pKa as a Predictive Descriptor for Electrochemical Anion Adsorption

Abstract

The adsorption of anions onto metal surfaces is important in many applications including effective (electro)catalyst design, metal surface modification, and contaminant removal in wastewater treatment. In electrocatalysis, anions can be both reactive intermediates or site‐blocking spectators, where their adsorption strength therefore dictates the rate of reaction. In this work, we have measured the adsorption energy of a series of carboxylic acids on a Pt (111) single‐crystal electrode surface from aqueous solution. We find that the adsorption strength of the carboxylate anion is linearly correlated with its acid‐dissociation constant (pKa) and therefore the heterolytic O‐H bond dissociation strength in solution. Using density functional theory modeling, we split the anion adsorption energy into a sum of the adsorption energy and electron affinity of a neutral (carboxyl) radical. Surprisingly, the adsorption energy of the carboxyl radicals are similar and therefore the large difference in electron affinity is what dictates anion adsorption strength; the greater the cost in energy to remove the electron from the anion upon adsorption, the weaker its binding. Therefore, at least within a class of anions with similar structure and surface binding atoms, both electron affinity and acidity are predictive descriptors of adsorption strength.

Bridging Machine Learning and Thermodynamics for Accurate pKa Prediction

“…Functional molecules universally contain acidic/basic chemical groups such as carboxyl groups, amino groups, and N -heterocyclic rings, where p K a is the key physical chemistry parameter describing their acid–base equilibria. p K a serves as an informative descriptor for designing catalysis systems − and environmental impact assessment . From a drug discovery perspective, it directly determines structures in physiological environments, influencing key properties such as solubility, membrane permeability, and biomolecular interactions.…”