Strong thickness dependence in thin film photocatalytic heterojunctions: the ZnO-Bi2O3 case study.

Semiconductor heterojunctions are an effective way to achieve efficient photocatalysts, as they can provide an adequate redox potential with visible light excitation. Several works have reported synergistic effects with nanoparticle semiconductor materials. The question is still open for thin film heterojunctions formed by stacked layers, as photocatalysis is considered a surface phenomenon. To investigate if the internal layer really affects or modifies the photocatalytic properties of the external material, we analyze the thin film heterojunction with ZnO and Bi2O3 semiconductors deposited by spray pyrolysis in two configurations: substrate/ZnO/Bi2O3 and substrate/Bi2O3/ZnO. Microstructural analysis was performed to verify the formation of the physical junction of the materials and discard new ternary phases. The photocatalytic activity was analyzed as a function of the thickness of the layers under blue light irradiation. We determined the conduction and valence bands positions, the carrier concentrations, mobilities, Fermi levels, etc. that allowed us to distinguish two reaction mechanisms depending on the configuration. There is a strong compromise between the order and thickness of the layers with the photocatalytic activity. The internal electric field produced in the interface defines the route of the photogenerated charges, and therefore the photocatalytic response. Thus, well-designed thin film heterojunctions can indeed improve the photocatalytic activity of the surface layer.

Synergistic photocatalytic effect of BiOBr-BiOI heterojunctions due to appropriate layer stacking.

The increasing interest in acquiring efficient visible-light active photocatalytic materials has led to the formation of heterojunctions with different combinations of semiconductors. Despite the fact that increasingly more complex structures are proposed, there are still many unclear factors affecting their performance and limiting their prompt implementation. In this work, we used the spray pyrolysis technique to deposit individual visible light-active BiOBr and BiOI films and formed the heterojunctions BiOBr-BiOI and BiOI-BiOBr to determine the effect of the stacking order of semiconductors. These materials were widely characterized; their structural, optical, (photo)electrochemical, and photocatalytic properties were evaluated, revealing that the configuration BiOI-BiOBr boosted the photocatalytic indigo carmine dye removal under simulated sunlight irradiation, but the opposite layout quenched it. The high efficiency is attributed to a better use of the incident radiation and the effective migration of the photogenerated carriers. BiOBr - with a wider band gap and a less negative conduction band with respect to BiOI - provides its good attributes to the heterostructure, such as high stability and low recombination rates, when it is at the surface. We demonstrated that in thin-film heterostructures, the order in which the layers are stacked becomes decisive for the photocatalytic performance and that the energy band gap and the relative band positions of both semiconductors are the principal features that govern the photocatalytic mechanism. These findings provide a key to designing more efficient photocatalysts without several unsuccessful trials.

The bismuth oxyhalide family: thin film synthesis and periodic properties.

Bismuth oxyhalides (BiOX, where X = F, Cl, Br, I) are interesting materials due to their layered structure, which can be useful for different applications. In this work, we present the synthesis of the complete BiOX family in the thin film form. The tetragonal phase Bi2O3 film deposited onto a glass substrate was transformed into BiOF, BiOCl or BiOBr by a simple immersion at ambient temperature in a halide (X = F, Cl, Br) containing solution. For these films, a residual phase from the oxide was present and for BiOF another phase (tentatively identified as Bi7O5F11) was present too. For the BiOI film synthesis, an iodine and bismuth containing solution was sprayed onto the glass substrate heated at 275 °C and a pure phase was obtained. Microstructural and morphological characterization was performed by X-ray diffraction and scanning electron microscopy, while the chemical environment was studied by X-ray photoelectron spectroscopy. Optical and photocatalytic properties were also obtained. The physical and chemical characteristics of the BiOX films follow a correlation with the atomic radius of the halogen atom incorporated into the corresponding lattice. All the BiOX films showed a photocatalytic response for the photodiscoloration of indigo carmine dye under simulated sunlight irradiation in an alkaline medium. The photocatalytic reactions occurred via 2 proton-electron transfer from the oxide or oxyhalide to the adsorbed IC dye, favoring its reduction to the corresponding leuco IC form.

Effect of 2,6-Bis-(1-hydroxy-1,1-diphenyl-methyl) Pyridine as Organic Additive in Sulfide NiMoP/γ-Al2O3 Catalyst for Hydrodesulfurization of Straight-Run Gas Oil.

The effect of 2,6-bis-(1-hydroxy-1,1-diphenyl-methyl) pyridine (BDPHP) in the preparation of NiMoP/γ-Al2O3 catalysts have been investigated in the hydrodesulfurization (HDS) of straight-run gas oil. The γ-Al2O3 support was modified by surface impregnation of a solution of BDPHP to afford BDPHP/Ni molar ratios (0.5 and 1.0) in the final composition. The highest activity for NiMoP materials was found when the molar ratio of BDPHP/Ni was of 0.5. X-ray diffraction (XRD) results revealed that NiMoP (0.5) showed better dispersion of MoO3 than the NiMoP (1.0). Fourier transform infrared spectroscopy (FT-IR) results indicated that the organic additive interacts with the γ-Al2O3 surface and therefore discards the presence of Mo or Ni complexes. Raman spectroscopy suggested a high Raman ratio for the NiMoP (0.5) sample. The increment of the Mo=O species is related to a major availability of Mo species in the formation of MoS2. The temperature programmed reduction (TPR) results showed that the NiMoP (0.5) displayed moderate metal-support interaction. Likewise, X-ray photoelectron spectroscopy (XPS) exhibited higher sulfurization degree for NiMoP (0.5) compared with NiMoP (1.0). The increment of the MoO3 dispersion, the moderate metal-support interaction, the increase of sulfurization degree and the increment of Mo=O species provoked by the BDPHP incorporation resulted in a higher gas oil HDS activity.

Preparation of efficient cadmium sulfide nanofibers for hydrogen production using ethylenediamine (NH2CH2CH2NH2) as template.

The preparation of CdS was performed by the precipitation method using ethylenediamine as template and tetrahydrofuran, acetonitrile or butanol as organic solvents. The formation of CdS with hexagonal structure was observed by XRD due to the template effect. FTIR studies showed that the amount of the template linked to the surface of the CdS depends on the organic solvent used. TEM observations evidenced the formations of CdS nanofibers and the EDS analysis show the chemical composition of the surface. The photocatalytic activity of CdS nanofibers under blue light irradiation was strongly influenced by the amount of ethylenediamine template on the nanofiber surface. It was observed that when the amount of the template on the samples diminishes by the heat treatment, the photocatalytic activity is affected. The role of the ethylenediamine template in the mechanism for the H2 production reaction is discussed.

Photoconversion of 4-nitrophenol in the presence of hydrazine with AgNPs-TiO2 nanoparticles prepared by the sol-gel method.

The photocatalytic properties of functionalized TiO2 with silver nanoparticles (AgNPs) for the conversion of 4-nitrophenol to 4-aminophenol in the presence of hydrazine were investigated. The TiO2 semiconductor synthesized by the sol-gel method was functionalized with AgNPs at different loadings, and their structural and optical properties were characterized by several techniques. The functionalized TiO2 with 1.5wt% AgNPs presented the highest photocatalytic activity for the conversion of 4-nitrophenol with appropriate hydrazine concentrations (0.5M). The photoefficiency enhancement under UV light irradiation was attributed to the electron transfer from the TiO2 semiconductor surface to the adsorbed acceptor reactant (4-nitrophenol) through the deposited AgNPs.

Photocatalytic hydrogen production by water/methanol decomposition using Au/TiO2 prepared by deposition-precipitation with urea.

Gold nanoparticles deposited on TiO2 Degussa P25, prepared by deposition-precipitation with urea, were studied in the photocatalytic hydrogen production. The effect of parameters such as mass of catalyst, gold loading, thermal treatment, and atmosphere of treatment was evaluated and optimized. The presence of metallic gold on the titania surface showed to have contributed to the high improvement in the activity of bare TiO2 for hydrogen generation under UV light (λ=254 nm) using a lamp of low energy (2W) consumption. The optimal gold loading for the photocatalysts was 0.5 wt.%, the mass of catalyst in the reactor was 0.5 g/L in a water/methanol 1:1 vol. solution, and the thermal treatment that produced the most active gold nanoparticles was found at 300°C. The photocatalysts thermally treated under hydrogen at 300°C produced 1492 µmol g(-1)h(-1) of hydrogen; the same catalyst activated in air produced 1866 µmo lg(-1)h(-1) of hydrogen.