Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts

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• 作者：YuPing Liu ; Si-Xuan Guo ; Liang Ding ; C. Andr茅 Ohlin ; Alan M. Bond ; Jie Zhang
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2015
• 出版时间：August 5, 2015
• 年：2015
• 卷：7
• 期：30
• 页码：16632-16644
• 全文大小：747K
• ISSN：1944-8252

文摘

A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb₆O₁₉]^{8鈥?/sup>. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40鈥?0 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb₆O₁₉]8鈥?/sup> and Co(OH)₂/Ni(OH)₂. The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s鈥? were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large amplitude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a CoIV species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from 尾-NiOOH is the more active form of the catalyst.}