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Zn metal atom doping on the surface plane of one-dimesional NiMoO4 nanorods with improved redox chemistry

Sharma, P., Minakshi Sundaram, M.ORCID: 0000-0001-6558-8317, Watcharatharapong, T., Laird, D.W.ORCID: 0000-0001-7550-4607, Euchner, H. and Ahuja, R. (2020) Zn metal atom doping on the surface plane of one-dimesional NiMoO4 nanorods with improved redox chemistry. ACS Applied Materials & Interfaces, 12 (40). pp. 44815-44829.

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The effect of zinc (Zn) doping and defect formation on the surface of nickel molybdate (NiMoO4) structures with varying Zn content has been studied to produce one-dimensional electrodes and catalysts for electrochemical energy storage and ethanol oxidation, respectively. Zn-doped nickel molybdate (Ni1-xZnxMoO4, where x = 0.1, 0.2, 0.4, and 0.6) nanorods were synthesized by a simple wet chemical route. The optimal amount of Zn is found to be around 0.25 above which the NiMoO4 becomes unstable, resulting in poor electrochemical activity. This result agrees with our density functional theory calculations in which the thermodynamic stability reveals that Ni1-xZnxMoO4 crystallized in the β-NiMoO4 phase and is found to be stable for x≤0.25. Analytical techniques show direct evidence of the presence of Zn in the NiMoO4 nanorods, which subtly alter the electrocatalytic activity. Compared with pristine NiMoO4, Zn-doped NiMoO4 with the optimized Zn content was tested as an electrode for an asymmetric supercapacitor and demonstrated an enhanced specific capacitance of 122 F g–1 with a high specific energy density of 43 W h kg–1 at a high power density of 384 W kg–1. Our calculations suggest that the good conductivity from Zn doping is attributed to the formation of excess oxygen vacancies and dopants play an important role in enhancing the charge transfer between the surface and OH– ions from the electrolyte. We report electrochemical testing, material characterization, and computational insights and demonstrate that the appropriate amount of Zn in NiMoO4 can improve the storage capacity (∼15%) due to oxygen vacancy interactions.

Item Type: Journal Article
Murdoch Affiliation: Chemistry and Physics
Engineering and Energy
Publisher: ACS Publications
Copyright: © 2020 American Chemical Society
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