Shape-controllable synthesis of GdVO4 photocatalysts and their tunable properties in photocatalytic hydrogen generation

Abstract

Novel visible light responsive materials for water splitting are essential for the efficient conversion of solar energy into hydrogen bond energy. Among other semiconductors, gadolinium orthovanadate has appropriate conduction and valence band edges positioned to split water molecules and a narrow band gap that allows the use of visible light for hydrogen generation. Thus, we present here that hydrogen evolution under visible light (λ > 420 nm) could be accomplished using hierarchical 3D GdVO₄ particles, obtained by a simple, one pot hydrothermal synthesis. We found that applying various reaction components, such as EDTA-Na₂ and EDTA, and adjusting the pH of the solution allow one to tune the shape of GdVO₄ (such as short nanowires, long nanowires, short nanorods, long nanorods, nanoparticles and spheres – all having a tetragonal crystal structure) as well as optical and photocatalytic properties. The highest ability to photocatalytically split methanol solution into hydrogen under UV-Vis irradiation was detected for the long nanowire sample (42 μmol h⁻¹), having almost 11 times higher efficiency in comparison with the weakest sample – short nanowires. In addition, GdVO₄ spheres generated H₂ more than 2 times (5.75 μmol h⁻¹) in comparison with the short nanorod sample (2.5 μmol h⁻¹) under visible light excitation. Photostable in three-hour work cycles, long nanowires and spheres were even able to generate hydrogen from pure water, reaching values of 17 and 3 μmol under UV-Vis and Vis light, respectively.