The synthesis of hafnium nanomaterials by alkali metal reduction of hafnium tetrachloride

Hafnium tetrachloride was reduced in organic solvents with lithium powder, sodium–potassium alloy, or lithium hydride/Et3B. All reductions required sonochemical agitation to proceed at an appreciable rate, with the notable exception of the reaction of HfCl4 with Li in diethyl ether. Activation of C–H bonds occurred in all reactions, which resulted in carbon-containing products. HfCl4 was reduced on a 50-g scale with LiH/Et3B, and a 10-g scale with Li powder in pentane. All the solid products from the reductions were converted to nanomaterials by annealing under vacuum from 500 to 1,000 °C, which also resulted in the sublimation of the alkali metal salts. The nanomaterials contain a mixture of products with the α-Hf (hexagonal) structure (crystallite size 8–250 nm) and the HfC (FCC) structure (crystallite size 3–80 nm), with the amount of hafnium in the bulk annealed product varying from 88 to 99 wt%. When toluene, pentane, or triethylamine solvents were used, the presence of amorphous graphitic or carbonaceous material was also detected by solid state 13C NMR. Thermally annealed products were additionally characterized by electron microscopy and thermal analysis under Ar/O2, and have BET surface areas ranging from 2.7 to 155 m2/g.