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Coralloid Co2P2O7 Nanocrystals Encapsulated by Thin Carbon Shells for Enhanced Electrochemical Water Oxidation

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Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials, Nanjing University of Posts & Telecommunications, Nanjing 210023, P. R. China
§ State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, P. R. China
*Phone: 86-25-85891051. Fax: +86-25-85891051. E-mail: [email protected] (M.H.).
*E-mail: [email protected] (J.B.).
Cite this: ACS Appl. Mater. Interfaces 2016, 8, 34, 22534–22544
Publication Date (Web):August 8, 2016
https://doi.org/10.1021/acsami.6b07209
Copyright © 2016 American Chemical Society
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Abstract

Core–shell nanohybrids containing cheap inorganic nanocrystals and nanocarbon shells are promising electrocatalysts for water splitting or other renewable energy options. Despite that great progress has been achieved, biomimetic synthesis of metal [email protected] core–shell nanohybrids remains a challenge, and their use for electrocatalytic oxygen evolution reaction (OER) has not been explored. In this paper, novel nanohybrids composed of coralloid Co2P2O7 nanocrystal cores and thin porous nanocarbon shells are synthesized by combination of the structural merits of supramolecular polymer gels and a controllable thermal conversion technique, i.e., temperature programmable annealing of presynthesized supramolecular polymer gels that contain cobalt salt and phytic acid under a proper gas atmosphere. Electrocatalytic tests in alkaline solution show that such nanohybrids exhibit greatly enhanced electrocatalytic OER performance compared with that of Co2P2O7 nanostructure. At a current density of 10 mA cm–2, their overpotential is 0.397 V, which is much lower than that of Co2P2O7 nanostructures, amorphous Co-Pi nanomaterials, Co(PO3)2 nanosheets, Pt/C, and some reported OER catalysts, and close to that of commercial IrO2. Most importantly, both of their current density at the overpotential over 0.40 V and durability are superior to those of IrO2 catalyst. As revealed by a series of spectroscopic and electrochemical analyses, their enhanced electrocatalytic performance results from the presence of thin porous nanocarbon shells, which not only improve interfacial electron penetration or transfer dynamics but also vary the coordination environment and increase the number of active 5-coordinated Co2+ sites in Co2P2O7 cores.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b07209.

  • Other typical HRTEM images and mapping figures as well as N2 adsorption–desorption test data of CL-Co2P2O7@C nanohybrids (Figures S1 and S2), characterization of the samples obtained by annealing polymer gels at 400–900 °C in Ar and air atmospheres (Figures S3–S8), characterization of Co2P2O7 nanostructures (Figure S9), and additional electrochemical and spectroscopic data for CL-Co2P2O7@C nanohybrids (Figures S10–S12) (PDF)

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