Single-ion chelation strategy for synthesis of monodisperse Pd nanoparticles anchored in MOF-808 for highly efficient hydrogenation and cascade reactions

Abstract

Ultrafine Pd nanoparticles are prepared using a single-ion precursor on a MOF-808 carrier. The ligand 2,3-pyrazinedicarboxylic acid (Pza) is dispersed in porous MOF-808 via grafting on formic acid sites, and thus Pd²⁺ ions are chelated by Pza to form a new single-ion precursor Pd@MOF-808-Pza. Then a Pd-nano@MOF-808-Pza catalyst is prepared by direct reduction of this precursor using NaBH₄. Material characterization reveals the homogeneous dispersion of 3–6 nm Pd nanoparticles within the MOF-808 matrix. Pd-nano@MOF-808-Pza exhibits excellent catalytic activity in the hydrogenation of unsaturated nitrogen-containing compounds, and other typical reactions, such as the Knoevenagel condensation, Suzuki/Heck cross-coupling, and hydrogen tandem reactions. In addition, density functional theory (DFT) calculations are carried out to elucidate the chelation of Pd²⁺ ions by Pza on MOF-808 and propose mechanisms of hydrogenation reactions. This work provides an effective reduction catalyst, and more importantly, a single-ion chelation strategy for design and synthesis of metal supported catalysts.