Title:	Electrocatalysis beyond aqueous solvation
DNr:	NAISS 2025/5-393
Project Type:	NAISS Medium Compute
Principal Investigator:	Magnus Gustafsson <Magnus.Gustafsson@ltu.se>
Affiliation:	Luleå tekniska universitet
Duration:	2025-06-25 – 2026-01-01
Classification:	10304 10407 10403
Homepage:	https://www.ltu.se/en/staff/m/michael-busch
Keywords:

Abstract

Converting CO2 into fuels or feedstocks (CO, methane, and ethanol) closes the carbon loop while electrocatalytic valorization of waste biomass delivers high-value chemicals. Catalysts are required to ensure the commercial viability of both processes, however the reaction mechanisms involved and their dependence on experimental conditions such as the pH, potential, and solvent, are not yet fully established. Direct interactions between the catalyst or the reactant with the solvent can dramatically alter proton transfer barriers and overall energetics. Metal oxide catalysts are particularly sensitive: solvent molecules can reconstruct the surface or form overlayer structures that alter the catalytic activity. Implicit solvent models fail in these cases and fully explicit solvation is often too costly. Furthermore, appropriate non-aqueous solvation strategies are not as well developed as for aqueous solvents. Therefore, a balanced solvation approach is required to capture solvation effects on reaction energetics beyond aqueous solvents. This project will map out the mechanism of CO2 reduction on single- and dual-atom catalysts such based on metal phthalocyanines by computing reaction energies and transitions states with density functional theory methods. Similarly, we will examine the redox mechanisms of simple sugars on gold surfaces and characterize the acid-base chemistry of metal oxide surfaces such as TiO2. We will also develop and validate an explicit-plus implicit solvation workflow based on ab initio molecular dynamics to accurately predict pKas and proton transfer energetics in aqueous and non-aqueous solvents. A more complete understanding of the reaction mechanisms and solvation effects will enable us to build microkinetic and kinetic-Monte Carlo models to link computed barriers to experimentally observed product distributions under varying pH and potential. The resulting insights into the reaction mechanisms and the fundamental acid-base chemistry will guide the rational design of electrocatalytic reaction systems where both the solvent and catalyst are optimized for the desired outcome.