Facet Engineering of Pd Nanocrystals for Enhancing Photocatalytic Hydrogenation: Modulation of the Schottky Barrier Height and Enrichment of Surface Reactants

Metal cocatalyst loading is one of the most widely explored strategies in promoting photocatalytic solar energy conversion. Engineering surface-active facets of metal cocatalyst and exploring how they modulate the reactivity is crucial for the further development of advanced photocatalysts. In this work, through controlled hybridization of two-dimensional (2D) TiO 2 nanosheets with well-designed Pd nanocube (Pd NC) with exposed {100} facet and Pd nano-octahedron (NO) with exposed {111} facet, we unravel the distinct crystal facet effect of Pd cocatalyst in promoting the selective hydrogenation of nitroarenes to amines of TiO 2 photocatalyst. The activity tests show that the Pd NO with {111} facet is a more efficient cocatalyst than the Pd NC with exposed {100} facet. The prepared TiO 2 -Pd NO composite displays a 900% enhancement of photocatalytic hydrogenation rate in comparison with bare TiO 2 , while the TiO 2 -Pd NC sample only shows a 200% photoactivity enhancement. Microscopic mechanism study discloses that the distinctive photoactivity improvement of Pd NO is ascribed to the concurrent modulation of the Schottky barrier height and enrichment of surface reactants: (i) the Pd NO with a lower Fermi level could result in steeper band bending of TiO 2 (i.e., higher Schottky barrier) than the Pd NC, which is more efficient in boosting interfacial separation and inhibiting the recombination of photoexcited charge pairs; and (ii) the {111} facet of Pd has higher nitroarenes adsorption ability and especially stronger hydrogen enrichment capability, thus accelerating the surface hydrogenation process and contributing to a higher reaction rate. This work emphasizes the rational facet control of cocatalysts for enhancing the photocatalytic hydrogenation performance.