Mechanisms for Charge Selectivity on Semiconducting Photocatalyst Particles

Abstract

Overall-water splitting on photocatalysts provides a direct-unassisted path in the conversion of solar energy to chemical energy. Optoelectronic properties (absorbing incident light with long excited state lifetimes) and carrier selective contacts (transporting and transferring the desired electronic carrier to the targeted redox active species) are two key parameters that govern photocatalyst behavior. However, the advantageous small geometry of the highest achieving photocatalysts makes measurement of their carrier selective contacts difficult. Additionally, several mechanisms that enable high energy-conversion efficiencies and large gradients in free energy manifest only at the nanoscale at individual nanoparticle sites. SrTiO3 has been extensively studied and shown to split water with high quantum yields when decorated with HER and OER catalysts. SrTiO3 is used, in this work, as a model system to study mechanisms for charge selectivity on overall-water splitting photocatalyst particles.Here, we use three sample geometries to measure local, facet, and catalyst-dependent, electrochemical driving forces and their synergistic enhancement of carrier selectivity, (single crystal planar (b), single crystal co-facet exposed planar (a), facetted nanoparticles (c) loaded with OER and HER catalysts [{Pt/CrO3, Rh/CrO3} and CoOOH respectively]). We use ex-situ conductive atomic force microscopy to individually interrogate the electrical properties of nano-scale catalyst/semiconductor junctions decorated on facet-engineered surfaces of SrTiO3. Supporting experiments of SECM and Operando AP-XPS will be used to measure the charge carrier selectivity when an electrolyte is present and connect the ex-situ characterization observations to operando conditions. In summary, these findings demonstrate the underlying mechanisms and the degree that they play, enabling directed research of photocatalyst systems under the two dominant engineering conditions, high optoelectronic properties and charge selective contacts. Figure 1