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

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. [ABSTRACT FROM AUTHOR]