High-Throughput Preparation of Metal Oxide Nanocrystals by Cathodic Corrosion and Their Use as Active Photocatalysts.

Nanoparticle metal oxide photocatalysts are attractive because of their increased reactivity and ease of processing into versatile electrode formats; however, their preparation is cumbersome. We report on the rapid bulk synthesis of photocatalytic nanoparticles with homogeneous shape and size via the cathodic corrosion method, a simple electrochemical approach applied for the first time to the versatile preparation of complex metal oxides. Nanoparticles consisting of tungsten oxide (H2WO4) nanoplates, titanium oxide (TiO2) nanowires, and symmetric star-shaped bismuth vanadate (BiVO4) were prepared conveniently using tungsten, titanium, and vanadium wires as a starting material. Each of the particles were extremely rapid to produce, taking only 2-3 min to etch 2.5 mm of metal wire into a colloidal dispersion of photoactive materials. All crystalline H2WO4 and BiVO4 particles and amorphous TiO2 were photoelectrochemically active toward the water oxidation reaction. Additionally, the BiVO4 particles showed enhanced photocurrent in the visible region toward the oxidation of a sacrificial sulfite reagent. This synthetic method provides an inexpensive alternative to conventional fabrication techniques and is potentially applicable to a wide variety of metal oxides, making the rapid fabrication of active photocatalysts with controlled crystallinity more efficient.

Influence of hydrazine-induced aggregation on the electrochemical detection of platinum nanoparticles.

To study the catalytic activity of single nanoparticles (NPs) electrochemically, we investigated the applicability of a novel method for nanoparticle detection as a means to immobilize individual NPs. This method consists of analyzing the current steps that can be measured at an ultramicroelectrode (UME) when a colloid of NPs is injected into an electrolyte containing an electroactive species, that is turned over at the NP but not the UME surface. We have measured these current steps for the hydrazine oxidation at Pt NPs landing on a lithographically fabricated Au UME, showing a mean step size comparable to theory and prior measurements. We found a reduced landing frequency with respect to values reported in the literature and those predicted from theory, while the current step distribution showed a long tail of large current steps. This could be explained by the particle aggregation, which would lower the effective NP concentration and therefore lower the landing frequency and would result in higher current steps when aggregates reach the electrode. Cyclic voltammetry (CV) measurements of the Pt-modified Au UME showed a signal characteristic of the presence of Pt, while electron microscopy revealed aggregated NPs, after landings were performed in the presence of hydrazine or hydrogen gas. Conversely, no aggregates were found after particles were injected in absence of such reducing agents, while CV still suggested the presence of Pt, indicating individual particles. The finding, that landing nanoparticles in the presence of hydrazine yields NP aggregates on the surface, means that this particular method is currently not suited for the preparation of individually immobilized particles to facilitate catalysis studies at individual nanoparticles.