Three-phase co-assembly of compositionally tunable WO3/TiO2 inverse opal photoelectrodes

Heterostructured WO3/TiO2 photonic crystal films in the form of three-dimensional macroporous inverse opals were developed by single-step, three-phase co-assembly of colloidal templates with water soluble precursors enabling simultaneous growth of both metal oxides into a firmly interconnected periodic pore framework whose skeletal walls consisted of uniformly distributed nanoscale type II WO3-TiO2 heterojunctions. A marked size- and composition-dependence of the binary WO3/TiO2 inverse opal properties was evidenced by controlling the W/Ti molar ratio and macropore diameter that allowed Fermi level and photonic band gap engineering according to optical and photoelectron spectroscopies supplemented by electrochemical measurements. Compositional tuning along with the reduction of WO3 nanocrystallite size and the concomitant W5+ defect growth with increasing TiO2 phase content were explored for the optimization of photocurrent generation by WO3/TiO2 inverse opal photoanodes combining reduced charge carrier recombination and optimal slow light trapping. One step co-assembly of mixed metal oxides is concluded as a promising route for the development of heterostructured inverse opal networks with tailored electronic properties and improved solar light harvesting for photo-induced applications.