α‑Fe₂O₃/NiOOH: An Effective Heterostructure for Photoelectrochemical Water Oxidation

The study of the semiconductor/electrocatalyst interface in electrodes for photoelectrochemical water splitting is of paramount importance to obtain enhanced solar-to-fuel efficiency. Here, we take into consideration the multiple effects that a thin layer of photodeposited amorphous Ni-oxyhydroxide (NiOOH) induces on hematite (α-Fe₂O₃) photoanodes. The reduction of overpotential produced a photocurrent onset potential advance of 150 mV and an increase of photocurrent of about 50% at 1.23 V vs RHE. To give an interpretation to these phenomena, we carried out deep electrochemical investigations by cyclic voltammetry and electrochemical impedance spectroscopy. The effective charge injection into the electrolyte due to the reduction of the charge transfer resistance at the electrode/electrolyte interface was observed and increased along with the amount of deposited NiOOH. The benefits of NiOOH deposition are ascribable to its ability to scavenge holes from hematite surface traps. This effect is mitigated at a potential higher than 1.25 V, since a fraction of photogenerated holes is consumed into the Ni redox cycle

Deciphering Local Structural Complexity in Zn/Ga-ZrO₂ CO₂ Hydrogenation Catalysts

In the last few decades, massive effort has been expended in heterogeneous catalysis to develop new materials presenting high conversion, selectivity, and stability even under high-temperature and high-pressure conditions. In this context, CO2 hydrogenation is an interesting reaction where the catalyst local structure is strongly related to the development of an active and stable material under hydrothermal conditions at T/P > 300 °C/30 bar. In order to clarify the relationship between catalyst local ordering and its activity/stability, we herein report a combined laboratory and synchrotron investigation of aliovalent element (Ce/Zn/Ga)-containing ZrO2 matrixes. The results reveal the influence of similar average structures with different short-range orderings on the catalyst properties. Moreover, a further step toward the comprehension of the oxygen vacancy formation mechanism in Ce- and Ga-ZrO2 catalysts is reported. Finally, the reported results illustrate a robust method to guide local structure determination and ultimately help to avoid overuse of the “solid solution” definition

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

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