Palladium(0) nanoparticles supported on hydroxyapatite nanospheres: active, long-lived, and reusable nanocatalyst for hydrogen generation from the dehydrogenation of aqueous ammonia–borane solution

Among the solid materials considered in the chemical hydrogen storage, ammonia–borane (NH₃BH₃) appears to be one of the promising candidates as it can release hydrogen throughout hydrolysis in the presence of suitable catalyst under mild conditions. Herein we report, for the first time, the preparation and characterization of palladium(0) nanoparticles supported on nanohydroxyapatite and their catalytic use in the hydrolysis of ammonia–borane under air at room temperature. These new palladium(0) nanoparticles were generated in situ during the catalytic hydrolysis of ammonia–borane starting with palladium(II) immobilized nanohydroxyapatite. The preliminary characterization of the palladium(0) nanoparticles supported on nanohydroxyapatite was done by the combination of complimentary techniques, which reveals that the formation of well-dispersed Pd(0)NPs nanoparticles (1.41 ± 0.52 nm) on the surface of hydroxyapatite nanospheres (60–150 nm). The resulting palladium nanocatalyst achieves hydrogen generation from the hydrolysis of ammonia–borane with an initial turnover frequency value (TOF) of 11 mol H₂ mol⁻¹ Pd × min at room temperature under air. In addition to their high activity, the catalytic lifetime experiment showed that they can also act as a long-lived heterogeneous catalyst for this reaction (TTON = 14,200 mol H₂ mol⁻¹ Pd) at room temperature under air. More importantly, nanohydroxyapatite-supported palladium(0) nanoparticles were found to be highly stable against to leaching and sintering throughout the catalytic runs that make them isolable, bottleable, and reusable heterogeneous catalyst for the hydrolysis of ammonia–borane.