Synthesis of Monodisperse Palladium Nanoclusters Using Metal–Organic Frameworks as Sacrificial Templates.

Abstract: An interfacial etching approach was developed for the synthesis of monodisperse and ultrasmall thiolated palladium nanoclusters (Pd NCs) using Zr‐UiO‐66‐NH₂ metal–organic frameworks (MOFs) as sacrificial templates. The Pd NCs were originally synthesized inside the cavities of the MOFs (Pd@UiO‐66‐NH₂). The Pd NCs released from the MOFs have a strikingly small size with narrow distribution (1.1±0.1 nm), amounting to a cluster size of ca. 40 Pd atoms. The ¹H NMR spectrum indicates that thiol is the only capping agent for these Pd NCs. We derived the composition of the thiolated Pd NCs using thermogravimetric analysis (TGA) and inductively coupled plasma mass spectrometry (ICP‐MS) analysis. Moreover, the Pd NCs size can be tuned by using MOF templates with different cavity sizes. The thiolated Pd NCs are catalytically active in a model Suzuki–Miyaura coupling reaction. [ABSTRACT FROM AUTHOR]