Effect of Cu2O Substrate on Photoinduced Hydrophilicity of TiO2 and ZnO Nanocoatings

The effect of a Cu2 O substrate on the photoinduced alteration of the hydrophilicity of TiO2 and ZnO surfaces was studied. It was demonstrated that the formation of heterostructures Cu2 O/TiO2 and Cu2 O/ZnO strongly changed the direction of the photoinduced alteration of surface hydrophilicity: while both TiO2 and ZnO demonstrate surface transition to superhydrophilic state under UV irradiation and no significant alteration of the surface hydrophilicity under visible light irradiation, the formation of Cu2 O/TiO2 and Cu2 O/ZnO heterostructures resulted in photoinduced decay of the surface hydrophilicity caused by both UV and visible light irradiation. All observed photoinduced changes of the surface hydrophilicity were compared and analyzed in terms of pho-toinduced alteration of the surface free energy and its polar and dispersive components. Alteration of the photoinduced hydrophilic behavior of TiO2 and ZnO surfaces caused by formation of the corresponding heterostructures with Cu2 O are explained within the mechanism of electron transfer and increasing of the electron concentration on the TiO2 and ZnO surfaces

Editorial: Special Issue on Photocatalytic Nanocomposite Materials (PNMs)

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Photoactive Heterostructures: How They Are Made and Explored

In our review we consider the results on the development and exploration of heterostructured photoactive materials with major attention focused on what are the better ways to form this type of materials and how to explore them correctly. Regardless of what type of heterostructure, metal–semiconductor or semiconductor–semiconductor, is formed, its functionality strongly depends on the quality of heterojunction. In turn, it depends on the selection of the heterostructure components (their chemical and physical properties) and on the proper choice of the synthesis method. Several examples of the different approaches such as in situ and ex situ, bottom‐up and top‐down, are reviewed. At the same time, even if the synthesis of heterostructured photoactive materials seems to be successful, strong experimental physical evidence demonstrating true heterojunction formation are required. A possibility for obtaining such evidence using different physical techniques is discussed. Particularly, it is demonstrated that the ability of optical spectroscopy to study heterostructured materials is in fact very limited. At the same time, such experimental techniques as high‐resolution transmission electron microscopy (HRTEM) and electrophysical methods (work function measurements and impedance spectroscopy) present a true signature of heterojunction formation. Therefore, whatever the purpose of heterostructure formation and studies is, the application of HRTEM and electrophysical methods is necessary to confirm that formation of the heterojunction was successful

Effect of the Type of Heterostructures on Photostimulated Alteration of the Surface Hydrophilicity: TiO2/BiVO4 vs. ZnO/BiVO4 Planar Heterostructured Coatings

Here, we report the results of comparative studies of the photostimulated hydrophilic behavior of heterostructured TiO2 /BiVO4 and ZnO/BiVO4, and monocomponent TiO2 and ZnO nanocoating surfaces. The chemical composition and morphology of the synthesized nanocoat-ings were characterized by XPS, SEM, and AFM methods. The electronic energy structure of the heterostructure components (band gap, top of the valence band, bottom of the conduction band, and Fermi level position) was determined on the basis of experimental results obtained by XPS, UV-V absorption spectroscopy and Kelvin probe methods. According to their electronic energy structure, the ZnO/BiVO4 and TiO2 /BiVO4 heterostructures correspond to type I and type II het-erostructures, respectively. The difference in the type of heterostructures causes the difference in the charge transfer behavior at heterojunctions: the type II TiO2 /BiVO4 heterostructure favors and the type I ZnO/BiVO4 heterostructure prevents the photogenerated hole transfer from BiVO4 to the outer layer of the corresponding metal oxide. The results of the comparative studies show that the interaction of the photogenerated holes with surface hydroxy-hydrated multilayers is responsible for the superhydrophilic surface conversion accompanying the increase of the surface free energy and work function. The formation of the type II heterostructure leads to the spectral sensitization of the photostimulated surface superhydrophilic conversion

Photoelectrochemical behavior of the ternary heterostructured systems CdS/WO3/TiO2

In this article, we report the results of comparative studies of photoelectrochemical behavior of the binary CdS/TiO2 and WO3/TiO2 and ternary CdS/WO3/TiO2 heterostructures based on titania nanotube and planar structures. Physical–chemical characterization by XRD, XPS, and electron microscopy methods together with electrochemical impedance spectroscopy measurements confirm a successful formation of heterostructured electrodes, both nanotube-based and planar. The results of photoelectrochemical studies of the heterostructures demonstrate a significant difference in their behavior depending on the structure geometry and the character of the formed heterojunctions. It is concluded that nanotube-based heterostructure electrodes can be characterized by a stochastic set of different heterojunctions while planar systems demonstrate well-ordered heterojunctions with a strictly defined electron transfer direction. Particularly, we demonstrate the possibility of the realization of Z-scheme of photoexcitation and charge separation in ternary planar systems under visible light irradiation

Sonochemical/hydration-dehydration synthesis of Pt-TiO2 NPs/decorated carbon nanotubes with enhanced photocatalytic hydrogen production activity

Modified Pt-TiO2 NPs/decorated carbon nanotubes were synthesized utilizing sonochemical/hydration-dehydration techniques. Pt was loaded on TiO2 by a photodeposition method keeping in mind the end goal to achieve electron-hole pair separation and promote the surface reaction. The morphological and basic properties of Pt-TiO2/fCNTs were investigated by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL) and Raman spectroscopy. The selected area electron diffraction (SAED) patterns of Pt-TiO2/fCNTs were obtained utilizing TEM-based energy dispersive X-ray spectroscopy (EDXS) analysis. It was found that the TiO2 nanoparticles were uniformly distributed on the fCNTs, and the Pt particles were decorated on the surface of TiO2/fCNTs. The photocatalytic hydrogen production activity of the Pt(0.5%)-TiO2/fCNTs(0.5%) nanoparticle composites was investigated using a sacrificial agent methanol solution. Pt-loaded TiO2 demonstrated a hydrogen evolution rate around 20 times that of TiO2/fCNTs(0.5%) (fSWCNTs, fMWCNTs). When compared with platinized TiO2 in methanol, which was utilized as a control material, Pt-TiO2/fCNTs demonstrated an almost 2-fold increment in hydrogen generation

Hybrid Organic–Inorganic Halide Post-Perovskite 3-Cyanopyridinium Lead Tribromide for Optoelectronic Applications

2D halide perovskite-like semiconductors are attractive materials for various optoelectronic applications, from photovoltaics to lasing. To date, the most studied families of such low-dimensional halide perovskite-like compounds are Ruddlesden–Popper, Dion–Jacobson, and other phases that can be derived from 3D halide perovskites by slicing along different crystallographic directions, which leads to the spatially isotropic corner-sharing connectivity type of metal-halide octahedra in the 2D layer plane. In this work, a new family of hybrid organic–inorganic 2D lead halides is introduced, by reporting the first example of the hybrid organic–inorganic post-perovskite 3-cyanopyridinium lead tribromide (3cp)PbBr3. The post-perovskite structure has unique octahedra connectivity type in the layer plane: a typical “perovskite-like” corner-sharing connectivity pattern in one direction, and the rare edge-sharing connectivity pattern in the other. Such connectivity leads to significant anisotropy in the material properties within the inorganic layer plane. Moreover, the dense organic cation packing results in the formation of 1D fully organic bands in the electronic structure, offering the prospects of the involvement of the organic subsystem into material's optoelectronic properties. The (3cp)PbBr3 clearly shows the 2D quantum size effect with a bandgap around 3.2 eV and typical broadband self-trapped excitonic photoluminescence at temperatures below 200 K