Investigation of Hydrogen Electrode Formation on the Surface of Noble Metals (Pd, Ir, Au) Exposed to Nitrogen Atmosphere: A Comprehensive Study Using Scanning Kelvin Probe
Authors: Ganapathi Arulkumar , Rohwerder Michael 
Published: July 2022

The importance of hydrogen evolution reaction (HER) in engineering and energy conversion related applications grows stronger and it is important to develop better catalysts to enhance the efficiency of the catalytic process. The introduction of computational chemistry (e.g., DFT) into the field of electrochemistry allows general prediction and understanding of activity trends. Great progress is made in modelling the electrochemical double layer under potentiostatic control [1]. However, a reliable and feasible experimental methodology providing in-depth experimental data for improving the theoretical model is lacking, as the electrochemical interface is usually buried under bulk electrolyte, which prevents most important surface analytical techniques to be applied for its investigation. However, it could be recently shown that a hydrogen electrode forms on a palladium surface even in nitrogen atmosphere, even at very low humidity [2] . The electrochemical double layer of this “hydrogen electrode in the dry” is confined just 1-2 monolayers of adsorbed water. However, it is still fully polarizable by adjusting the hydrogen activity from the backside of the electrode and it is even possible to measure full current-potential dependencies for reactions such as e.g. oxygen reduction [3]. Hence, this could be revolutionary new approach for investigating electrochemical electrodes in operando by standard surface analytical techniques. For this however, it needs to be investigated in how far this approach can be also applied beyond palladium. Since the potential of such “electrodes in the dry” cannot be measured with standard reference electrode a Kelvin probe is used instead [2,3]. Basically, the Kelvin probe measures the Volta potential difference between sample and probe (ψ
KP - ψ
S), and upon suitable calibration such measurement provides the electrode potential of the sample.
Evers et.al has proposed the “Hydrogen electrode in dry” concept based on adjusting the hydrogen activity (cathodic charging) from one side of a palladium sample and measuring the work function on the other side using Kelvin probe [2]. In this work, the hydrogen electrode formation in dry (<0.1% R.H) as well as humid condition (>95% R.H) for Palladium (Pd), iridium (Ir) and gold (Au) was carried out using scanning Kelvin probe method by electrochemical charging of hydrogen from entry side and subsequently measuring the Volta potential on exit side (see fig.1). The measured potential on the exit side can be related to electrode potential. Palladium showed a 1:1 correlation between applied potential and measured potential at higher hydrogen activities (between 0 to 300 mVSHE) by establishing electrochemical equilibrium in both conditions, in accordance with [1]. Though the partial pressure of water is very low (0.23mbar) in dry condition, still the hydrogen electrode formation occurred on the palladium. In the case of Ir, it shows 1:1 correlation only in humid condition and not in dry condition. Further, the hydrogen electrode formation on Ir at different partial pressures of water was investigated by controlling the humidity on the exit side of the sample and the obtained results can be attributed to slight differences of thickness of the water layer in the monolayer and even sub-monolayer range. A linear decrease in the potential was observed when increasing the humidity from low to high humidity and the correlation between potential applied from the back and potential measure in the “dry” shows a decrease in responsiveness with decreasing humidity. No correlation was observed for iridium in dry conditions and it can be attributed to presence of insufficient amount of adsorbed water. For gold no correlation was observed in both the conditions. However, a slight behavior was observed at very high activities of hydrogen. This may be due to the initial hydrophobicity of gold, which has first to overcome by a formation of a double layer. On the whole, the effect of water layer adsorption on different metals and its influence on the establishment of a hydrogen electrode at a dry surface was studied.
References:
[1] F. Deißenbeck, C. Freysoldt, M. Todorova, J. Neugebauer, S. Wippermann, Dielectric Properties of Nanoconfined Water: A Canonical Thermopotentiostat Approach, Phys. Rev. Lett. 126 (2021) 136803.
[2] S. Evers, M. Rohwerder, The hydrogen electrode in the dry: A Kelvin probe approach to measuring hydrogen in metals, Electrochem. Commun. 24 (2012) 85–88.
[3] X. Zhong, M. Schulz, C.H. Wu, M. Rabe, A. Erbe, M. Rohwerder, Limiting Current Density of Oxygen Reduction under Ultrathin Electrolyte Layers: From the Micrometer Range to Monolayers, ChemElectroChem. 8 (2021) 712–718.

Figure 1