heterophase metal nanocrystals remains a great challenge due to their unstable nature. Herein, we report the in situ and direct synthesis of heterophase Ni nanocrystals on graphene. The heterostructure of face-centered cubic (fcc) and hexagonal close-packed (hcp) phase was generated via the epitaxial growth of hcp Ni and the partial transformation of fcc Ni and stabilized by the anchoring effect of graphene toward fcc Ni nanocrystal and the preferential adsorption of surfactant polyethylenimine (PEI) toward epitaxial hcp Ni. Comparing with the fcc Ni nanocrystals grown on graphene, the heterophase (fcc/hcp) Ni nanocrystals in situ grown on graphene showed a greatly improved catalytic activity and reusability in 4-nitrophenol (4-NP) reduction to 4-aminophenol (4-AP). The measured apparent rate constant and the activity parameter were 2.958 min–1 and 102 min–1·mg–1, respectively, higher than that of the best reported non-noble metal catalysts and most noble metal catalysts. The control experiments and density functional theory calculations reveal that the interface of the fcc and hcp phases enhances the adsorption of substrate 4-NP and thus facilitates the reaction kinetics. This work proves the novel idea for the rational design of heterophase metal nanocrystals by employing the synergistic effect of surfactant and support, and also the potential of creating the heterostructure for enhancing their catalytic reactivity.


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Electronic supplementary material
About this article

In-situ growth of heterophase Ni nanocrystals on graphene for enhanced catalytic reduction of 4-nitrophenol

Show Author's information Jiahao Zhuang1,2,§, Feng He3,§, Xianglin Liu4, Pengchao Si1,2, Fangna Gu2( ), Jing Xu4, Yu Wang2, Guangwen Xu3, Ziyi Zhong5,6( ), Fabing Su2,3( )
School of Chemical Engineering University of Chinese Academy of SciencesBeijing 100049 China
State Key Laboratory of Multiphase Complex Systems Institute of Process Engineering Chinese Academy of SciencesBeijing 100190 China
Key Laboratory on Resources Chemicals and Materials of Ministry of Education Shenyang University of Chemical TechnologyShenyang 110142 China
State Key Laboratory of Chemical Engineering School of Chemical EngineeringEast China University of Science and TechnologyShanghai 200237 China
Department of Chemical Engineering Guangdong Technion-Israel Institute of Technology (GTIIT)Shantou 515063 China
Technion-Israel Institute of Technology (IIT)Haifa 32000 Israel

§ Jiahao Zhuang and Feng He contributed equally to this work.

Abstract

Generating heterophase structures in nanomaterials, e.g., heterophase metal nanocrystals, is an effective way to tune their physicochemical properties because of their high-energy nature and unique electronic environment of the generated interfaces. However, the direct synthesis of heterophase metal nanocrystals remains a great challenge due to their unstable nature. Herein, we report the in situ and direct synthesis of heterophase Ni nanocrystals on graphene. The heterostructure of face-centered cubic (fcc) and hexagonal close-packed (hcp) phase was generated via the epitaxial growth of hcp Ni and the partial transformation of fcc Ni and stabilized by the anchoring effect of graphene toward fcc Ni nanocrystal and the preferential adsorption of surfactant polyethylenimine (PEI) toward epitaxial hcp Ni. Comparing with the fcc Ni nanocrystals grown on graphene, the heterophase (fcc/hcp) Ni nanocrystals in situ grown on graphene showed a greatly improved catalytic activity and reusability in 4-nitrophenol (4-NP) reduction to 4-aminophenol (4-AP). The measured apparent rate constant and the activity parameter were 2.958 min–1 and 102 min–1·mg–1, respectively, higher than that of the best reported non-noble metal catalysts and most noble metal catalysts. The control experiments and density functional theory calculations reveal that the interface of the fcc and hcp phases enhances the adsorption of substrate 4-NP and thus facilitates the reaction kinetics. This work proves the novel idea for the rational design of heterophase metal nanocrystals by employing the synergistic effect of surfactant and support, and also the potential of creating the heterostructure for enhancing their catalytic reactivity.

Keywords: graphene, catalysts, Ni nanocrystals, heterophase structure, 4-nitrophenol (4-NP) reduction

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Publication history
Copyright
Acknowledgements

Publication history

Received: 20 March 2021
Revised: 12 May 2021
Accepted: 30 May 2021
Published: 09 July 2021
Issue date: February 2022

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Acknowledgements

Acknowledgements

This research was funded by the National Natural Science Foundation of China (No. 21776286). Z. Zhong also thanks the support of the Guangdong Key Discipline Fund for this research.

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