Synthesis and Catalytic Application of Ag44 Clusters Supported on Mesoporous Carbon

4-(Fluorophenyl)thiolate-protected Ag44 clusters (Ph4P)4[Ag44(SC6H4F)30] were calcined on mesoporous carbon (MPC) under vacuum at 300–500 °C for 2 h. X-ray absorption spectroscopy, transmission electron microscopy, and thermal-desorption mass spectrometry revealed that sulfur-free Ag44 clusters were successfully produced by the calcination of [Ag44(SC6H4F)30]4– at 300 °C, in sharp contrast to the formation of silver sulfide nanoparticles by the calcination of dodecanethiolate-protected Ag nanoparticles (3.0 ± 0.6 nm). Ag44/MPC was applied in the catalytic dehydrogenation of ammonia–borane (NH3BH3) as a test reaction. It turned out that the Ag44/MPC catalysts produced 1 equiv of H2 from NH3BH3 but only in the presence of O2 (turnover frequency 1.9 × 103 h–1 Ag atom–1). Given that nanoparticles of other metals (Pt, Pd, Rh, Ni, or Ru) produced 3 equiv of H2 under an inert atmosphere, this result indicates that the Ag44/MPC-catalyzed dehydrogenation of NH3BH3 proceeds by a different mechanism from that on other nanoparticles.