Cooperative selective benzyl alcohol oxidation and hydrogen production over Pd6(SC12H25)12 cluster-coupled CdS nanorods: the key role of water in photocatalytic benzyl alcohol splitting

Abstract

Photocatalytic splitting of alcohols into hydrogen and the corresponding carbonyl compounds has potential applications in the production of clean H₂ fuel and high-value chemicals using solar light as the sole energy input. Here, we demonstrated that a highly efficient photocatalyst could be constructed for photocatalytic cooperative highly selective oxidation of benzyl alcohol to benzaldehyde and H₂ production by confining atomically precise Pd₆(SC₁₂H₂₅)₁₂ clusters on CdS nanorods, which dramatically enhanced the photocatalytic activity. Ultrafast transient absorption (TA) spectroscopy investigations disclosed that well-defined Pd₆(SC₁₂H₂₅)₁₂ clusters could assist the photo-generated charge separation of CdS nanorods. Density functional theory (DFT) calculations clearly revealed the mechanism of benzyl alcohol decomposition and highlighted the crucial role of water molecules at atomic precision. This work provides fresh insights into the photocatalytic application of atomically precise metal clusters and sheds light on the water promotion effects in photocatalytic splitting of benzyl alcohol.