Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting.

Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni(1-x)Fe(x)OOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe(3+) in Ni(1-x)Fe(x)OOH occupies octahedral sites with unusually short Fe-O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni(1-x)Fe(x)OOH are not active sites for the oxidation of water.

Cluster size effects in the photocatalytic hydrogen evolution reaction.

The photocatalytic water reduction reaction on CdS nanorods was studied as function of Pt cluster size. Maximum H2 production is found for Pt46. This effect is attributed to the size dependent electronic properties (e.g., LUMO) of the clusters with respect to the band edges of the semiconductor. This observation may be applicable for the study and interpretation of other systems and reactions, e.g. H2O oxidation or CO2 reduction.

Size-selected subnanometer cluster catalysts on semiconductor nanocrystal films for atomic scale insight into photocatalysis.

We introduce size-selected subnanometer cluster catalysts deposited on thin films of colloidal semiconductor nanocrystals as a novel platform to obtain atomic scale insight into photocatalytic generation of solar fuels. Using Pt-cluster-decorated CdS nanorod films for photocatalytic hydrogen generation as an example, we determine the minimum amount of catalyst necessary to obtain maximum quantum efficiency of hydrogen generation. Further, we provide evidence for tuning photocatalytic activities by precisely controlling the cluster catalyst size.

Enabling Overall Water Splitting on Photocatalysts by CO-Covered Noble Metal Co-catalysts.

Photocatalytic overall water splitting requires co-catalysts that efficiently promote the generation of H2 but do not catalyze its reverse oxidation. We demonstrate that CO chemisorbed on metal co-catalysts (Rh, Pt, Pd) suppresses the back reaction while maintaining the rate of H2 evolution. On Rh/GaN:ZnO, the highest H2 production rates were obtained with 4-40 mbar of CO, the back reaction remaining suppressed below 7 mbar of O2. The O2 and H2 evolution rates compete with CO oxidation and the back reaction. The rates of all reactions increased with increasing photon absorption. However, due to different dependencies on the rate of charge carrier generation, the selectivities for O2 and H2 formation increased in comparison to CO oxidation and the back reaction with increasing photon flux and/or quantum efficiency. Under optimum conditions, the impact of CO to prevent the back reaction is identical to that of a Cr2O3 layer covering the active metal particle.