Correlation between phase composition and physicochemical properties in Cu-, Mo-, and W- doped bismuth vanadate

Abstract

We report a detailed study about the correlation between the physicochemical properties of solvothermally synthesized pristine and 1 %, 2.5 %, and 5 % Cu, Mo, and W-doped bismuth vanadate (BiVO4, BVO) with its phase composition. The effect of the dopant and the duration of synthesis (8 h and 20 h) on the physicochemical properties of BVO allowed us to tune the ratio of monoclinic scheelite to tetragonal zircon phase in BVO powders. This approach helped us to establish the relationship between the presence of monoclinic scheelite or tetragonal zircon phase with structural, morphological and optical properties of BVO powders, obtained by different physicochemical methods (e.g. X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS), Diffuse Reflectance Spectroscopy (DRS) and Photoluminescence spectroscopy (PL)). The results indicated that, in addition to XRD, Raman, and DRS, several other methods could distinguish between the two phases. For example, SEM analysis revealed that monoclinic scheelite BVO exhibits either elongated assemblies of cube-like particles or prismatic particles with sizes ∼500 nm. In contrast, tetragonal zircon BVO exclusively exhibited porous spherical particles with diameter ∼2 μm. DRS and Raman spectroscopy indicated that there is a possibility of distinguishing between the two phases if their shares are large enough. For instance, monoclinic BVO showed band gap values in the range of 2.35–2.52 eV, while tetragonal zircon BVO exhibited values in the range of 2.80–3.00 eV. XPS showed a correlation between phase composition and surface chemistry of BVO only for Cu-doped samples, revealing the presence of Cu+ in monoclinic BVO and the presence of both Cu+ and Cu2+ in tetragonal zircon BVO. PL showed that monoclinic scheelite BVO displayed decreased charge recombination compared to tetragonal zircon BVO. Deeper insight into the correlation between the physicochemical properties and phase composition of Cu, Mo, and W-doped bismuth vanadate (BiVO4, BVO) was based on water/pentanol medium (2:1 vol%) as a novel synthesis pathway. This may open new avenues for the broader methodological exploration of surface chemistry, particle size, and morphology of BVO particles through the use of diverse functionalization agents. Finally, the established links between phase composition and structural, morphological, and other physicochemical properties provide new and more predictable opportunities for further improvement of BVO properties for various applications.