Titanium Substitution Effects on the Structure, Activity, and Stability of Nanoscale Ruthenium Oxide Oxygen Evolution Electrocatalysts: Experimental and Computational Study

Proton-exchange membrane water electrolyzers produce hydrogen from water and electricity and can be powered using renewable energy; however, the high overpotential, high cost, and limited supply of the oxygen evolution reaction (OER) electrocatalyst are key factors that hinder wide-scale adoption. Ruthenium oxide (RuO2) has a lower overpotential, lower cost, and higher global supply compared with iridium oxide (IrO2), but RuO2 is less stable than IrO2. As an approach to improve the catalytic stability, we report the effect of titanium substitution at different concentrations within nanoscale RuO2, Ru1-xTixO2 (x = 0-50 at. %), on the structure, OER activity, and stability using combined experiments and theory. Titanium substitution within rutile RuO2 affects the electronic structure, resulting in regions of electron accumulation and electron depletion at the surface, and shifts the d -band and O 2p band centers to higher binding energies. Calculations show that the effects of Ti on the electronic structure are highly dependent on not only the concentration but also the specific dopant location. From electrochemical testing and analysis of the electrolyte and simulations, titanium substitution at low concentrations (12.5 and 20 at. %) improves catalyst stability and lowers Ru dissolution. Experiments of OER activity agree with the theory that Ti substitution results in a higher overpotential when averaging over all adsorption sites. Theoretical analysis shows that specific sites predominately act as catalytic sites for the OER, while metal dissolution occurs at different sites. Specifically, OER has the lowest barriers at penta-coordinated Ru sites, while hexa-coordinated Ru sites have the lowest energetic barriers for dissolution.