Integration of Lanthanide-Transition-Metal Clusters onto CdS Surfaces for Photocatalytic Hydrogen Evolution

Abstract

Heterometallic lanthanide-transition-metal (4f-3d) clusters with well-defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f-3d clusters Ln₅₂ Ni₅₆ on a CdS photoabsorber surface. Interestingly, some Ni²⁺ ions in the clusters Ln₅₂ Ni₅₆ were exchanged by the Cd²⁺ to form Ln₅₂ Ni_56-x Cd_x /CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu₅₂ Ni_56-x Cd_x cluster enable high visible-light-driven hydrogen evolution at 25 353 μmol h^-1 g^-1 . This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f-3d clusters on semiconductor materials.

Keywords: cadmium sulfide; clusters (4f-3d); hydrogen evolution; photocatalysis.