Enhancement of hydrogen evolution reaction kinetics in alkaline media by fast galvanic displacement of nickel with rhodium – From smooth surfaces to electrodeposited nickel foams

催化作用 原电池 制氢 电解 碱性水电解 化学 无机化学 单排替反应 电化学 电解水 分解水 旋转圆盘电极 化学工程 材料科学 电解质 冶金 电极 循环伏安法 物理化学 有机化学 光催化 工程类
作者
Aleksandar Z. Jovanović,Lazar Bijelić,Ana S. Dobrota,Natalia V. Skorodumova,Slavko Mentus,Igor A. Pašti
出处
期刊:Electrochimica Acta [Elsevier BV]
卷期号:414: 140214-140214 被引量:14
标识
DOI:10.1016/j.electacta.2022.140214
摘要

• Fast galvanic displacement of Ni with Rh significantly improves hydrogen evolution activity. • After 30 s of exchange, smooth Ni disk shows higher HER activity than polycrystalline Pt. • The same exchange protocols are applied for commercial Ni foam and electrodeposited Ni. • After 10 min of exchange modified Ni foam shows HER overpotential of −0.07 V at −10 mA cm −2 . • Surface modification of Ni with Rh has minor impact on the price of the catalyst compared to energy savings. Energy-efficient hydrogen production is one of the key factors for advancing hydrogen-based economy. Alkaline water electrolysis is the main route for the production of high-purity hydrogen, but further improvements of hydrogen evolution reaction (HER) catalysts are still needed. Industrial alkaline electrolysis relies on Ni-based catalysts, and here we describe a drastic improvement of HER activity of Ni in alkaline media using several model catalysts for HER, obtained upon nickel surface modification in the aqueous solution of rhodium salts, where a spontaneous deposition of rhodium takes place, based on the chemical displacement reaction 3Ni + 2Rh 3+ = 3Ni 2+ + 2Rh. In the case of smooth Ni-poly electrodes, HER activity surpasses the activity of Pt-poly after just 30 s of exchange with Rh. SEM analysis showed that Rh is uniformly distributed, and that surface roughness changes are lower than 10%, which is in agreement with the electrochemical measurements. Furthermore, XPS analysis has shown effective incorporation of Rh in the surface, while DFT calculations suggest that hydrogen binding is significantly weakened on the Rh-modified Ni surfaces. Such tuning of the hydrogen binding energy is seen as the main factor governing HER activity improvements. The same galvanic displacement protocols were employed for nickel foam electrodes and electrodeposited Ni on Ti mesh. In both cases, somewhat longer Rh exchange times are needed to obtain superior activities than for the smooth Ni surface, but within 10 min. HER overpotentials corresponding to −10 mA cm −2 for nickel foam and electrodeposited Ni electrodes, after modification with Rh, amounted to only −0.07 and −0.09 V, respectively. Thus, it is suggested that a fast spontaneous displacement of Ni with Rh could effectively boost HER in alkaline media with minor cost penalties with regards to energy saving in the electrolysis process.
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