Carbon supported trimetallic PdNiAg nanoparticles as highly active, selective and reusable catalyst in the formic acid decomposition

Abstract

Trimetallic PdNiAg nanoparticles supported on activated carbon were simply and reproducibly prepared by wet-impregnation followed by simultaneous reduction method without using any stabilizer at room temperature. The characterization of the resulting material was done by the combination of complimentary techniques and the sum of their results shows that the formation of well-dispersed 5.6 +/- 2.2 nm PdNiAg nanoparticles in alloy form on the surface of activated carbon. These carbon supported PdNiAg nanoparticles were employed as heterogeneous catalyst in the catalytic decomposition of formic acid, which has great potential as a safe and convenient hydrogen carrier for fuel cells, under mild conditions. It was found that PdNiAg/C can catalyze the dehydrogenation of formic acid with high selectivity (similar to 100%) and activity (TOF = 85 h(-1)) at 50 degrees C. More importantly, the exceptional stability of PdNiAg nanoparticles against to agglomeration, leaching and CO poisoning make PdNiAg/C reusable catalyst in the formic acid dehydrogenation. PdNiAg/C catalyst retains almost its inherent activity (>94%) even at 5th reuse in the dehydrogenation of formic acid with high selectivity (similar to 100%) at complete conversion. The work reported here also includes the compilation of kinetic data for PdNiAg/C catalyzed dehydrogenation of formic acid depending on catalyst [PdNiAg], substrate [HCOOH], promoter [HCOONa] concentrations and temperature to determine the rate expression and the activation parameters (Ea, Delta H-#, and Delta S-#) of the catalytic reaction. (C) 2014 Elsevier B.V. All rights reserved.