The electrochemical hydrogenation (ECH) of bio-mass derived compounds is an attractive alternative to traditional thermochemical hydrogenation (TCH) methods that are used in the U.S. chemical and petroleum industries to produce value-added fuels and chemicals. TCH uses high pressures and temperatures, along with an external source of hydrogen gas typically produced via methane reformation; these requirements make it an energy intensive process. ECH has the advantages of operating near ambient conditions and sourcing the participating hydrogen from the aqueous electrolyte solution, resulting in reduced energy costs and CO₂ emissions compared to TCH. The applied potential provides an additional parameter for controlling selectivity, which makes ECH more suitable to handle the wide chemical variability of biomass-derived feedstocks.

Aromatic hydrocarbons are of interest as model compounds for lignocellulosic bio-oil [1]. The ECH of aromatic hydrocarbons proceeds with high faradaic efficiency (FE) at low overpotentials, however, the ECH turnover rate remains low at these potentials. There is no simple fix to this, as any increase in overpotential, to increase ECH rate, will reduce the reaction FE due to competition with the hydrogen evolution reaction (HER). In this work we address the need for a more fundamental understanding of ECH systems to promote high turnover rates at low overpotentials. Specifically for phenol TCH, it is well known that the hydrogenation is limited by the formation/addition of surface adsorbed hydrogen. The current ECH literature draws on these TCH studies and assumes that phenol ECH is also limited by surface adsorbed hydrogen [2]. Thus, most ECH work is done is acidic media, where the kinetics of surface adsorbed hydrogen formation are fastest on platinum [3]. HER, however, is also faster on platinum in acidic media [4], making it more difficult to achieve high faradaic efficiency.

Because of this limited scope of investigation, the impact of electrolyte chemistry, i.e. pH, on ECH kinetics has only been sparingly investigated. In this work, we investigate a new pathway for enhanced rates at low overpotentials, driven by the acid-base chemistry of reactants and using electrolyte pH to promote dissociative adsorption. By tailoring the electrolyte pH based on the pKa of the reactant molecule, we can lower the barrier associated with the first hydrogenation step, improving overall reaction kinetics. We demonstrate this effect with phenol ECH at various pH electrolyte on low-index single crystal electrodes using rotating disk electrode voltammetry and chrono-amperometry with product analysis. The ECH of acetophenone and benzaldehyde are also included to compare the effect of different functionalities on the phenyl ring. We report on the structural sensitivity, influence of pH and resulting electric field effects, and present new mechanistic insights for phenol ECH. With these insights we propose methods to promote higher ECH rates at lower overpotentials.

References:

[1] J. Yan et al., "Characterizing Variability in Lignocellulosic Biomass: A Review," ACS Sustainable Chemistry & Engineering, vol. 8, no. 22, pp. 8059-8085, 2020, doi: 10.1021/acssuschemeng.9b06263.

[2] N. Singh et al., "Aqueous phase catalytic and electrocatalytic hydrogenation of phenol and benzaldehyde over platinum group metals," Journal of Catalysis, vol. 382, pp. 372-384, 2020, doi: 10.1016/j.jcat.2019.12.034.

[3] S. Intikhab, J. D. Snyder, and M. H. Tang, "Adsorbed Hydroxide Does Not Participate in the Volmer Step of Alkaline Hydrogen Electrocatalysis," ACS Catalysis, vol. 7, no. 12, pp. 8314-8319, 2017, doi: 10.1021/acscatal.7b02787.

[4] I. Ledezma-Yanez, W. D. Z. Wallace, P. Sebastián-Pascual, V. Climent, J. M. Feliu, and M. T. M. Koper, "Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes," Nature Energy, vol. 2, no. 4, 2017, doi: 10.1038/nenergy.2017.31.