Electrochemistry of Nickelocene-Ferrocene Organometallic Complexes for Electrodeposition of Nickel–Iron–Based Nanostructured Film under Ambient Conditions for Oxygen Evolution Reaction

IF 5.3 2区 材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY ACS Applied Nano Materials Pub Date : 2024-10-22 DOI:10.1021/acsanm.4c0408410.1021/acsanm.4c04084
Kamlesh, Parul Aggarwal, Manish Mudgal, Avanish Kumar Srivastava, Pankaj Raizada, Pardeep Singh, Amit Paul and Archana Singh*, 
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Abstract

This study explores the interesting redox chemistry of organometallic complexes nickelocene (Nc) and ferrocene (Fc) as well as their instability as metal inorganic complexs in electrolytes on the application of bias to derive bimetallic NiFe-based nanostructured films at room temperature conditions in the presence of atmospheric oxygen. The cyclic voltammogram of the two complexes under optimized conditions revealed that the redox peaks for Fc lie between the two redox peaks of Nc, which gave us the freedom of individual potential windows for the deposition of Ni and Fe in one step. The transformation of the metal inorganic complex to the respective nanostructured oxides was investigated using in situ UV–visible spectroscopy method, and the electrodeposited product was characterized using XRD, TEM, Raman, and XPS techniques. Furthermore, the bimetallic films were tested for their catalytic activity toward oxygen evolution reaction (OER) and urea oxidation reaction (UOR). The optimized nanoscale thicknesses of Ni and NiFe films deposited in 15 cyclic voltammetry (CV) cycles showed the best performance toward both urea and water oxidation, respectively. The NiFe-15 showed only 258 mV overpotential to achieve a current density of 10 mAcm–2 and an impressive TOF of 1.02 s–1 at 300 mV overpotential. Electrocatalytic studies reveal that the presence of iron increases the OER efficiency and adversely affects UOR. In-situ ultraviolet–visible (UV–vis) spectroscopy combined with in situ Raman spectroscopy revealed that the active site for the OER is higher valence oxo species of NiOOH while for UOR, NiOOH was found to be an active species. Our research reports an improved, user-friendly approach for electrode fabrication of an NiFe-based catalyst but also opens a different pathway toward the application of organometallic complexes for the design of catalysts for the oxygen evolution reaction.

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在环境条件下电沉积镍-铁基纳米结构薄膜的二茂镍-二茂铁有机金属配合物的电化学作用,用于氧进化反应
本研究探讨了有机金属络合物二茂镍 (Nc) 和二茂铁 (Fc) 有趣的氧化还原化学性质,以及它们作为金属无机络合物在电解质中的不稳定性。两种络合物在优化条件下的循环伏安图显示,Fc 的氧化还原峰位于 Nc 的两个氧化还原峰之间,这为我们一步沉积镍和铁提供了独立的电位窗口。我们使用原位紫外可见光谱法研究了金属无机复合物向各自纳米结构氧化物的转化过程,并使用 XRD、TEM、拉曼和 XPS 技术对电沉积产物进行了表征。此外,还测试了双金属薄膜对氧进化反应(OER)和尿素氧化反应(UOR)的催化活性。在 15 个循环伏安法(CV)周期中沉积的镍和镍铁薄膜的优化纳米级厚度分别显示出对尿素和水氧化的最佳性能。NiFe-15 仅显示出 258 mV 的过电位,就能达到 10 mAcm-2 的电流密度,在 300 mV 过电位下的 TOF 为 1.02 s-1,令人印象深刻。电催化研究表明,铁的存在提高了 OER 效率,并对 UOR 产生不利影响。原位紫外-可见(UV-vis)光谱结合原位拉曼光谱发现,OER 的活性位点是 NiOOH 的较高价氧物种,而对于 UOR,NiOOH 是活性物种。我们的研究为镍铁合金催化剂的电极制造提供了一种改进的、用户友好的方法,同时也为有机金属复合物在氧进化反应催化剂设计中的应用开辟了一条不同的途径。
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来源期刊
CiteScore
8.30
自引率
3.40%
发文量
1601
期刊介绍: ACS Applied Nano Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics and biology relevant to applications of nanomaterials. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important applications of nanomaterials.
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