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.

The activity of many water‐splitting photocatalysts could be improved by the use of RhIII–CrIII mixed oxide (Rh2−xCrxO3) particles as cocatalysts. Although further improvement of water‐splitting activity could be achieved if the size of the Rh2−xCrxO3 particles was decreased further, it is difficult to load ultrafine (<2 nm) Rh2−xCrxO3 particles onto a photocatalyst by using conventional loading methods. In this study, a new loading method was successfully established and was used to load Rh2−xCrxO3 particles with a size of approximately 1.3 nm and a narrow size distribution onto a BaLa4Ti4O15 photocatalyst. The obtained photocatalyst exhibited an apparent quantum yield of 16 %, which is the highest achieved for BaLa4Ti4O15 to date. Thus, the developed loading technique of Rh2−xCrxO3 particles is extremely effective at improving the activity of the water‐splitting photocatalyst BaLa4Ti4O15. This method is expected to be extended to other advanced water‐splitting photocatalysts to achieve higher quantum yields.

Atomically precise chemically synthesized gold clusters protected by diphenylphosphine ligands [(Au 13 (dppe) 5 Cl 2 )Cl 3 ] (dppe = 1,2-bis(diphenylphosphino)ethane) were deposited onto a defect-rich, atomic layer deposited titania surface prepared by heating and subsequently sputtering the titania under ultrahigh vacuum (UHV). The gold clusters deposited onto the pretreated titania were heated at 200 °C for 20 min under UHV with the aim to remove the ligands protecting the gold core of the clusters. The change in the electronic structure and the chemical composition after deposition after aforementioned heat treatment was investigated using metastable induced electron spectroscopy (MIES) and X-ray photoelectron spectroscopy (XPS). The MIES data allow identification of the density of states (DOS) of the deligated Au 13 clusters on the titania to be made. The DOS of the Au 13 are found to be similar to those previously found for Au 9 clusters on sputtered ALD titania but have shifted binding energies. The differences in DOS of Au 13 and Au 9 are discussed.

Metal-organic Framework (MOFs) materials are well known for their ultra-high surface areas and gas storage and separation properties. One strategy for enhancing the performance characteristics of MOFs is to post-synthetically line the pores with metal ions. Although this technique has led to improved gas separations the precise structural characterization of the 'metalated' MOF has proved elusive. Here we present that the post-synthetic addition of metals can give rise to materials with the potential to be developed for catalysis and gas adsorption. In addition the high crystallinity of MOFs allow for following reaction products via single crystal X-ray diffraction analysis [1]. 1. Burgun et. al. Angew. Chem. Int. Ed.

We recently found that [Pt 17 (CO) 12 (PPh 3 ) 8 ] z (Pt = platinum; CO = carbon monoxide; PPh3 = triphenylphosphine; z = 1+ or 2+) is a Pt nanocluster (Pt NC) that can be synthesized...