Size Tailored Nanoparticles of ZrN Prepared by Single-Step Exothermic Chemical Route

Abstract

ZrN nanoparticles were prepared by an exothermic reduction of <TEX>$ZrCl_4$</TEX> with <TEX>$NaN_3$</TEX> in the presence of NaCl flux in a nitrogen atmosphere. Using a solid-state combustion approach, we have demonstrated that the zirconium nitride nanoparticles synthesis process can be completed in only several minutes compared with a few hours for previous synthesis approaches. The chemistry of the combustion process is not complex and is based on a metathesis reaction between <TEX>$ZrCl_4$</TEX> and <TEX>$NaN_3$</TEX>. Because of the low melting and boiling points of the raw materials it was possible to synthesize the ZrN phase at low combustion temperatures. It was shown that the combustion temperature and the size of the particles can be readily controlled by tuning the concentration of the NaCl flux. The results show that an increase in the NaCl concentration (from 2 to 13 M) results in a temperature decrease from 1280 to <TEX>$750^{\circ}C$</TEX>. ZrN nanoparticles have a high surface area (50-70 <TEX>$m^2/g$</TEX>), narrow pore size distribution, and nano-particle size between 10 and 30 nm. The activation energy, which can be extracted from the experimental combustion temperature data, is: E = 20 kcal/mol. The method reported here is self-sustaining, rapid, and can be scaled up for a large scale production of a transition metal nitride nanoparticle system (TiN, TaN, HfN, etc.) with suitable halide salts and alkali metal azide.