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

Angew Chem Int Ed Engl. 2021 Jul 26;60(31):16994-16998. doi: 10.1002/anie.202106786. Epub 2021 Jun 26.

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.

Keywords: cluster compounds; hydrogen; polyoxometalates; silver nanoclusters.