Charge State of Au₂₅(SG)₁₈ Nanoclusters Induced by Interaction with a Metal Organic Framework Support and Its Effect...

We investigated the charge transfer between Au₂₅(SG)₁₈ nanoclusters and metal-organic framework (MOF) supports including Mil-101-Cr, Mil-125-Ti, and ZIF-8 by an X-ray photoemission technique and discussed the influence of resulted charge states of supported Au₂₅(SG)₁₈ nanoclusters on the 4-nitrophenol reduction reaction. Charge transfer from Au₂₅(SG)₁₈ to Mil-101-Cr induces positive charge Au^δ+ (0 < δ < 1) while charge transfer from ZIF-8 to Au₂₅(SG)₁₈ generates negative charge Au^δ- due to different metal-support interactions. Au₂₅(SG)₁₈ on Mil-125 shows metallic Au⁰, similar to unsupported Au₂₅(SG)₁₈, due to negligible charge transfer. The resulted charge state of Au^δ- inhibits the formation of adsorbed hydride (H^-) species because of electrostatic repulsion, while Au^δ+ impairs the reductive ability of adsorbed hydride (H^-) species due to strong affinity between them. In comparison, metallic Au⁰ in Au₂₅(SG)₁₈/Mil-125 and unsupported Au₂₅(SG)₁₈ presents the optimum catalytic activity. The current work provides guidelines to design effective metal nanoclusters in heterogeneous catalysis through metal-support interaction exerted by metal-oxo/nitric clusters within MOFs.