Surface Modification on Pd-TiO₂ Hybrid Nanostructures towards Highly Efficient H₂ Production from Catalytic Formic...

Metal-containing nanocrystals with well-designed surface structures represent a class of model systems for revealing the fundamental physical and chemical processes involved in heterogeneous catalysis. Herein it is shown how surface modification can be utilized as an efficient strategy for controlling the surface electronic state of catalysts and, thus, for tuning their catalytic activity. As model catalysts, the Pd-tetrahedron-TiO₂ nanostructures, modified on the surface with different foreign atoms, showed a varied activity in the catalytic decomposition of formic acid towards H₂ production. The catalytic activity increases with a reduction in the work function of modified atoms; this reduction can be well explained by a surface polarization mechanism. In this hybrid system, the difference in the work functions of Pd and modified atoms results in surface polarization on the Pd surface and, thus, in the tuning of its charge state. Together with the Schottky junction between TiO₂ and metals, the tuned charge state enables the promotion of catalytic efficiency in the catalytic decomposition of formic acid to H₂ and CO₂ .