Journal of Electroanalytical Chemistry, Vol.819, 114-122, 2018
Hydrogen evolution at mixed alpha-Fe-1 (-) xCrxOOH
The activity of mixed alpha-Fe-1 (-) xCrxOOH oxides towards hydrogen evolution in alkaline solution is discussed based on Density Functional Theory (DFT) calculations, cyclic voltammetry and steady state measurements. Thermogravimetric and XRD measurements indicate an isomorphic substitution of Fe by Cr. Electrochemical characterization shows increasingly sluggish hydrogen evolution reaction (HER) kinetics with increased Cr loadings. This decrease in activity is accompanied by the inhibition of the reduction of iron in alpha-Fe-1 (-) xCrxOOH To investigate the origin of this decrease in activity, DFT calculations were performed for mixtures of Fe and Cr placed at Fe(OH)(2). Based on phase diagrams, the most stable structures under HER conditions are identified and used to estimate the theoretical overpotential. In contrast to experiment, no decrease in HER activity is observed. Instead, mixed FeCr sites display an overpotential comparable to that of Pt. Taking into account the inhibition of the bulk reduction in the presence of Cr, the activity decreases in agreement with experiment. These results are very important in the search for cathodes in the chlorate process that are active also in the absence of chromate in solution and may offer a new route for Pt free HER catalysts in alkaline solution.