Ag⁺-Mediated Structural Reconstruction of a Metastable Cu Cluster Toward Cu-Ag Heterometallic Architectures for Superior Electrocatalytic CO-to-Ethanol Conversion.

Controlled structural transformations of metal nanoclusters (NCs) via dynamic bond reorganization provide fundamental insights into cluster reactivity and open avenues for functionality tuning. Here, we report a thiacalix[4]arene-protected Cu(I)-alkynide cluster, {NaCu(TC4A)(Ph-C≡C)} (Cu), which exhibits remarkable structural plasticity. This metastable cluster can grow into a Cu species via ion substitution or undergo thermal-induced fragmentation to form a smaller Cu cluster.

Atomic-level engineering of single Ag site distribution on titanium-oxo cluster surfaces to boost CO electroreduction.

Precise control over the distribution of active metal sites on catalyst surfaces is essential for maximizing catalytic efficiency. Addressing the limitations of traditional cluster catalysts with core-embedded catalytic sites, this work presents a strategy to position catalytic sites on the surfaces of oxide clusters. We utilize a calixarene-stabilized titanium-oxo cluster (TiL) as a scaffold to anchor Ag , forming the unique nanocluster TiAg with six surface-exposed Ag sites.