Optimised photocatalytic hydrogen production using core–shell AuPd promoters with controlled shell thickness

The development of efficient photocatalytic routines for producing hydrogen is of great importance as society moves away from energy sources derived from fossil fuels. Recent studies have identified that the addition of metal nanoparticles to TiO2 greatly enhances the photocatalytic performance of these materials towards the reforming of alcohols for hydrogen production. The core–shell structured Au–Pd bimetallic nanoparticle supported on TiO2 has being of interest as it exhibited extremely high quantum efficiencies for hydrogen production. However, the effect of shell composition and thickness on photocatalytic performance remains unclear. Here we report the synthesis of core–shell structured AuPd NPs with the controlled deposition of one and two monolayers (ML) equivalent of Pd onto Au NPs by colloidal and photodeposition methods. We have determined the shell composition and thickness of the nanoparticles by a combination of X-ray absorption fine structure and X-ray photoelectron spectroscopy. Photocatalytic ethanol reforming showed that the core–shell structured Au–Pd promoters supported on TiO2 exhibit enhanced activity compared to that of monometallic Au and Pd as promoters, whilst the core–shell Au–Pd promoters containing one ML equivalent Pd provide the optimum reactivity