Enhanced visible-light photoelectrochemical activity of TiO<Subscript>2</Subscript> nanorod arrays decorated by Sb<Subscript>2</Subscript>S<Subscript>3</Subscript> particles

Single-crystal TiO₂ nanorod arrays (NRAs) were synthesized successfully onto transparent conducting substrates through a facile hydrothermal route for photo-electrochemical (PEC) water-splitting. Further, the ordered TiO₂ NRAs were treated by SbCl₃ solution for preparing a layer of Sb₂S₃ and enhancing their PEC activity. A series of methods were employed to compare and analyze the differences between the TiO₂ NRA samples with/without Sb₂S₃ decoration. It was demonstrated that the PEC performance were enhanced significantly after being treated with SbCl₃ aqueous solution (precursor) under a hydrothermal environment. Compared to pure TiO₂ NRAs, the sample that decorated with Sb₂S₃ showed a more positive flat-band level as well as a higher donor density (i.e. electron density). Thus, it suggested that the enhanced PEC performance after Sb₂S₃ modification might be attributed to the widening of spectral response as well as the improvement of charge transfer / transport occurring at the solid/liquid interfaces.     

TiO<Subscript>2</Subscript> nanotube arrays: hydrothermal fabrication and photocatalytic activities

Titanium dioxide nanotube arrays (TiO₂ NTAs) with rutile phase have been fabricated successfully via a two-step hydrothermal method. TiO₂ nanorod arrays (TiO₂ NRAs) are first hydrothermally grown on FTO substrate. Then the TiO₂ NTAs can be obtained by controlling the HCl concentration of the hydrothermal etching process. The TiO₂ NTAs have been characterized by X-ray diffractometer, scanning electron microscope, transmission electron microscopy, X-ray photoelectron spectroscopy, and ultraviolet–visible spectroscope. Evolution of TiO₂ nanoarrays are accompanied by enhanced of the surface area and optical properties. Compared with TiO₂ NRAs, the prepared TiO₂ NTAs is more efficient in the photodegradation of methyl orange. These results reveal that the hydrothermal chemical etching provide a flexible and straightforward route for design and preparation of TiO₂ NTAs, promising for new opportunities in photocatalysts and other fields.     

Photoreduction synthesis of silver on Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposites and their catalytic activity for the degradation of methyl orange

This paper demonstrates the preparation of pure TiO₂, 40% of Bi₂O₃ in TiO₂ and Ag loaded Bi₂O₃/TiO₂ nanocomposites by the hydrothermal method followed by the photoreduction process. The crystal structure, morphology and composition of the samples were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy respectively. The dispersion of Ag nanoparticles on the surface of Bi₂O₃/TiO₂ nanocomposites are found to bring the conduction band near to the valence band, resulting in the narrow band gap compared to pure TiO₂ and Bi₂O₃/TiO₂ nanocomposites. The XRD analysis demonstrated that silver nanoparticles were dispersed finely on the surface of Bi₂O₃/TiO₂ nanocomposites. All the characterization results revealed that the Ag/Bi₂O₃/TiO₂ nanocomposites were smaller crystallite size, stronger absorbance in the visible region and greater surface area than pure TiO₂ and Bi₂O₃/TiO₂ nanocomposites. The photoluminescence intensity decreases with an increase in the UV-illumination time of Ag loaded Bi₂O₃/TiO₂ revealing a decrease in the recombination rate of electron–hole pairs. In order to test them as a photocatalyst, methyl orange was used as a standard. The photocatalytic degradation of methyl orange shows that the ABT5 sample exhibits the maximum degradation efficiency of 99% within 180 min of irradiation.     

Construction of hierarchical TiO<Subscript>2</Subscript> nanorod array/graphene/ZnO nanocomposites for high-performance photocatalysis

The photocatalytic performance of heterostructure photocatalysts is limited in practical use due to the charge accumulation at the interface and its low efficiency in utilizing solar energy during photocatalytic process. In this work, a ternary hierarchical TiO₂ nanorod arrays/graphene/ZnO nanocomposite is prepared by using graphene sheets as bridge between TiO₂ nanorod arrays (NRAs) and ZnO nanoparticles (NPs) via a facile combination of spin-coating and chemical vapor deposition techniques. The experimental study reveals that the graphene sheets provide a barrier-free access to transport photo-excited electrons from rutile TiO₂ NRAs and ZnO NPs. In addition, there generates an interface scattering effect of visible light as the graphene sheets provide appreciable nucleation sites for ZnO NPs. This synergistic effect in the ternary nanocomposite gives rise to a largely enhanced photocurrent density and visible light-driven photocatalytic activity, which is 2.6 times higher than that of regular TiO₂ NRAs/ZnO NPs heterostructure. It is expected that this hierarchical nanocomposite will be a promising candidate for applications in environmental remediation and energy fields.     

Ultrasonic-assisted synthesis of amorphous Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> coupled (BiO)<Subscript>2</Subscript>CO<Subscript>3</Subscript> catalyst with improved visible light-responsive photocatalytic activity

A series of Bi₂S₃/(BiO)₂CO₃ composite photocatalysts with different loadings of amorphous Bi₂S₃ were successfully synthesized through an ultrasonic-assisted ion-exchange reaction between thioacetamide (CH₃CSNH₂) and (BiO)₂CO₃, and characterized by XRD, XPS, BET, EELS, EDX, SEM, TEM/HRTEM, UV–Vis, and photoluminescence (PL) techniques. The results of TEM/HRTEM, EELS, and EDX indicate that the composite catalyst Bi₂S₃/(BiO)₂CO₃ has been successfully synthesized with the deposited Bi₂S₃ present in amorphous state on the surface of (BiO)₂CO₃. The activities of the catalysts for RhB degradation under visible light show that the catalyst prepared under ultrasonic is more active than the one synthesized without ultrasonic. The optimized sample Bi₂S₃/(BiO)₂CO₃ (U5.0) exhibits a much higher activity, about 4.8 times to that of pure (BiO)₂CO₃. Based upon the band structures of Bi₂S₃/(BiO)₂CO₃, it is deduced that the migration of the visible light-induced electrons from the conduction band of Bi₂S₃ to that of (BiO)₂CO₃ should have facilitated the separation of photogenerated carriers, as confirmed by the suppressed photoluminescence spectra. Using different scavengers, the ·O₂ ^? and holes are clearly identified as the main oxidative species for RhB photodegradation. In light of these observations, a potential photocatalytic mechanism of RhB degradation over Bi₂S₃/(BiO)₂CO₃ is proposed.     

The effects of electronic structure of non-metallic doped TiO<Subscript>2</Subscript> anode and co-sensitization on the performance of dye-sensitized solar cells

N/TiO₂, S/TiO₂, and N S/TiO₂ nanocrystalline films anode were obtained by doping non-metallic element N and S which could change the LUMO of anode, leading to the easy injection of electron from the excited state of dye molecule to the conduction band of semiconductor, and thus improving the photoelectric conversion efficiency and reducing the impedance of solar cells. The anode films treated by titanium tetrachloride and co-sensitized by P3HT/N719 were also studied. The absorption region of P3HT/N719 covered the entire visible region in the solar cells. The solar cell based on N/TiO₂ anode film treated by titanium tetrachloride and P3HT/N719 showed a short-circuit current density of 10.20 mA/cm², open-circuit voltage of 0.557 V, and photoelectric conversion efficiency of 2.55%.     

Sn<Superscript>4+</Superscript> and La<Superscript>3+</Superscript> co doped TiO<Subscript>2</Subscript> nanoparticles and their optical,photocatalytic and antibacterial properties under visible light

Sn⁴⁺ and La³⁺ co-doped TiO₂ photocatalytic material with nanoparticle structure have been successfully prepared using SnCl₂·2H₂O and La(NO₃)₃·6H₂O as precursors. Scanning electron microscopy, X-ray diffraction, transmission electron microscopy and UV–visible spectroscopy have been used to for the characterization of the morphology, crystal structure, particle size and optical properties of the samples. The photocatalytic properties of sample with various amount of La doped TiO₂ have been studied by photo degradation of methyl orange (MO) in water under visible light. XRD patterns showed both rutile and anatase phases for 5 mol% of Sn and 5–10 mol% of La. But anatase phase with a little rutile phase was formed for 5 mol%Sn and 10 mol%La. The prepared Sn and La co doped TiO₂ photo-catalyst showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of MO solution under visible irradiation. Antibacterial behavior towards E. coli was then studied under visible irradiation. The synthesized T-5%Sn-10%La powder exhibited superior antibacterial activity under visible irradiation compared to the pure TiO₂.     

Efficient visible-light driven photocatalysts: coupling TiO<Subscript>2</Subscript>(AB) nanotubes with g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> nanoflakes

The wide application of the titanium dioxide (TiO₂) as the photocatalysts is greatly hindered by its intrinsic large band gap and usually fast electron–hole recombination. Here, we reported the exploration of coupling g-C₃N₄ nanoflakes to TiO₂ nanotubes with the anatase and TiO₂(B) mixed phases (TiO₂(AB)) toward the efficient visible-light-driven hybrid photocatalyst. It is found that coupling TiO₂(AB) nanotubes with g-C₃N₄ nanoflakes could bring a profoundly extension the visible light adsorption capacity and enhanced photogenerated carrier separation. Accordingly, they exhibit much higher efficient photocatalytic activities toward the degradation of sulforhodamine B under the visible light irradiation, which is enhanced for nearly 15 times to those of the TiO₂(AB) and g-C₃N₄, suggesting their promising practical applications as novel and efficient semiconductor photocatalysts for the water purification.     

Formation of solid solutions in the TiO<Subscript>2</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The phase formation and reaction kinetics in the TiO₂-Cr₂O₃ system have been studied by x-ray diffraction and electron microscopy. The Cr₂O₃ solubility in TiO₂ has been accurately determined, and the rate parameters of the formation of solid solutions in this system have been evaluated. The results demonstrate that Cr₂O₃ dissolves in rutile and not in anatase. Cr₂O₃ markedly reduces the temperature of the anatase-rutile phase transition.     

Construction of 3D marigold-like Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Ag<Subscript>2</Subscript>O/CQDs heterostructure with superior visible-light active photocatalytic activity toward tetracycline degradation and selective oxidation

A novel visible-light-driven photocatalyst Bi₂WO₆/Ag₂O/CQDs (BWO/Ag₂O/CQDs), which possesses hierarchical superstructure with marigold-like appearance, was fabricated via a hydrothermal method, followed by a simple precipitation process. Ag₂O nanoparticles sized around 25 nm and CQDs with diameters of about 10 nm were evenly deposited on Bi₂WO₆ to form a unique heterostructure. The obtained BWO/Ag₂O/CQDs heterostructure showed excellent adsorption and remarkably enhanced photocatalytic performance in the photodegradation of antibiotic tetracycline (TC) under visible-light irradiation compared to pristine Bi₂WO₆. The degradation rate of TC over BWO/Ag₂O/CQDs photocatalyst is 16.2 times higher than that of pristine Bi₂WO₆ and a possible mechanism for the enhanced photocatalytic performance was discussed. In addition, BWO/Ag₂O/CQDs was applied in the selective oxidation of benzyl alcohol to benzaldehyde under visible-light illumination. The result demonstrated that the conversion rate and product selectivity are greatly improved over BWO/Ag₂O/CQDs compared to pristine Bi₂WO₆ in the same reaction conditions, making it a promising photocatalyst in the application of green chemical transformation. The co-coupling of CQDs and Ag₂O with matched band potentials gives a substantial promotion for the light harvesting ability and effective separation of photogenerated charge carriers, synergistically accounting for the improvement of photocatalytic efficiency.     

Fabrication of plate-on-plate Z-scheme SnS<Subscript>2</Subscript>/Bi<Subscript>2</Subscript>MoO<Subscript>6</Subscript> heterojunction photocatalysts with enhanced photocatalytic activity

A class of direct plate-on-plate Z-scheme heterojunction SnS₂/Bi₂MoO₆ photocatalysts was synthesized via a two-step hydrothermal method. The materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectra, Fourier transform infrared photoluminescence emission spectra, and UV–vis diffuse reflectance spectroscopy. The photocatalytic activity was estimated via the degradation of crystal violet (CV) and ciprofloxacin (CIP). The experimental results indicated that the 5 wt% SnS₂/Bi₂MoO₆ composites exhibited significantly enhanced performance in contrast to pure Bi₂MoO₆ or SnS₂ nanoflakes, and were also superior to the popular TiO₂ (P25). The degradation reaction accorded well with the first-order reaction kinetics equation; the rate constant of CV using a SnS₂ content of 5 wt% photocatalyst was ~?3.6 times that of the Bi₂MoO₆ and 2.4 times that of SnS₂. Furthermore, a SnS₂ content of 5 wt% exhibited a 1.7 times higher photocatalytic activity of CIP than that of pure Bi₂MoO₆, and 1.3 times that of pure SnS₂. Radical trapping experiments and an electron spin resonance technique indicated that h⁺ and ·OH were the dominant active species involved in the degradation process. A plasmonic Z-scheme photocatalytic mechanism was proposed to explain the superior photocatalytic activities and efficient separation of photogenerated electrons and holes.     

Novel Bi<Subscript>12</Subscript>TiO<Subscript>20</Subscript>/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> composite with enhanced photocatalytic performance through Z-scheme mechanism

Novel Bi₁₂TiO₂₀/g-C₃N₄ composite was successfully prepared with Bi₁₂TiO₂₀ nanoparticles embedded within the fluffy crumpled g-C₃N₄ nanosheets. Bi₁₂TiO₂₀/g-C₃N₄ composites exhibit superior photoactivity and stability. As compared with g-C₃N₄ and Bi₁₂TiO₂₀, the photocatalytic efficiency of Bi₁₂TiO₂₀/g-C₃N₄ is effectively enhanced about 1.8- and 4.9-fold, respectively. Based on the trapping experiment, ^·OH and ^·O₂^? radicals are the dominant reactive oxygen species involved in the photocatalytic process. The proposed Z-scheme mechanism of charge transfer markedly promotes the carriers’ migration and separation, leading to the enhanced photocatalytic performance.     

Structural investigations on lead-free Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript>-based piezoceramics

In this study, recent results from our electron, X-ray, and neutron-diffraction experiments with emphasis on the binary Bi_1/2Na_1/2TiO₃-BaTiO₃ (BNT–BT) and ternary Bi_1/2Na_1/2TiO₃–BaTiO₃–K_0.5Na_0.5NbO₃ (BNT–BT–KNN) system are presented and contrasted with literature. The experimental results clearly revealed a phase coexistence on the nanoscale level. A systematic study of superlattice reflections in conjunction with microstructural characteristics showed that the BNT-based systems have specific properties in common, which, however, strongly depend on composition. In situ transmission electron microscopy (TEM) electric field experiments unequivocally demonstrated the evolution of lamellar domains. Combining in situ TEM results with published in situ neutron-diffraction experiments, we proposed an electric field-induced phase transition that results in the giant unipolar and bipolar strain observed in specific compositions of the ternary system.     

Effect of cerium additive and secondary phase analysis on Ag<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> ceramics

Cerium-doped silver bismuth titanate—Ag_0.5Bi_0.5TiO₃ (ABT) ceramics have been synthesized by the high-temperature solid-state reaction method. The structure and elemental examination of the prepared ceramic was analysed by X-ray diffraction (XRD), Fourier transform infrared, scanning electron microscopy and energy-dispersive spectroscopy. XRD analysis showed the presence of pyrochlore structure and secondary phase when more than 5 mol% cerium was added. The impact of temperature on cerium-doped silver bismuth titanate samples was analysed by differential thermal analysis and differential scanning calorimetry. Cerium doping caused the flaky morphology comparing with undoped sample. The homogeneity of all the samples was discussed in detail by diffuse reflectance spectrum. This is the first time the reflection process is analysed for the cerium-doped ABT system to the best of our knowledge.     

Fabrication of Ag<Subscript>3</Subscript>PO<Subscript>4</Subscript>-AgBr-PTh composite loaded on Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript> with enhanced visible-light photocatalytic activity

A novel Ag₃PO₄-AgBr-PTh composite loaded on Na₂SiO₃ was synthesized for enhanced visible-light photocatalytic activity. The photocatalytic activity of the samples was evaluated by photodegrading rhodamine B (RhB) under visible light irradiation. The main reactive species and possible photocatalytic mechanism were also discussed. As a result, the Ag₃PO₄-AgBr-PTh composite loaded on Na₂SiO₃ exhibited enhanced photocatalytic activity for RhB compared with Ag₃PO₄ under visible-light irradiation. Additionally, it was demonstrated that the hole (h⁺) and superoxide radical (?O ₂ ^? ) were the major reactive species involving in the RhB degradation. PTh played vital role for the enhanced photocatalytic activity of Ag₃PO₄-AgBr-PTh-Na₂SiO₃ composite, which offered an electron transfer expressway and accelerated the transfer of the electrons from the CB of AgBr into Ag₃PO₄. This work could provide a new perspective for the synthesis of Ag₃PO₄-based composites and the improvement of photocatalytic activity of Ag₃PO₄.     

Low-temperature sintering and microwave dielectric properties of TiO<Subscript>2</Subscript>-based LTCC materials

Temperature stable high-K LTCC material was prepared. The influence of fabrication process on the crystalline phases, microstructures and microwave dielectric properties of TiO₂-Bi₂O₃-CuO ceramics were investigated. The crystalline phases and microstructures of TiO₂-Bi₂O₃-CuO ceramics were investigated by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. It was found that rutile TiO₂ phase and Bi₂Ti₄O₁₁ phase co-existed in the TiO₂-Bi₂O₃-CuO ceramics. Separate TiO₂ grains and Bi₂Ti₄O₁₁ grains distributed uniformly in the ceramic matrix. The composition 0.92TiO₂-0.08Bi₂Ti₄O₁₁ with 2 wt% CuO addition that was sintered at 900 °C for 2 h showed high dielectric constant (ε_r ~ 81), high quality factor (Q × f ~ 3,500 GHz) and near zero temperature coefficient of resonant frequency (τ_f ~ −5.1 ppm/°C), meanwhile the compatibility test showed that it could co-fire with silver electrode. The processing-microstructure-property interrelationship was also studied.     

Synthesis of graphene oxide/Ag<Subscript>3</Subscript>PO<Subscript>4</Subscript> composite with enhanced visible-light photocatalytic activity

The nano-scale Ag₃PO₄ was successfully synthesized by the silver ammonia complexing precipitation method at room temperature. And the Graphene oxide (GO)/Ag₃PO₄ nanocomposites with different contents of GO were successfully synthesized using the electrostatic driving method. The as-prepared GO/Ag₃PO₄ nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV–visible diffuse reflectance spectroscopy (UV–Vis DRS), confirming that Ag₃PO₄ were highly dispersed to GO sheet. The photocatalytic properties of GO/Ag₃PO₄ were evaluated by the degradation of Methyl Orange (MO) under visible light irradiation and solar irradiation respectively. The results showed that the photocatalytic efficiencies of GO/Ag₃PO₄ nanocomposites had enhanced largely and the kinetics reaction models were followed first-order. Furthermore, 5% GO/Ag₃PO₄ exhibited the highest photocatalytic activity on degradation of MO under visible-light irradiation. The improved photocatalytic performances of the GO/Ag₃PO₄ nanocomposites mainly attributed to the introducing of GO, which benefit for electron transfer and inhibit the recombination of electron–hole pairs, promoting the practical application of Ag₃PO₄ in water purification.     

Rutile TiO<Subscript>2</Subscript> films as electron transport layer in inverted organic solar cell

Titanium dioxide (TiO₂) thin films were prepared by sol–gel spin coating method and deposited on ITO-coated glass substrates. The effects of different heat treatment annealing temperatures on the phase composition of TiO₂ films and its effect on the optical band gap, morphological, structural as well as using these layers in P3HT:PCBM-based organic solar cell were examined. The results show the presence of rutile phases in the TiO₂ films which were heat-treated for 2 h at different temperatures (200, 300, 400, 500 and 600 °C). The optical properties of the TiO₂ films have altered by temperature with a slight decrease in the transmittance intensity in the visible region with increasing the temperature. The optical band gap values were found to be in the range of 3.28–3.59 eV for the forbidden direct electronic transition and 3.40–3.79 eV for the allowed direct transition. TiO₂ layers were used as electron transport layer in inverted organic solar cells and resulted in a power conversion efficiency of 1.59% with short circuit current density of 6.64 mA cm^?2 for TiO₂ layer heat-treated at 600 °C.     

Crystallization of amorphous Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> films

The crystallization kinetics of amorphous Bi₂S₃ films have been studied by kinematic electron diffraction. The results have been used to evaluate the activation energies for activation energy and crystal growth.     

Effects of sodium oleate on synthesis and photocatalytic activity of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>@RGO

In this study, the effects of sodium oleate on synthesis of Bi₂WO₆/Bi₂O₃ loaded reduced graphene oxide photocatalyst was studied. The as-prepared composites were characterized by X-ray diffraction, Fourier transform infrared, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance and photoluminescence spectroscopy. The results suggested that addition of sodium oleate not only promoted synthesis of Bi₂O₃, but also enhanced the reduction of GO to graphene. When the amount of sodium oleate was 4 mol (Bi:SO?=?1:1), Bi₂WO₆/Bi₂O₃@RGO to the best visible-light photocatalytic activity can be synthesized by a facile one-step solvothermal process without further reduction reaction. Hence, it indicated that sodium oleate could affect the synthesis of the as-prepared composites and the photocatalytic activity for degradation of RhB. This study did provide not only a facile method to synthesize Bi₂WO₆/Bi₂O₃@RGO, but also a method to reduce graphene oxide to graphene.