Boosting the photocatalytic hydrogen production of TiO₂ by using copper hexacyanocobaltate as co-catalyst

The development of cheap and efficient co-catalysts is crucial to improve the performance of well-known photocatalysts towards the hydrogen evolution reaction. Here, copper hexacyanocobaltate was evaluated for the first time as a potential candidate to be used as co-catalyst coupled with conventional TiO₂. Copper hexacyanocobaltate was formed by chemical precipitation in the presence of TiO₂, without needing further treatments. The composite exhibited paramount performance towards hydrogen generation, surpassing by up to 16 times the behavior reached with bare TiO₂. This composite also overcome the performance of conventional TiO₂ modified with copper and cobalt oxides derived from copper hexacyanocobaltate. The enhanced behavior of TiO₂/Cu₃[Co(CN)₆]₂ composite was promoted by the efficient separation of photogenerated charge carries, and the faster charge transfer from photocatalyst towards species in solution, as it was proved by the photoelectrochemical characterization of the materials. Furthermore, the composite experienced a slight detriment (15%) in its hydrogen production rate after four consecutive photocatalyst tests. This variation was attributed to the slow leaching of copper in the co-catalyst caused by its partial transformation into metal hydroxides, as it was suggested by the ex-situ XPS characterization. Nevertheless, the structural characterization evinced the presence of the Cu₃[Co(CN)₆]₂ in the composite after long-term use. This study should be considered a proof of concept on a reliable route to obtain appropriate composites for hydrogen production using light as primary energy source.