Fabrication of electrocatalytic Ta nanoparticles by reactive sputtering and ion soft landing

About 40 years ago, it was shown that tungsten carbide exhibits similar catalytic behavior to Pt for certain commercially relevant reactions, thereby suggesting the possibility of cheaper and earth-abundant substitutes for costly and rare precious metal catalysts. In this work, reactive magnetron sputtering of Ta in the presence of three model hydrocarbons (2-butanol, heptane, and m-xylene) combined with gas aggregation and ion soft landing was employed to prepare organic-inorganic hybrid nanoparticles (NPs) on surfaces for evaluation of catalytic activity and durability. The electrocatalytic behavior of the NPs supported on glassy carbon was evaluated in acidic aqueous solution by cyclic voltammetry. The Ta-heptane and Ta-xylene NPs were revealed to be active and robust toward promotion of the oxygen reduction reaction, an important process occurring at the cathode in fuel cells. In comparison, pure Ta and Ta-butanol NPs were essentially unreactive. Characterization techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were applied to probe how different sputtering conditions such as the flow rates of gases, sputtering current, and aggregation length affect the properties of the NPs. AFM images reveal the focused size of the NPs as well as their preferential binding along the step edges of graphite surfaces. In comparison, TEM images of the same NPs on carbon grids show that they bind randomly to the surface with some agglomeration but little coalescence. The TEM images also reveal morphologies with crystalline cores surrounded by amorphous regions for NPs formed in the presence of 2-butanol and heptane. In contrast, NPs formed in the presence of m-xylene are amorphous throughout. XPS spectra indicate that while the percentage of Ta, C, and O in the NPs varies depending on the sputtering conditions and hydrocarbon employed, the electron binding energies of the elements are similar for all of the NPs. The difference in reactivity between the NPs is attributed to their Ta/C ratios. Collectively, the findings presented herein indicate that reactive magnetron sputtering and gas aggregation combined with ion soft landing offer a promising physical approach for the synthesis of organic-inorganic hybrid NPs that have potential as low-cost durable substitutes for precious metals in catalysis.