Unveiling the Remarkable Stability and Catalytic Activity of a 6-Electron Superatomic Ag30 Nanocluster for CO2 Electroreduction

Nanocluster catalysts face a significant challenge in striking the right balance between stability and catalytic activity. Here, we present a thiacalix[4]arene-protected 6-electron [Ag30(TC4A)4(iPrS)8] nanocluster that demonstrates both high stability and catalytic activity. The Ag30 nanocluster features a metallic core, Ag104+, consisting of two Ag3 triangles and one Ag4 square, shielded by four {Ag5@(TC4A)4} staple motifs. Based on DFT calculations, the Ag104+ metallic kernel can be viewed as a trimer comprising 2-electron superatomic units, exhibiting a valence electron structure similar to that of the Be3 molecule. Notably, this is the first crystallographic evidence of the trimerization of 2-electron superatomic units. Ag30 can reduce CO2 into CO with a Faraday efficiency of 93.4% at -0.9 V versus RHE along with excellent long-term stability. Its catalytic activity is far superior to that of the chain-like AgI polymer ∞1{[H2Ag5(TC4A)(iPrS)3]} (∞1Agn), with the composition similar to Ag30. DFT calculations elucidated the catalytic mechanism to clarify the contrasting catalytic performances of the Ag30 and ∞1Agn polymers and disclosed that the intrinsically higher activity of Ag30 may be due to the greater stability of the dual adsorption mode of the *COOH intermediate on the metallic core.