Ceria supported rhodium nanoparticles: Superb catalytic activity in hydrogen generation from the hydrolysis of ammonia borane

Abstract

We investigated the effect of various oxide supports on the catalytic activity of rhodium nanoparticles in hydrogen generation from the hydrolysis of ammonia borane. Among the oxide supports (CeO2, SiO2, Al2O3, TiO2, ZrO2, HfO2) ceria provides the highest catalytic activity for the rhodium(0) nanoparticles in the hydrolysis of ammonia borane. Rhodium(0) nanoparticles supported on nanoceria (Rh0/CeO2) were prepared by the impregnation of rhodium(III) ions on the surface of ceria followed by their reduction with sodium borohydride in aqueous solution at room temperature. They were isolated from the reaction solution by centrifugation and characterized by a combination of advanced analytical techniques. The catalytic activity of Rh0/CeO2 samples with various rhodium loading in the range of 0.1–4.0% wt. Rh was also tested in hydrogen generation from the hydrolysis of ammonia borane at room temperature. The highest catalytic activity was achieved by using 0.1% wt. rhodium loaded nanoceria. The resulting Rh0/CeO2 with a metal loading of 0.1% wt. Rh show superb catalytic activity in hydrogen generation from the hydrolysis of ammonia borane with a record turnover frequency value (TOF) of 2010min−1 at 25.0±0.1°C. The superb catalytic activity of Rh0/CeO2 is ascribed to the reducible nature of ceria. The reduction of cerium(IV) to cerium(III) leads to a build-up of negative charge on the oxide surface which favors the bonding of rhodium(0) nanoparticles on the surface and, thus, their catalytic activity. Rh0/CeO2 are also reusable catalysts preserving 67% of their initial catalytic activity even after the fifth use in hydrogen generation from the hydrolysis of ammonia borane at room temperature (TOF=1350min−1. The work reported here also includes the kinetic studies depending on the temperature to determine the activation energy (Ea=43±2kJ/mol) and the effect of catalyst concentration on the rate of hydrolysis of ammonia borane.