Journal
SMALL
Volume 16, Issue 12, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.201903334
Keywords
cobalt phosphates; electrocatalysis; micro-Raman; nanocarbon supports; OER
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Funding
- SERB [SB/S2/JCB-85/2014, EMR/2017/002767]
- DST-Nanomission [SR/NM/TP-56]
- Council of Scientific and Industrial Research, India
- University Grants Commission, New Delhi
- Industrial Research and Consultancy Centre
- Indian Institute of Technology Bombay
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Compositional interplay of two different cobalt phosphates (Co(H2PO4)(2); Co-DP and Co(PO3)(2); Co-MP) loaded on morphologically engineered high surface area nanocarbon leads to an increased electrocatalytic efficiency for oxygen evolution reaction (OER) in near neutral conditions. This is reflected as significant reduction in the onset overpotential (301 mV) and enhanced current density (30 mA cm(-2) @ 577 mV). In order to achieve uniform surface loading, organic-soluble thermolabile cobalt-bis(di-tert-butylphosphate) is synthesized in situ inside the nanocarbon matrix and subsequently pyrolyzed at 150 degrees C to produce Co(H2PO4)(2)/Co(PO3)(2) (80:20 wt%). Annealing this sample at 200 or 250 degrees C results in the redistribution of the two phosphate systems to 55:45 or 20:80 (wt%), respectively. Detailed electrochemical measurements clearly establish that the 55:45 (wt%) sample prepared at 200 degrees C performs the best as a catalyst, owing to a relay mechanism that enhances the kinetics of the 4e(-) transfer OER process, which is substantiated by micro-Raman spectroscopic studies. It is also unraveled that the engineered nanocarbon support simultaneously enhances the interfacial charge-transfer pathway, resulting in the reduction of onset overpotential, compared to earlier investigated cobalt phosphate systems.
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