Distinct chemical fixation of CO₂ enabled by exotic gold nanoclusters

Atomically precise metal nanoclusters, especially the metal nanoclusters with an exotic core structure, have given rise to a great deal of interest in catalysis, attributing to their well-defined structures at the atomic level and consequently unique electronic properties. Herein, the catalytic performances of three gold nanoclusters, such as Au₃₈S₂(S-Adm)₂₀ with a body-centered cubic (bcc) kernel structure, Au₃₀(S-Adm)₁₈ with a hexagonal close-packed (hcp) core structure, and Au₂₁(S-Adm)₁₅ with a face-centered cubic (fcc) kernel structure, were attempted for the CO₂ cycloaddition with epoxides toward cyclic carbonates. Due to the excess positive charge with a strong Lewis acidity and large chemical adsorption capacity, the bcc-Au₃₈S₂(S-Adm)₂₀ nanocluster outperformed the hcp-Au₃₀(S-Adm)₁₈ and fcc-Au₂₁(S-Adm)₁₅ nanoclusters. Additionally, the synergistic effect between the gold nanocluster and co-catalyst played a crucial role in CO₂ cycloaddition.