Abstract
This study addresses common misunderstandings surrounding using Hg/HgO reference electrodes in alkaline water electrolysis (AWE) research. Historically, numerous AWE investigations have relied on Hg/HgO reference electrodes, typically employing 1 M NaOH/KOH internal solutions, in three-electrode systems. Conventionally, the Hg/HgO (1 M NaOH/KOH) electrode potentials have been regarded as the half-cell standard reduction potential of the Hg/HgO electrode [0.0983 V vs SHE (standard hydrogen electrode) at 25 °C].1 However, it is crucial to note that the actual Hg/HgO (1 M NaOH/KOH) electrode potentials deviate from the half-cell standard reduction potential of the Hg/HgO electrode. To address this disparity, we present discussions and propose methodologies to calculate and experimentally determine real Hg/HgO electrode potentials.2 This approach enhances the precision of reporting AWE overpotentials and other performance parameters in various energy conversion devices operating in alkaline environments. References S. Niu, S. Li, Y. Du, X. Han, and P. Xu, ACS Energy Lett., 5, 1083–1087 (2020).K. Kawashima et al., ACS Catal., 13, 1893–1898 (2023).
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