On the thermodynamics of hydrogen adsorption over Pt(111) in 0.05M NaOH.

The reasons for the sluggish kinetics of the hydrogen adsorption reaction in alkaline media remain a question still to be solved. This information is important to achieve a complete understanding of the mechanistic details that could lead to the production of key catalytic materials necessary for the development of a future hydrogen economy. For a better understanding of this reaction, it is important to acquire information about the thermodynamic parameters characteristic of the different steps in the reaction. Among these, the hydrogen adsorption is a key step in the process of hydrogen evolution. Although some debate still remains about the difference between adsorbed hydrogen in the underpotential deposition (UPD) region and at the overpotential deposition region, there is no doubt that understanding the former can help in the understanding of the latter. Making use of charge density measurements, we report on this paper a thermodynamic study of the hydrogen UPD process on Pt(111) in 0.05M NaOH over the range of temperatures from 283 ≤ T/K ≤ 313. The coulometric features corresponding to HUPD allow for the calculation of the hydrogen coverage and a fit to a Generalized Frumkin isotherm. From these values, different thermodynamic functions for the UPD reaction have been calculated: ΔGads, ΔSads, ΔHads, and the Pt-H bond energy. From extrapolation, a value of ΔSads ◦=-7.5±4Jmol-1K-1 was found, which is very close to 0, much lower than previously reported measurements both in acid and in alkaline solutions. Such value has an effect on the enthalpy and bond energy calculations, the latter having a decreasing tendency with pH and coverage. This tendency is completely different from the acidic systems and implies that the change in the thermodynamic functions due to the formation of the double layer and the reorganization of interfacial water has a strong influence on the process in high pH solutions.

Activation Energy of Hydrogen Adsorption on Pt(111) in Alkaline Media: An Impedance Spectroscopy Study at Variable Temperatures.

The hydrogen evolution reaction is one of the most studied processes in electrochemistry, and platinum is by far the best catalyst for this reaction. Despite the importance of this reaction on platinum, detailed and accurate kinetic measurements of the steps that lead to the main reaction are still lacking, particularly because of the fast rate of the reaction. Hydrogen adsorption on Pt(111) has been taken as a benchmark system in a large number of computational studies, but reliable experimental data to compare with the computational studies is very scarce. To gain further knowledge on this matter, a temperature study of the hydrogen adsorption reaction has been carried out to obtain kinetic information for this process on Pt(111) in alkaline solution. This was achieved by measuring electrochemical impedance spectra and cyclic voltammograms in the range of 278 ≤ T ≤ 318 (K) to obtain the corresponding surface coverage by adsorbed species and the faradaic charge transfer resistance. From this data, the standard rate constant has been extracted with a kinetic model assuming a Frumkin-type isotherm, resulting in values of 2.60 × 10-7 ≤ k0 ≤ 1.68 × 10-6 (s-1). The Arrehnius plot gives an activation energy of 32 kJ mol-1. Comparisons are made with values calculated by computational methods and reported values for the overall HER, giving a reference frame to support future studies on hydrogen catalysis.