Flat-Band Potential Determination and Catalytical Properties of Sn3O4/SnO2 Heterostructures in the Photo-Electrooxidation of Small Organic Molecules under Ultraviolet (370 nm) and Blue (450 nm) Light.

Sn3O4 are promising semiconductor materials due to their visible light absorption ability. In this work, a series of materials, such as SnO2, Sn3O4 and Sn3O4/SnO2 heterostructures, with different phase ratios were prepared using hydrothermal synthesis. The materials were characterized using X-ray diffraction (XRD), Raman and diffuse reflectance spectroscopy (DRS), high resolution transmission electron microscopy (HRTEM), nitrogen adsorption (BET). Flat-band potentials (EFB) of the samples were determined using the photocurrent onset potential (POP) method. It was shown that the potentials obtained with open circuit potential measurements versus illumination intensity (OCP) likely corresponded to the EFB of SnO2 nanoparticles in heterostructures due to interfacial electron transfer from the conducting band of Sn3O4 to that of SnO2. The photo-electrooxidation processes of a series of organic substrates were studied in the potential range of 0.6-1.4 V vs. RHE under irradiation with ultraviolet (λ = 370 nm) and visible (λ = 450 nm) light. The Sn3O4 sample showed high activity in the photo-electrooxidation of acetone and formic acid in visible light. The Sn3O4/SnO2 samples exhibited noticeable activity only in the oxidation of formic acid. The presence of the SnO2 phase in the Sn3O4/SnO2 samples increased the photocurrent values under ultraviolet illumination, but significantly reduced the oxidation efficiency in visible light.

Photoelectrochemical Methods for the Determination of the Flat-Band Potential in Semiconducting Photocatalysts: A Comparison Study.

In addition to the band gap of a semiconducting photocatalyst, its band edges are important because they play a crucial role in the analysis of charge transfer and possible pathways of the photocatalytic reaction. The Mott-Schottky method using electrochemical impedance spectroscopy is the most common experimental technique for the determination of the electron potential in photocatalysts. This method is well suited for large crystals, but in the case of nanocatalysts, when the thickness of the charged layer is comparable with the size of the nanocrystals, the capacitance of the Helmholtz layer can substantially affect the measured potential. A contact between the electrolyte and the substrate, used for deposition of the photocatalyst, also affects the impedance. Application of other photoelectrochemical methods may help to avoid concerns in the interpretation of impedance data and improve the reliability of measurements. In this study, we have successfully prepared five visible-light active photocatalysts (i.e., N-doped TiO2, WO3, Bi2WO6, CoO, and g-C3N4) and measured their flat-band potentials using four (photo)electrochemical methods. The potentials are compared for all methods and discussed regarding the type of semiconducting material and its properties. The effect of methanol as a sacrificial agent for the enhanced transfer of charge carriers is studied and discussed for each method.

Kinetic Aspects of Benzene Degradation over TiO2-N and Composite Fe/Bi2WO6/TiO2-N Photocatalysts under Irradiation with Visible Light.

In this study, composite materials based on nanocrystalline anatase TiO2 doped with nitrogen and bismuth tungstate are synthesized using a hydrothermal method. All samples are tested in the oxidation of volatile organic compounds under visible light to find the correlations between their physicochemical characteristics and photocatalytic activity. The kinetic aspects are studied both in batch and continuous-flow reactors, using ethanol and benzene as test compounds. The Bi2WO6/TiO2-N heterostructure enhanced with Fe species efficiently utilizes visible light in the blue region and exhibits much higher activity in the degradation of ethanol vapor than pristine TiO2-N. However, an increased activity of Fe/Bi2WO6/TiO2-N can have an adverse effect in the degradation of benzene vapor. A temporary deactivation of the photocatalyst can occur at a high concentration of benzene due to the fast accumulation of non-volatile intermediates on its surface. The formed intermediates suppress the adsorption of the initial benzene and substantially increase the time required for its complete removal from the gas phase. An increase in temperature up to 140 °C makes it possible to increase the rate of the overall oxidation process, and the use of the Fe/Bi2WO6/TiO2-N composite improves the selectivity of oxidation compared to pristine TiO2-N.

Enhanced Photocatalytic Activity and Stability of Bi2WO6 - TiO2-N Nanocomposites in the Oxidation of Volatile Pollutants.

The development of active and stable photocatalysts for the degradation of volatile organic compounds under visible light is important for efficient light utilization and environmental protection. Titanium dioxide doped with nitrogen is known to have a high activity but it exhibits a relatively low stability due to a gradual degradation of nitrogen species under highly powerful radiation. In this paper, we show that the combination of N-doped TiO2 with bismuth tungstate prevents its degradation during the photocatalytic process and results in a very stable composite photocatalyst. The synthesis of Bi2WO6-TiO2-N composites is preformed through the hydrothermal treatment of an aqueous medium containing nanocrystalline N-doped TiO2, as well as bismuth (III) nitrate and sodium tungstate followed by drying in air. The effect of the molar ratio between the components on their characteristics and photocatalytic activity is discussed. In addition to an enhanced stability, the composite photocatalysts with a low content of Bi2WO6 also exhibit an enhanced activity that is substantially higher than the activity of individual TiO2-N and Bi2WO6 materials. Thus, the Bi2WO6-TiO2-N composite has the potential as an active and stable photocatalyst for efficient purification of air.

Method for correction of experimental action spectrum using actual overlapping spectra of radiation sources.

Experimental dependency of the photosystem's response on the wavelength of exciting radiation, also known as action spectrum, may be substantially affected by the spectrum shape of this radiation. This is especially important in the case, when different radiation sources are used for the investigation of action spectrum. For instance, too wide emission peaks of radiation sources can blur the scopes of actual action spectrum and distort information about the properties of photosystem at certain wavelength regions. Here, we propose a method for the correction of experimental action spectrum by the recalculation of experimental data of photoresponse according to actual spectra of exciting radiation. In the case of overlapping radiation spectra from different radiation sources, this method results in much better correlation of experimental action spectrum to actual action spectrum or absorption spectrum of photosystem. The data on photoactivity of several photocatalysts are presented to illustrate and validate the proposed method.•Activity of photosystem depends on the actual spectrum of the radiation source•Single-peak optical radiation sources with the same basic wavelength may cause a different photoactivity•Effect of actual spectrum of the light source on the photoactivity is to be considered.

Synthesis, Characterization and Visible-Light Photocatalytic Activity of Solid and TiO2-Supported Uranium Oxycompounds.

In this study, various solid uranium oxycompounds and TiO2-supported materials based on nanocrystalline anatase TiO2 are synthesized using uranyl nitrate hexahydrate as a precursor. All uranium-contained samples are characterized using N2 adsorption, XRD, UV-vis, Raman, TEM, XPS and tested in the oxidation of a volatile organic compound under visible light of the blue region to find correlations between their physicochemical characteristics and photocatalytic activity. Both uranium oxycompounds and TiO2-supported materials are photocatalytically active and are able to completely oxidize gaseous organic compounds under visible light. If compared to the commercial visible-light TiO2 KRONOS® vlp 7000 photocatalyst used as a benchmark, solid uranium oxycompounds exhibit lower or comparable photocatalytic activity under blue light. At the same time, uranium compounds contained uranyl ion with a uranium charge state of 6+, exhibiting much higher activity than other compounds with a lower charge state of uranium. Immobilization of uranyl ions on the surface of nanocrystalline anatase TiO2 allows for substantial increase in visible-light activity. The photonic efficiency of reaction over uranyl-grafted TiO2, 12.2%, is 17 times higher than the efficiency for commercial vlp 7000 photocatalyst. Uranyl-grafted TiO2 has the potential as a visible-light photocatalyst for special areas of application where there is no strict control for use of uranium compounds (e.g., in spaceships or submarines).

Synthesis of Cd1-xZnxS photocatalysts for gas-phase CO2 reduction under visible light.

Novel photocatalysts for CO2 reduction, which consist of a cadmium and zinc sulfide solid solution (Cd1-xZnxS), were successfully prepared by a simple two-step technique. The photocatalysts were characterized by X-ray diffraction, UV-VIS diffuse reflectance spectroscopy, and low-temperature N2 adsorption techniques and were tested in the gas-phase photocatalytic reduction of CO2 under visible light (λ = 450 nm). All the synthesized Cd1-xZnxS solid solutions were capable of enabling the chemical transformations of CO2 under the conditions considered. Carbon monoxide was the major product during the CO2 reduction over Cd1-xZnxS (x = 0-0.87). Methane and hydrogen were also detected in the gas phase in low amounts. The activity of the prepared samples and the distribution of the reduction products strongly depended on the actual cadmium to zinc ratio. The Cd0.94Zn0.06S photocatalyst showed the highest activity, 2.9 µmol CO per gram per hour, and selectivity, 95%, during CO2 reduction under visible light in the presence of water vapor. The achieved values are very high for the sulfide-based photocatalysts.