Polymer hydrogel supported Pd–Ni–B nanoclusters as robust catalysts for hydrogen production from hydrolysis of sodium borohydride

Abstract

Catalyzed sodium borohydride hydrolysis is a highly valuable method to produce clean hydrogen energy for portable applications. This study provides a new and fast route to preparation of reusable hybrid materials composed of nickel-boron based nanoclusters dispersed in nanoporous poly(acrylamide) hydrogels for catalyzed hydrogen production. Palladium was added to the Ni–B catalysts during chemical reduction under the protection of poly(N-vinylpyrrolidone). The resulting nanoclusters immobilized in the hydrogels were essentially alloy particles with uni-modal size distributions and average diameters ranging from ca. 4–8 nm. Pd exerted significant promoting effects on the activities of the Ni–B catalysts. The highest activity was achieved for Pd–Ni–B nanoclusters with a charge ratio of Pd/Ni = 1/20 in moles, which exhibited activity nearly twice that of a Ni–B catalyst and good recyclability for consecutive uses. The hydrogen production rates also increased with the decreasing particle sizes. The activation energy, enthalpy and entropy for the reaction were determined to be 31.10 kJ mol−1, 28.39 kJ mol−1 and -45.22 J mol−1 K−1, respectively. The activation energy is lower than that of previously reported polymer-stabilized Co(0), Fe(0), or Ni(0) nanoparticle catalysts.