Nanoscale ZnS/TiO2 composites: Preparation, characterization, and visible-light photocatalytic activity

Photoactive ZnS/TiO₂ nanocomposites were prepared via microemulsion-mediated solvothermal method. The structure, composition, physicochemical property, and morphology of the composites were characterized by powder X-ray diffraction (XRD), Raman scattering studies, UV diffuse reflectance spectroscopy (UV/DRS), photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM). It showed that the composites were cube-shaped with particle sizes of 10 to 15 nm, and the phase structure for ZnS and TiO₂ in the composites was cubic and anatase, respectively. The content of the ZnS in the composites was 2.1%, 10.7%, and 19.9%, respectively. Compared with the solitary anatase TiO₂, the ZnS/TiO₂ exhibited enhanced visible-light photocatalytic activity for the aqueous parathion-methyl degradation. Factors including the interactions between the phases of ZnS and TiO₂, strong adsorption of the substrate at the surface of the ZnS/TiO₂ nanocomposites, and preassociation of the substrate and composites are responsible for this enhancement photocatalytic activity.     

WO3/BiVO4 composite photoelectrode prepared by improved auto-combustion method for highly efficient water splitting

We report on the improvement in the water splitting efficiency of a WO₃/BiVO₄ composite photoelectrode by the application of an improved auto-combustion method to the preparation of porous BiVO₄ thin films. The unique feature of this preparation method is the addition of both NH₄NO₃, as a strong oxidizing agent, and an organic additive into BiVO₄ precursor solution. The local decomposition heat of the organic additive and oxidizing agent created a porous film with small, highly crystalline BiVO₄ particles. The photoelectrode has many advantages over existing ones, such as the high light-harvesting efficiency (LHE), a single BiVO₄ phase, the facile access of the holes to the photoelectrode/electrolyte interface, and the ease of water and oxygen diffusion. The maximum incident photon-to-current efficiency (IPCE) was estimated to be 64% (at 440 nm, 1.23 V vs. RHE) and the applied bias photon-tocurrent efficiency (ABPE) reached as high as 1.28%. This ABPE value is highest among all oxide semiconductor photoelectrodes reported previously, except for the case of a stacking photoelectrode system.     

SnO2 nanocrystallines decorated g-C3N4 composites with enhanced visible-light photocatalytic activity

Abstract

A series of SnO₂ nanocrystallines decorated g-C₃N₄ architectures were synthesized using a facile solvothermal method. The structural, morphological, and optical properties of the as-prepared nanocomposites were characterized in detail, indicating that SnO₂ nanocrystallines with diameter ～ 4?nm were well-dispersed on the surface of g-C₃N_4. The photocatalytic activity of the composites was investigated by degrading rhodamine B (RhB) under visible light irradiation. The CNS2 heterostructure exhibits enhanced photocatalytic activity than bare SnO₂ and g-C₃N₄. Kinetic study revealed a promising degradation rate constant of 0.0593?min^?1 for the CNS2, which is 118 and 7 times higher than that of pure SnO₂ and g-C₃N₄, respectively. What’s more, the CNS2 still retained the photocatalytic activity after three cycle measurements. The enhanced photocatalytic performances of the nanocomposite may be due to its large surface area (116.2 m²/g), appropriate ratio of SnO₂/g-C₃N₄ and the compact structure of the junction between the SnO₂ nanocrystallines and the g-C₃N₄, which inhibits the recombination of photogenerated electrons and holes.     

Novel dual-layer photoelectrode prepared by RF magnetron sputtering for photocatalytic water splitting

Visible-light absorbing TiO₂ and WO₃ photocatalytic thin films were prepared by radio-frequency (RF) magnetron sputtering. The effects of sputtering condition on the structural, optical, as well as photocatalytic properties of the prepared thin films were explored. In addition, a novel dual-layer photocatalytic thin film that combines both visible-light TiO₂ and WO₃ was prepared by the same deposition technique to further enhance the photocatalytic performance. Instrumental analyses such as XRD, SEM-EDX, and UV–visible absorption spectrometry were performed to reveal the crystallinity, surface morphology, chemical composition, and light absorption of the prepared photocatalytic thin films. The activities of the prepared photocatalytic thin films under both UV and visible-light irradiations were evaluated by conducting photovoltammetry and water-splitting reaction in an H-type reactor. The enhanced photocurrent of dual-layer photocatalytic thin film was proved to be resulted from the improved charge separation of the dual-layer structure. The H₂ and O₂ yields obtained from the water-splitting reactions were consistent with the photocurrent results, showing dual-layer photocatalyst with higher photoactivity than mono-layer photocatalyst.     

Construction of hierarchical FeIn2S4/BiOBr S-scheme heterojunction with enhanced visible-light photocatalytic performance for antibiotics degradation

Constructing heterojunction provides a promising tactic to improve the photocatalytic efficiency of catalysts. In this paper, hierarchical FeIn₂S₄/BiOBr heterostructure photocatalysts were prepared by facile two step methods and applied to effectively remove ciprofloxacin (CIP) and tetracycline (TC) under visible light. Compared to single catalyst, FeIn₂S₄/BiOBr hybrids display significantly improved photocatalytic activity. Among the series, 6 wt% FeIn₂S₄/BiOBr shows the optimal photocatalytic performance, where the degradation efficiencies of TC and CIP are 3.15 and 2.88 times greater than pure BiOBr, respectively. Such an improvement could arise from the S-scheme heterojunctions and unique hierarchical structures, which brings stronger light absorption, higher photoexcited charge separation efficiency and superior redox ability. Furthermore, 6 wt% FeIn₂S₄/BiOBr composite exhibits excellent stability and reusability. Radical capture experiments and EPR analyses uncover that O₂^–, h⁺ and OH are primarily reactive substances during photocatalytic removal of TC. The products of TC were detected by LC-MS analyses and possible decomposition paths are proposed. Eventually, a possible photodegradation mechanism over FeIn₂S₄/BiOBr S-scheme heterojunction is proposed. These findings supply new perspective for the simple synthesis of S-scheme photocatalysts with promising applications in environment remediation.     

TiO2–CdS supported CuNi nanoparticles as a highly efficient catalyst for hydrolysis of ammonia borane under visible-light irradiation

TiO₂–CdS nanotubes (NTs) were used for the first time as a support to load metal nanoparticles (NPs) for the hydrolysis of ammonia borane (AB) which is a new strategy. The TiO₂–CdS NTs support was first synthesized using a hydrothermal method, and then the CuNi NPs were loaded using a liquid-phase reduction method. The synthesized samples were characterized by XRD, SEM-EDS, TEM, XPS, ICP, UV–Vis, and PL analyses. The characterization results show that the CuNi NPs existed in the form of an alloy with a size of ~1.2 nm and uniformly dispersed on the support. Compared with their single metal counterparts, the bimetallic CuNi-supported catalysts showed a higher catalytic activity in the hydrolysis of AB under visible-light irradiation: Cu_0·45Ni_0·55/TiO₂–CdS catalyst had the fastest hydrogen evolution rate with a high conversion frequency (TOF) of 25.9 mol_H2·mol_cat⁻¹ min⁻¹ at 25 °C and low activation energy of 32.8 kJ mol⁻¹. Cu_0.45Ni_0.55/TiO₂–CdS catalyst showed good recycle performance, maintaining 99.3% and 85.6% of the original hydrogen evolution rate even after five and ten recycles, respectively. Strong absorption of visible light, improved electron–hole separation efficiency, and metal synergy between Cu and Ni elements played a crucial role in improving the catalytic hydrolysis performance of AB. The catalyst prepared in this study provides a new strategy for the application of photocatalysts.     

Preparation and enhanced photoelectrocatalytic properties of a three-dimensional TiO2-Au porous structure fabricated using superaligned carbon nanotube films

Three dimensional TiO₂–Au cross-nanoporous structure (3D TiO₂–Au CNS) as an efficient photoelectrocatalytic system was fabricated using superaligned carbon nanotube films as etching masks and electron-beam evaporation. The 3D TiO₂–Au CNS exhibited a broad absorption band in the visible region, and the incident photon-to-current conversion efficiency of 3D TiO₂–Au CNS/Ti electrode was 3–4 times higher than that of pure TiO₂ electrode. The photocurrent density of the 3D TiO₂–Au CNS device was 0.079 mA cm⁻² at 0 V vs. Ag/AgCl with a solar irradiance of 100 mW cm⁻². This developed preparation method was simple, of high flexibility and can be adopted for mass production due to its low cost and good compatibility with other processing technologies. The 3D TiO₂–Au CNS and its preparation method have important value in design of photoelectrocatalytic system for research and practical applications, which may have a potential utility in photocatalytic and other photoelectrocatalytic reactions.     

Structure and properties of nitrogen-doped titanium dioxide thin films grown by atmospheric pressure chemical vapor deposition

Using TiCl₄, O₂, and N₂O as precursors, N-doped titanium dioxide thin films with large area and continuous surface were obtained by atmospheric pressure chemical vapor deposition. Measurements of X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope, transmission electron microscope and ultravoilet-Visible transmission spectra were performed. Using N₂O as N-doped source, anatase-rutile transformation is accelerated through oxygen vacancies formation, and the mean grain size of rutile crystallites decreases with the increase of N₂O flow rate. Compared to the pure TiO₂, N-doped TiO₂ films give a relative narrow optical band-gap, and their visible-light induced photocatalysis is much enhanced. Visible-light-induced hydrophilicity of the TiO₂ thin films enhances with the increase of N₂O flow rate, which might be due to the dentritic islands structure on the surface of the N-doped TiO₂ thin films.     

Fabrication of 1D long chain-like metal porphyrin-based coordination complexes for high-efficiency hydrogen evolution and photoelectric response

Hydrogen production from electrocatalytic water splitting has aroused extensive attention in many fields recently. Fabrication of low-cost and high-efficiency electrocatalysts are still an urgent and challenging work. Porphyrins as visible-light photosensitizers have been extensively utilized in visible-light photocatalysts and photoelectronic materials. So, fabrication of novel porphyrin-based complexes will be benefited for high-efficiency hydrogen evolution and photoelectric response. Here a series of zirconium porphyrin-based coordination complexes were successfully fabricated via a facile two-step strategy. Due to the unique long chain-like structure and low charge-transfer resistance, the zirconium porphyrin-based coordination complexes displayed excellent electrocatalytic performance for hydrogen evolution reaction. The ZrTPP-PTA-1 showed a low overpotential of 60 mV at the current density 10 mA cm⁻² and a Tafel slope of 87 mV dec⁻¹ with an ultralow electron transfer resistance of 17.5 Ω. In addition, a quick photocurrent response occurred for these coordination complexes with a visible-light illumination. The photocurrent of the ZrTPP-OA-2 rised up to 2.5 μA under visible-light irradiation. With this pleasant result, these zirconium porphyrin-based coordination complexes have a great potential to become available alternative of current noble electrocatalysts for photoelectric application.