Re-Structuring of Interfacial Water into Strongly Hydrogen Bonded “Ice-like” Structures as the Unifying Descriptor for Improving Sluggish HOR/HER in Alkaline Electrolyte
Authors: Oliveira Nicholas J , Yan Yushan 
Published: September 2023

The 2 orders of magnitude loss of Platinum Group Metal (PGM) activity toward Hydrogen Oxidation and Reduction reactions (HOR/HER) has hindered implementation of alkaline based electrolyzers and fuel cells and demonstrated a significant knowledge gap in our fundamental understanding of electrochemical interfaces.1 Beneath the seemingly simple reaction lies a potentially convoluted mechanism, with various researchers assigning the activity loss to shifts in electrode potential of zero free charge,2 changed binding energies of adsorbates and reactive intermediates,3,4 and the re-arrangement of interfacial water.5 Recently, Monteiro et al. showed an activity dependence on interfacial cation concentration and identity, suggesting that charge dense cations are able to better stabilize the OH- produced from the unfavorable but necessary water splitting in the HER direction near the negatively charged surface.6,7 In this work, we challenge this notion by demonstrating that competition for water molecules between Outer Helmholtz Plane (OHP) cations and the interfacial water structure is responsible for the activity loss. Through the use of traditional Rotating Disk Electrode, in situ Attenuated Total Reflection-Surface Enhanced Infrared Reflection Absorption Spectroscopy (ATR-SEIRAS) and judicious choice of crown ether additives to hinder the water-interfacial cation interaction, we show a positive correlation between the strength and number of interfacial water-water hydrogen bonds and platinum’s HOR/HER activity.
The typical double layer structure in an aqueous electrochemical system consists of specifically adsorbed species in the Inner Helmholtz Plane (IHP), the first layer of non-adsorbates at the OHP, and water hydrating the charged species. ATR-SEIRAS has previously been used to analyze the structure of these hydration shells on a CO covered Pt surface, demonstrating hydrating waters interacting mainly with alkali metal cations through the increase of a 3600 cm-1 ν(O-H) stretch and weak interactions with surrounding interfacial water.8 Through chelation with crown ether, these hydration shells convert from strongly to weakly cation interacting, favoring instead hydrogen bonding with other water molecules, shown with increasing absorption bands at lower wavenumbers (3400 cm-1). This transition is accompanied by an increase in 3000 cm-1 on the CO-free Pt surface, previously assigned to strongly hydrogen bonded “ice-like” interfacial water.9 We further show a similar increase in the 3000 cm-1 band for other kinetic enhancing additives recently reported in the literature, supporting the notion that increasing water-water hydrogen bonding is the unifying descriptor for promoting a rigid interfacial “ice-like” structure and improving PGM HOR/HER activity.

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