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

Abstract

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 Ag 30 nanocluster features a metallic core, Ag10 4+, consisting of two Ag3 triangles and one Ag4 square, shielded by four {Ag5@(TC4A)4} staple motifs. Based on DFT calculations, the Ag10 4+ 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. Ag 30 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]} (∞ 1 Ag n ), with the composition similar to Ag 30 . DFT calculations elucidated the catalytic mechanism to clarify the contrasting catalytic performances of the Ag 30 and ∞ 1 Ag n polymers and disclosed that the intrinsically higher activity of Ag 30 may be due to the greater stability of the dual adsorption mode of the *COOH intermediate on the metallic core.

Synthesis and characterization of Ag(I) alkynyl nanoclusters utilizing Mo VI-anchored thiacalix[4]arene metalloligands: Application in electrocatalytic CO 2 reduction

“…In 2016, the Wang group achieved an important milestone by reporting the first structurally defined TC4A-protected Ag 35 NC [35][36][37][38]. Building upon this pioneering work, subsequent studies achieved the synthesis of TC4A-based Ag NCs, including Ag 34 , Ag 42 , and Ag 88 [39][40][41][42][43][44]. Recently, the Sun group reported an extraordinary Ag 155 NC featuring a multishell structure with Ag 13 @Ag 42 @Ag 30 @Ag 70 core protected by five TC4A ligands.…”

Atomically Precise Mo2Cu17 Bimetallic Nanocluster: Synergistic Mo2O4–Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance

“…Recently, atomic precision coin metal nanoclusters (NCs) have been used as innovative catalysts for electrocatalysis. − Their ultrasmall size, clear structure, and uniform chemical environment at the atomic level position metal NCs as model catalysts, providing insights into the complex relationship between the structure and catalytic performance. Although the ternary systems of Au, Ag, and Cu have common properties, these metals exhibit different catalytic properties and NC assembly behaviors due to their inherent chemical properties.…”

Ag1+ incorporation via a Zr4+-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCO2RR-to-CO activity

“…19–22 As such, TC4A emerges as a promising scaffold for constructing nanosized clusters, rendering it a viable candidate for cluster assembly. 23–30 By leveraging the principles of soft and hard acid-base theory, Zr 4+ is classified as a hard Lewis acid with a propensity for phenolic oxygen, while Ag + is identified as a soft Lewis acid with an affinity for soft bases such as sulfur atoms. 31–34 By capitalizing on these principles, the interaction of Zr 4+ and Ag + with TC4A holds the tantalizing potential to yield uncharted bimetallic clusters characterized by distinctive geometric and electronic configurations.…”