Plasmonic Au@Pd Nanoparticles Supported on a Basic Metal–Organic Framework: Synergic Boosting of H₂ Production from Formic Acid

We report synergistic catalysis of plasmonic Au@Pd nanoparticles supported on titanium-doped zirconium-based amine-functionalized metal–organic frameworks (MOFs) (UiO-66(Zr 100– x Ti x )) for boosting room-temperature hydrogen production from formic acid (HCOOH) under visible light irradiation. Our results revealed that the electronically promoted Pd sites by the localized surface plasmon resonance (LSPR) effect of Au as well as doping of amine functionality in the MOFs with titanium ions play crucial roles in achieving exceptional catalytic performance. Remarkably, a high H 2 production rate of 42000 mL h –1 g –1 (Pd) with high a turnover frequency (TOF) of 200 h –1 based on Pd was obtained under visible light irradiation. Kinetic isotope effect (KIE) measurements demonstrated that dissociations of O–H and C–H bonds of formic acid, which are two important steps for hydrogen production from HCOOH, are individually facilitated by the assistance of amine groups within MOFs and active electron-rich Pd sites induced by the LSPR effect under visible light irradiation.