The puzzling pH dependence of HOR/HER leading to the approximately 2 orders of magnitude loss in platinum group metal (PGM) activity in base has hindered both the practical design of electrochemical devices as well as the fundamental understanding of electrode/electrolyte interfaces.¹ Explanations for this effect have ranged from the presence of adsorbates specific to alkaline conditions,² shifts in the electrode potential of zero free charge (pzfc) and subsequent strengthening of the interfacial electric field,³ the orientation of interfacial water molecules, and changes in the binding energy of reaction intermediates.^4–6 Recently, several innovative in situ techniques have been used to probe these theories, ranging from Fourier Transform Infrared Spectroscopy (FTIR) to X-Ray Absorption Spectroscopy (XAS), as well as novel computational studies to isolate the contributions of surface adsorbed hydroxide and water.^2–4,7 Additionally, the identification of caffeine as a “double-layer dopant” capable of improving HOR/HER activity 5-fold on Pt(111) has provided the field with a model system with which to systematically test these theories.⁸ Despite this, an overarching understanding of the mechanism and caffeine’s promoting role is still unclear, and a more rigorous analysis of the electrode surface is necessary.

The electrochemical interface is traditionally viewed with a double layer model, with specific electrochemical adsorbates existing in the Inner Helmholtz Plane (IHP), the first layer of non-adsorbates at the Outer Helmholtz Plane (OHP), and water in abundance. One leading theory used to understand the activity loss from acid to alkaline environments is the decrease in surface potential relative to the pzfc in base resulting in stronger electric fields which restrict the approach of reactive intermediates to the IHP/OHP. Caffeine is suspected of reducing the IEF strength through decreasing the pzfc to relevant HOR/HER potentials, creating an acidic like environment. In this work, we challenge this notion by using SEIRAS with CO as a probe molecule to directly measure the interfacial field strength in 0.1 M KOH solutions with the model caffeine system showing HOR/HER enhancement, as well as different concentrations of various organic species with no promoting kinetic impact. FTIR studies using CO as a probe molecule to measure stark tuning rates have long been used to directly measure the interfacial electric field strength, dictated by the majority species in the OHP.^9,10 The low ST rate of 22 cm^-1V^-1 found for all of these species in our experiments, regardless of their impact on HOR/HER kinetics, implies reductions in IEF are not solely responsible for the KOH-caffeine system’s increased activity. Rather, caffeine induces changes to the interfacial water structure as evidenced by differences in water’s ν(O-H) stretching modes, allowing for more facile kinetics, the main parameter responsible for the “apparent pH dependence” of PGM HOR/HER.

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