Controlling the structural and optical properties of tungsten oxide films synthesized under environmentally friendly conditions

The conversion, storage, and utilization of renewable energy have all become more important than ever before as a response to ever-growing energy and environment concerns. The performance of energy-related technologies strongly relies on the structure and property of the material used. The earth-abundant family of tungsten oxides (WOx ≤3 ) receives considerable attention in photocatalysis, electrochemistry, and phototherapy due to their highly tunable structures and unique physicochemical properties. Great breakthroughs have been made in enhancing the optical absorption, charge separation, redox capability, and electrical conductivity of WOx ≤3 through control of the composition, crystal structure, morphology, and construction of composite structures with other materials, which significantly promotes the efficiency of processes and devices based on this material. Herein, the properties and synthesis of WOx ≤3 family are reviewed, and then their energy-related applications are highlighted, including solar-light-driven water splitting, CO2 reduction, and pollutant removal, electrochromism, supercapacitors, lithium batteries, solar and fuel cells, non-volatile memory devices, gas sensors, and cancer therapy, from the aspect of function-oriented structure design and control.

Mesoporous semiconducting films consisting of preferentially orientated monoclinic-phase nanocrystals of tungsten trioxide have been prepared using a novel version of the sol-gel method. Transformations undergone by a colloidal solution of tungstic acid, stabilized by an organic additive such as poly(ethylene glycol) (PEG) 300, as a function of the annealing temperature have been followed by means of a confocal Raman microscope. The shape and size of WO3 nanoparticles, the porosity, and the properties of the films depend critically on preparation parameters, such as the tungstic acid/PEG ratio, the PEG chain length, and the annealing conditions. Well-crystallized WO3 films combine excellent photoresponse to the blue region of the solar spectrum, up to 500 nm, with good transparency at wavelengths larger than 550 nm. Particular applications of these nanocrystalline WO3 films include photoelectrochemical and electrochromic devices.

Some recent studies mainly addressing the preparation and the modification of nanostructured thin films based on WO(3) and their application to photoelectrolysis of aqueous electrolytes are reviewed with the aim of rationalizing the main factors at the basis of an efficient photoanodic response. WO(3) represents one of the few materials which can achieve efficient water photo-oxidation under visible illumination, stably operating under strongly oxidizing conditions; thus the discussion of the structure-related photoelectrochemical properties of WO(3) thin films and their optimization for achieving almost quantitative photon to electron conversion constitutes the core of this contribution.