Synergistic Activation of Palladium Nanoparticles by Polyoxometalate‐Attached Melem for Boosting Formic Acid Dehydrogenation Efficiency

Pd nanoparticles (NPs) anchored on a phosphotungstic acid attached melem porous hybrid (PW/melem) were prepared by hybridization of phosphotungstic acid Pd salt and melem, followed by chemical reduction. PW/melem was demonstrated to be an outstanding support that can stabilize and disperse small Pd NPs (2 nm), and significantly boost their efficiency for H2 generation from the dehydrogenation of formic acid (FA). Experimental results and mechanistic investigations indicate that a strong electronic interaction exists between Pd NPs and the PW anions; the PW anions accept electrons from Pd first and, during FA dehydrogenation, the reduced blue PW donates electrons to Pd. Moreover, melem plays an important role in hydrogen transfer and can accelerate H2 generation. The overall synergistic effect of PW and melem endows Pd NPs with extremely high activity and stability for complete FA conversion at 50 °C, achieving a high turnover frequency of 15 393 h−1. Heterogeneous Catalysis: Pd nanoparticles stabilized by a phosphotungstic acid attached melem porous hybrid are demonstrated to be excellent catalysts for H2 generation from the dehydrogenation of formic acid, achieving a high turnover frequency (TOF) of 15 393 h−1.