Switchable High-Valent Ag 3+ /Ag + Redox Pair Stabilized in Polyoxometalate as Highly Oxidative “Electron Shuttle” Catalysts

Journal article

We report the isolation and characterization of the first example of a crystallized high-valent Ag3+-containing polyoxometalate (POM) complex, Cs7K4[P2W19AgIIIO69(OH2)]·17H2O (1), as a “catalyst bearing catalyst” capable of catalyzing the formation of the high-valent Ni3+-containing POMs in the presence of peroxydisulfate. The oxidation state and exotic chemical behaviors of Ag in 1 were confirmed by crystallographic, spectroscopic, and electrochemical characterizations. The Ag3+/Ag+ redox pair embedded in 1 showed good electrochemical reversibility and the ability to accelerate electron transfer, contributing to the observed catalytic activity of 1 in both formation of other high-valent metal-containing POMs and electrochemical oxidative C–H activation.

Authors: Li, X; Hui, H; Ren, Y; Liu, Z; Li, Y

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: JACS Au
• Volume: 5
• Issue: 10
• Pages: 5089-5097
• Publication date: 2025-10-14
• Acceptance date: 2025-10-03
• DOI: 10.1021/jacsau.5c00987
• EISSN: 2691-3704
• ISSN: 2691-3704
• Language: English
• Keywords: electrochemistry; oxidation; redox chemistry; silver; polyoxometalates; electrocatalysis