Study of Oxygen Reduction Reaction on Polycrystalline Rhodium in Acidic and Alkaline Media

Catalysts Pub Date : 2024-05-16 DOI:10.3390/catal14050327
Jelena Golubović, M. Varničić, S. Štrbac
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Abstract

This study examines the kinetics and mechanism of the oxygen reduction reaction (ORR) on a polycrystalline rhodium electrode (Rh(poly)) in acidic and alkaline media, using rotating disc electrode measurements. This study found that the ORR activity of the Rh(poly) electrode decreases in the order of 0.1 M NaOH > 0.1 M HClO4 > 0.05 M H2SO4 concerning the half-wave potentials. The Tafel slopes for ORR on Rh(poly) in the cathodic direction are 60 and 120 mV dec−1 at low and high overpotentials, respectively, in perchloric acid and alkaline solutions. However, strongly adsorbed sulfate anions hinder the ORR on Rh(poly) in sulfuric acid, leading to higher Tafel slopes. The highest ORR activity of Rh(poly) in an alkaline media suggests the promoting role of the specifically adsorbed OH− anions and RhOH. In all cases, ORR on Rh(poly) proceeds through the 4e-series reaction pathway.
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酸性和碱性介质中多晶铑的氧还原反应研究
本研究采用转盘电极测量法,研究了多晶铑电极(Rh(poly))在酸性和碱性介质中氧还原反应(ORR)的动力学和机理。研究发现,Rh(poly) 电极的氧还原反应活性在半波电位上依次为 0.1 M NaOH > 0.1 M HClO4 > 0.05 M H2SO4。在高氯酸和碱性溶液中,Rh(poly) 上的 ORR 阴极方向的塔菲尔斜率分别为 60 和 120 mV dec-1,过电位分别为低和高。然而,强烈吸附的硫酸根阴离子阻碍了 Rh(poly)在硫酸中的 ORR,导致较高的塔菲尔斜率。Rh(poly) 在碱性介质中的 ORR 活性最高,这表明特别吸附的 OH- 阴离子和 RhOH 起到了促进作用。在所有情况下,Rh(poly) 上的 ORR 都是通过 4e 系列反应途径进行的。
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