Title: Controlled One‐pot Synthesis of Nickel Single Atoms Embedded in Carbon Nanotube and Graphene Supports with High Loading

Abstract

Abstract Single‐atom catalysts (SACs) have attracted much attentions due to the advantages of high catalysis efficiency and selectivity. However, the controllable and efficient synthesis of SACs remains a significant challenge. Herein, we report a controlled one‐pot synthesis of nickel single atoms embedded on nitrogen‐doped carbon nanotubes (NiSA−N−CNT) and nitrogen‐doped graphene (NiSA−N−G). The formation of NiSA−N−CNT is due to the solid‐to‐solid rolling up mechanism during the high temperature pyrolysis at 800 °C from the stacked and layered Ni‐doped g‐C ₃ N ₄ , g‐C ₃ N ₄ −Ni structure to a tubular CNT structure. Addition of citric acid introduces an amorphous carbon source on the layered g‐C ₃ N ₄ −Ni and after annealing at the same temperature of 800 °C, instead of formation of NiSA−N−CNT, Ni single atoms embedded in planar graphene type supports, NiSA−N−G were obtained. The density functional theory (DFT) calculation indicates the introduction of amorphous carbon source substantially reduces the structure fluctuation or curvature of layered g‐C ₃ N ₄ ‐Ni intermediate products, thus interrupting the solid‐to‐solid rolling process and leading to the formation of planar graphene type supports for Ni single atoms. The as‐synthesized NiSA−N−G with Ni atomic loading of ∼6 wt% catalysts shows a better activity and stabilitymore » for the CO ₂ reduction reaction (CO ₂ RR) than NiSA−N−CNT with Ni atomic loading of ∼15 wt% due to the open and exposed Ni single atom active sites in NiSA−N−G. This study demonstrates for the first time the feasibility in the control of the microstructure of carbon supports in the synthesis of SACs.« less

Authors:

Zhao, Shiyong ^[1]; Wang, Tianshuai ^[2]; Zhou, Guangmin ^[3]; Zhang, Liji ^[4]; Lin, Chao ^[2]; Veder, Jean‐Pierre ^[5]; Johannessen, Bernt ^[6]; Saunders, Martin ^[7]; Yin, Lichang ^[8]; Liu, Chang ^[8]; De Marco, Roland ^[9]; Yang, Shi‐Ze ^[10]; Zhang, Qianfan ^[2]; Jiang, San Ping  ^[1]

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+ Show Author Affiliations

1. Fuels and Energy Technology Institute &, WA School of Mines: Minerals, Energy and Chemical Engineering Curtin University Perth, Western Australia 6102 Australia
2. School of Materials Science and Engineering Beihang University Beijing 100191 China
3. Department of Materials Science and Engineering Stanford University Stanford, California 94305 USA
4. School of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 China, Engineering Alloys Division Shenyang National Laboratory for Materials Science Institute of Metal Research Chinese Academy of Sciences Shenyang, Liaoning 110016 China
5. John de Laeter Centre Curtin University Perth, Western Australia 6102 Australia
6. Australian Synchrotron Clayton, Victoria 3168 Australia
7. Centre for Microscopy Characterization and Analysis (CMCA) and School of Molecular Sciences The University of Western Australia Perth, Western Australia 6009 Australia
8. Advanced Carbon Division Shenyang National Laboratory for Materials Science Institute of Metal Research Chinese Academy of Sciences Shenyang, Liaoning 110016 China
9. Faculty of Science Health, Education and Engineering University of Sunshine Coast Maroochydore DC, Queensland 4558 Australia, School of Chemistry and Molecular Biosciences The University of Queensland Brisbane, Queensland 4072 Australia
10. Materials Science and Technology Division Oak Ridge National Laboratory Oak Ridge, TN 37831 United States

Publication Date:

Wed Apr 29 00:00:00 EDT 2020

Sponsoring Org.:

USDOE

OSTI Identifier:

1616494

Resource Type:

Publisher's Accepted Manuscript

Journal Name:

ChemNanoMat

Additional Journal Information:

Journal Name: ChemNanoMat Journal Volume: 6 Journal Issue: 7; Journal ID: ISSN 2199-692X

Publisher:

Wiley Blackwell (John Wiley & Sons)

Country of Publication:

Germany

Language:

English