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Nano Research 2018, 11(4): 2217-2228 https://doi.org/10.1007/s12274-017-1840-8
Research Article | Issue | Published: 19 March 2018

In situ trapped high-density single metal atoms within graphene: Iron-containing hybrids as representatives for efficient oxygen reduction

Show Author's Information Daobin Liu1,  Chuanqiang Wu1,  Shuangming Chen1,  Shiqing Ding1,  Yaofeng Xie1,  Changda Wang1,  Tao Wang1,  Yasir A. Haleem1,  Zia ur Rehman1,  Yuan Sang1,  Qin Liu1,  Xusheng Zheng1,  Yu Wang2,  Binghui Ge3,  Hangxun Xu1,  Li Song1( )
National Synchrotron Radiation LaboratoryDepartment of PhysicsDepartment of Polymer Science and EngineeringCAS Center for Excellence in NanoscienceUniversity of Science and Technology of ChinaHefei230026China
Shanghai Synchrotron Radiation FacilityShanghai Institute of Applied PhysicsChinese Academy of SciencesShanghai201204China
Beijing National Laboratory for Condensed Matter PhysicsInstitute of PhysicsChinese Academy of SciencesBeijing100190China
Keywords:
oxygen reduction reaction (ORR), high loading, single metal atoms (SMAs), X-ray absorption fine structure spectroscopy (XAFS), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM)
Cite this article:
Liu D, Wu C, Chen S, et al. In situ trapped high-density single metal atoms within graphene: Iron-containing hybrids as representatives for efficient oxygen reduction. Nano Research, 2018, 11(4): 2217-2228. https://doi.org/10.1007/s12274-017-1840-8
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Abstract Full text Electronic supplementary material About this article

Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid (the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid). Furthermore, the single iron-doped hybrid (Fe@N-doped graphene) showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was ~199 mW·cm-2 at a current density of 310 mA·cm-2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms (SMAs) catalysts for potential energy applications.


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Electronic supplementary material
About this article

In situ trapped high-density single metal atoms within graphene: Iron-containing hybrids as representatives for efficient oxygen reduction

Show Author's information Daobin Liu1, Chuanqiang Wu1, Shuangming Chen1, Shiqing Ding1, Yaofeng Xie1, Changda Wang1, Tao Wang1, Yasir A. Haleem1, Zia ur Rehman1, Yuan Sang1, Qin Liu1, Xusheng Zheng1, Yu Wang2, Binghui Ge3, Hangxun Xu1, Li Song1( )
National Synchrotron Radiation LaboratoryDepartment of PhysicsDepartment of Polymer Science and EngineeringCAS Center for Excellence in NanoscienceUniversity of Science and Technology of ChinaHefei230026China
Shanghai Synchrotron Radiation FacilityShanghai Institute of Applied PhysicsChinese Academy of SciencesShanghai201204China
Beijing National Laboratory for Condensed Matter PhysicsInstitute of PhysicsChinese Academy of SciencesBeijing100190China

Abstract

Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid (the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid). Furthermore, the single iron-doped hybrid (Fe@N-doped graphene) showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was ~199 mW·cm-2 at a current density of 310 mA·cm-2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms (SMAs) catalysts for potential energy applications.

Keywords: oxygen reduction reaction (ORR), high loading, single metal atoms (SMAs), X-ray absorption fine structure spectroscopy (XAFS), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM)

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Publication history
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Acknowledgements

Publication history

Received: 16 June 2016
Revised: 21 August 2017
Accepted: 01 September 2017
Published: 19 March 2018
Issue date: April 2018

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany 2017

Acknowledgements

Acknowledgements

This work is financially supported partly by Ministry of Science and Technology (MOST) (Nos. 2017YFA0303500 and 2014CB848900), the National Natural Science Foundation of China (NSFC) (Nos. U1532112, 11574280 and 11605201), CAS Interdisciplinary Innovation Team and CAS Key Research Program of Frontier Sciences (No. QYZDB-SSW-SLH018). L. S. acknowledges the recruitment program of global experts, the CAS Hundred Talent Program and Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Nankai University. We thank the Shanghai Synchrotron Radiation Facility (14W1, SSRF), the Beijing Synchrotron Radiation Facility (1W1B and soft-X-ray endstation, BSRF), the Hefei Synchrotron Radiation Facility (Photoemission, MCD and Catalysis/Surface Science Endstations, NSRL), and the USTC Center for Micro and Nanoscale Research and Fabrication for helps in characterizations.

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