This study demonstrates that controlling intra-cluster ligand interactions is important to obtain an assembled structure with the desired connecting structures.

Recently, the creation of new heterogeneous catalysts using the unique electronic/geometric structures of small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important to establish methods to remove the ligands from ligand‐protected metal NCs while preventing the aggregation of metal NCs. In this study, the ligand‐desorption process during calcination was followed for metal‐oxide‐supported 2‐phenylethanethiolate‐protected gold (Au) 25‐atom metal NCs using five experimental techniques. The results clearly demonstrate that the ligand‐desorption process consists of ligand dissociation on the surface of the metal NCs, adsorption of the generated compounds on the support and desorption of the compounds from the support, and the temperatures at which these processes occurred were elucidated. Based on the obtained knowledge, we established a method to form a metal‐oxide layer on the surface of Au NCs while preventing their aggregation, thereby succeeding in creating a water‐splitting photocatalyst with high activity and stability.

Ligand-protected metal nanoclusters controlled by atomic accuracy (i. e. atomically precise metal NCs) have recently attracted considerable attention as active sites in heterogeneous catalysts. Using these atomically precise metal NCs,...

This feature article describes our previous efforts for creating active water-splitting photocatalysts by using atomically precise metal nanoclusters as cocatalysts.