A Molecular Hybrid of an Atomically Precise Silver Nanocluster and Polyoxometalates for H₂ Cleavage into Protons and Electrons

Abstract

Atomically precise silver (Ag) nanoclusters are promising materials as catalysts, photocatalysts, and sensors because of their unique structures and mixed-valence states (Ag⁺ /Ag⁰ ). However, their low stability hinders the in-depth study of their intrinsic reactivity and catalytic property accompanying their redox processes. Herein, we demonstrate that a molecular hybrid of an atomically precise {Ag₂₇ }¹⁷⁺ nanocluster and polyoxometalates (POMs) can efficiently cleave H₂ into protons and electrons. The Ag nanocluster accommodates electrons through the redox reaction from {Ag₂₇ }¹⁷⁺ to {Ag₂₇ }¹³⁺ , and the POM ligands play the following important roles: (i) a significant stabilization of the typically unstable Ag nanocluster to preserve its structure during the redox reaction with H₂ , (ii) formation of a unique interface between the Ag nanocluster and metal oxides for efficient H₂ cleavage, and (iii) storage of the generated protons on the negatively charged basic surface.