Inhomogeneous RVO4 Photocatalyst Systems (R = V. Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

By resorting on first-principles dynamical simulations and supporting experiments, we present a systematic and detailed inspection of a new series of inhomogeneous photocatalytic RVO4 systems (R = Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), where YVO, is the most representative member. We evidenced a carrier separation, promoted by Pt acting as a cocatalyst, which allows for a clear understanding of the electronic properties of these inhomogeneous systems. These, in turn, are shown to be of crucial importance in enhancing the photocatalytic activity in the cases of water or methanol aqueous solutions. The presence of f electrons, acknowledged as essential for an optimal photocatalytic performance, is clearly rationalized and the possibility of using Lu, in view of its smaller ionic radius, to enhance hydrogen generation is disclosed. Experiments confirm that YVO4, GdVO4, and LuVO4 have a potentially much higher efficiency than compounds containing other rare earth lanthanides. Hence, we provide a comprehensive guideline for designing a new generation of photocatalysts possessing unprecedented efficiencies.