Dramatically Enhanced Li-Ion Storage of ZnO@C Anodes through TiO2 Homogeneous Hybridization

Amorphous nanoparticles of ZnO and TiO₂ embedded in carbon nanocages (AZT⊂CNCs) were successfully synthesized through a simple annealing process of TiO₂-coated zeolitic imidazolate framework-8 (ZIF-8). In the current anode of AZT⊂CNCs, tiny ZnO and TiO₂ nanoparticles were uniformly distributed in the carbon matrix (carbon nanocages), which could effectively buffer the volume expansion of electroactive ZnO and provide excellent electric conductivity. After fully investigating the electrochemical performance of the AZT⊂CNCs samples obtained with different additive amounts of tetrabutyl orthotitanate (TBOT) for TiO₂ coating, it has been found that AZT-30 (0.1 g ZIF-8 with 30 mL TBOT) shows the best cycle stability (510 mA h g⁻¹ after 350 cycles at 200 mA g⁻¹) and a superior rate capability (610 mA h g⁻¹ after 3500 cycles at 2 A g⁻¹). The greatly enhanced Li-ion storage performance could be ascribed to the fact that the introduction of amorphous TiO₂ could activate the reversible lithiation/delithiation reaction of ZnO during the charge/discharge process.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with nitrogen and cerium

Nitrogen and cerium codoped TiO₂ photocatalysts were prepared by a modified sol-gel process with doping precursors of cerium nitrate and urea, and characterized by X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC), X-ray photoelectron spectra (XPS) and ultraviolet-visible light diffuse reflectance spectra (UV-vis DRS). Results indicate that anatase TiO₂ is the dominant crystalline type in as-prepared samples, and CeO₂ crystallites appear as the doping ratio of Ce/Ti reaches to 3.0 at%. The TiO₂ starts to transform from amorphous phase to anatase at 987.1 K during calcination, according to the TG-DSC curves. The XPS show that three major metal ions of Ce³⁺, Ce⁴⁺, Ti⁴⁺ and one minor metal ion of Ti³⁺ coexist on the surface. The codoped TiO₂ exhibits significant absorption within the range of 400-500 nm compared to the non-doped and only nitrogen-doped TiO₂. The enhanced photocatalytic activity of the codoped TiO₂ is demonstrated through degradation of methyl orange under visible light irradiation.     

Synthesis and photocatalytic activity for water-splitting reaction of nanocrystalline mesoporous titania prepared by hydrothermal method

Nanocrystalline mesoporous TiO₂ was synthesized by hydrothermal method using titanium butoxide as starting material. XRD, SEM, and TEM analyses revealed that the synthesized TiO₂ had anatase structure with crystalline size of about 8 nm. Moreover, the synthesized titania possessed a narrow pore size distribution with average pore diameter and high specific surface area of 215 m²/g. The photocatalytic activity of synthesized TiO₂ was evaluated with photocatalytic H₂ production from water-splitting reaction. The photocatalytic activity of synthesized TiO₂ treated with appropriate calcination temperature was considerably higher than that of commercial TiO₂ (Ishihara ST-01). The utilization of mesoporous TiO₂ photocatalyst with high crystallinity of anatase phase promoted great H₂ production. Furthermore, the reaction temperature significantly influences the water-splitting reaction.     

Surface properties,adherence, and photocatalytic activity of sol–gel dip-coated TiO2–ZnO films on glass plates

In this study, TiO₂–ZnO nanostructured films prepared from different Ti/water mole ratios were deposited on glass plates by a sol–gel dip-coating method. The structural and surface properties, adherence, and photoactivity of synthesized TiO₂–ZnO coatings in methylene blue degradation were investigated. Among the as-prepared TiO₂–ZnO coatings from sols with different Ti/water mole ratios (1, 0.66, 0.5, and 0.4), the highest sol concentration (Ti/water mole ratio of 1) showed the highest methylene blue photodegradation of almost 80% after 400 min of UV irradiation. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Energy-dispersive X-ray (EDX), and UV-vis diffuse reflectance spectra (DRS) confirmed that at high sol concentrations (Ti/water mole ratios of 1 and 0.66), a mixed phase of anatase and rutile is formed, whereas at a Ti/water mole ratio of 0.5, just pure rutile is formed. In detail, decreasing the sol concentration increases the cracks, degree of agglomeration, and the thickness of coatings. UV-vis DRS studies also confirm that decreasing the sol concentration in synthesized TiO₂–ZnO films leads to a shift in the absorption region of the coating to the UV region. Moreover, decreasing the sol concentration declines the coating adherence onto glass plates. TEM images of the TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 revealed the formation of ZnO nanorods around a spherical TiO₂, which indicates the presence of strong interaction between TiO₂ and ZnO nanoparticles. The TiO₂–ZnO coating synthesized from sol with a Ti/water mole ratio of 1 was then evaluated at different methylene blue concentrations, pH values, and number of coatings. After five consecutive runs, no significant decrease in the photodegradation efficiency was observed. Scanning electron microscopy (SEM) picture of used coating showed a smooth and stable layer without any detachment. Thermogravimetric analysis (TG) and sonication test confirmed thermal and mechanical stabilities of this coating as well.     

Microstructure and luminescence of transparent glass ceramic containing Er:BaF2 nano-crystals

Transparent BaF₂-SiO₂ glass ceramics doped with different content of Er³⁺ were prepared by sol-gel method. The microstructural evolution of the samples was studied with X-ray diffraction (XRD), transmission electron microscope (TEM), absorption and infrared spectra (IR). BaF₂ nano-crystals with 2-15 nm in size, depending on the crystallization temperature, distributed homogeneously among the amorphous silica matrix. The BaF₂ lattice parameters decreased with the increasing of Er³⁺ doping, indicating the incorporation of Er³⁺ into nano-crystals, which was further confirmed by energy dispersive X-ray spectroscopy (EDS) and absorption spectra analysis. The upconversion emissions of Er³⁺ emerged under the excitation at 980 nm for glass ceramic heat-treated at 800 °C.     

CTAB-assisted synthesis of mesoporous F-N-codoped TiO2 powders with high visible-light-driven catalytic activity and adsorption capacity

This article describes the preparation of mesoporous rod-like F-N-codoped TiO₂ powder photocatalysts with anatase phase via a sol-gel route at the temperature of 373 K, using cetyltrimethyl ammonium bromide (CTAB) as surfactant. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra (UV-vis DRS). The results showed that the photocatalysts possessed a homogeneous pore diameter and a high surface area of 106.3-160.7 m³ g⁻¹. The increasing CTAB reactive concentration extended the visible-light absorption up to 600 nm. The F-N-codoped TiO₂ powders exhibited significant higher adsorption capacity for methyl orange (MO) than that of Degussa P25 and showed more than 6 times higher visible-light-induced catalytic degradation for MO than that of P25.     

Structural and Optical Properties of Novel Surfactant Coated TiO<Subscript>2</Subscript>–Ag Based Nanoparticles

Stable dispersions of surfactant-coated TiO₂–Ag based nanoparticles in apolar medium have been prepared by performing sequentially the hydrolysis of titanium(IV) isopropoxide and the reduction of Ag⁺ in the confined space of sodium bis(2-ethylhexyl)sulfosuccinate (NaAOT) reverse micelles. Depending on the sequence length, this novel procedure allowed the synthesis of semiconductor–metal nanoparticles, nominally indicated as TiO₂/Ag, TiO₂/Ag/TiO₂, and TiO₂/Ag/TiO₂/Ag, stabilized by a monolayer of oriented surfactant molecules. The structural characterization of these nanoparticles has been performed by High Resolution Transmission Electron Microscopy (HR-TEM), while optical properties were investigated by UV–Vis absorption and fluorescence spectroscopies. TEM investigation showed the presence of globular nanoparticles with an average diameter of about 10 nm composed by distinct amorphous TiO₂ and crystalline Ag glued domains whose structure depends on the sequence length. UV–Vis absorption measurements highlighted the mutual metal–semiconductor influence on the TiO₂ energy band gap and on the Ag plasmon resonance. Steady-state fluorescence spectra analysis allowed to reveal the strong inhibition of the electron–hole radiative recombination in the TiO₂ domains due to the Ag and the appearance of a new emission band centred in the 484–545 nm range. Possible attributions of the involved electronic transition of this last emission are discussed.     

Mesoporous TiO2 nanoparticles for highly sensitive solid-phase microextraction of organochlorine pesticides

Mesoporous TiO₂ nanoparticles were synthesized with the hydrothermal method and characterized by powder X-ray diffraction (PXRD) and transmission electron microscope (TEM). Then a superior solid-phase microextraction (SPME) fiber was fabricated by sequentially coating the stainless steel fiber with silicone sealant film and mesoporous TiO₂ powder. The developed fiber possessed a homogeneous surface and a long life-span up to 100 times at direct immersing (DI) extraction mode. Under the optimized conditions, the extraction efficiencies of the self-made 17 μm TiO₂ fiber for six organochlorine pesticides (OCPs) were higher than those of the two commercial fibers (65 μm PDMS/DVB and 85 μm PA fibers) which were much thicker than the former. As for analytical performance, low detection limits (0.08–0.60 ng L⁻¹) and wide linearity (5–5000 ng L⁻¹) were achieved under the optimal conditions. The repeatabilities (n = 5) for single fiber were between 2.8 and 12.3%, while the reproducibilities (n = 3) of fiber-to-fiber were in the range of 3.7–15.7%. The proposed fiber was successfully applied to the sensitive analysis of OCPs in real water samples and four of the six analytes were detected from the rainwater and the lake water samples.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

Photoluminescence properties of BaMoO4 amorphous thin films

BaMoO₄ amorphous and crystalline thin films were prepared from polymeric precursors. The BaMoO₄ was deposited onto Si wafers by means of the spinning technique. The structure and optical properties of the resulting films were characterized by FTIR reflectance spectra, X-ray diffraction (XRD), atomic force microscopy (AFM) and optical reflectance. The bond Mo-O present in BaMoO₄ was confirmed by FTIR reflectance spectra. XRD characterization showed that thin films heat-treated at 600 and 200 °C presented the scheelite-type crystalline phase and amorphous, respectively. AFM analyses showed a considerable variation in surface morphology by comparing samples heat-treated at 200 and 600 °C. The reflectivity spectra showed two bands, positioned at 3.38 and 4.37 eV that were attributed to the excitonic state of Ba²⁺ and electronic transitions within MoO²⁻₄, respectively. The optical band gaps of BaMoO₄ were 3.38 and 2.19 eV, for crystalline (600 °C/2 h) and amorphous (200 °C/8 h) films, respectively. The room-temperature luminescence spectra revealed an intense single-emission band in the visible region. The PL intensity of these materials was increased upon heat-treatment. The excellent optical properties observed for BaMoO₄ amorphous thin films suggested that this material is a highly promising candidate for photoluminescent applications.     

TiO2 nanoparticles incorporated with CuInS2 clusters: preparation and photocatalytic activity for degradation of 4-nitrophenol

TiO₂ nanoparticles incorporated with CuInS₂ clusters were prepared in a solvothermal process and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersion X-ray analysis (EDX). Compared with pure TiO₂ nanoparticles, the TiO₂ nanoparticles incorporated with CuInS₂ clusters display higher photocatalytic activity with 99.9% of degradation ratio of 4-nitrophenol after 2 h irradiation. In order to investigate the effect of the CuInS₂ clusters on the photocatalytic activity of TiO₂ nanoparticles, diffuse reflectance UV–Vis spectra (DRS), photoluminescence (PL) spectra, and photocurrent action spectra were measured. The results indicate that the enhanced photocatalytic activity is probably due to the interface between TiO₂ and CuInS₂ as a trap of the photogenerated electrons to decrease the recombination of electrons and holes.     

Porosity, structural and fractal study of sol-gel TiO2-CeO2 mixed oxides

Sol-gel TiO₂-CeO₂ materials were synthesized at pH=3 employing HNO₃ as hydrolysis agent. Gels were thermally treated at 473, 673, 873, and 1073 K, respectively. Morphologies of the final substrates were studied via N₂ sorption, XRD and TEM. N₂ isotherms indicated a steady porosity in TiO₂-CeO₂ samples treated up to 873 K. Adsorption-desorption isotherms and TEM micrographs were used to perform fractal analyses of annealed samples. A dominant anatase phase was detected by XRD between 473 and 873 K while a rutile phase was evident at 1073 K. The presence of cerium conferred an increased thermal stability to the TiO₂ materials against particle sintering and pore collapse. The structure of cerium-doped anatase lattice was visualized through crystal simulation to investigate the possible substitution of Ti⁴⁺ by Ce⁺⁴ ions. This effect and the progressive segregation of CeO₂ crystals with temperature on the surface of TiO₂ grains lead to substrates of assorted morphologies.     

Preparation and characterization of poly(l-lactic acid)/TiO2 nanoparticle nanocomposite films with high transparency and efficient photodegradability

Poly(l-lactic acid)-TiO₂ nanoparticle nanocomposite films were prepared by incorporating surface modified TiO₂ nanoparticles into polymer matrices. In the process of preparing the nanocomposite films, severe aggregation of TiO₂ nanoparticles could be reduced by surface modification by using carboxylic acid and long-chain alkyl amine. As a result, the nanocomposite films with high transparency, similar to pure PLA films, were obtained without depending on the amount of added TiO₂ nanoparticles. A TEM micrograph of the nanocomposite films suggests that the TiO₂ nanoparticles of 3-6 nm in diameter were uniformly dispersed in polymer matrices. Photodegradation of PLA-TiO₂ nanoparticle nanocomposite films was also investigated. The results showed that nanocomposite films could be efficiently photodegraded by UV irradiation in comparison with pure PLA.     

Photoinduced interactions between colloidal TiO2 nanoparticles and calf thymus-DNA

The interaction of colloidal TiO₂ nanoparticles with calf thymus-DNA was studied by using absorption, FT-IR, steady state and time resolved fluorescence spectroscopic techniques. The apparent association constant has been deduced (K_app = 2.85 × 10³ M⁻¹) from the absorption spectral changes of the DNA-colloidal TiO₂ nanoparticles using the Benesi–Hildebrand equation. Addition of colloidal TiO₂ nanoparticles quenched the fluorescence of EtBr–DNA. The number of binding sites (n = 0.97) and the apparent binding constant (K = 6.68 × 10³ M⁻¹) were calculated from relevant fluorescence quenching data. The quenching, through a static mechanism, was confirmed by time resolved fluorescence spectroscopy.     

Preparation of magnetic CoFe2O4-functionalized graphene sheets via a facile hydrothermal method and their adsorption properties

Magnetic CoFe₂O₄-functionalized graphene sheets (CoFe₂O₄-FGS) nanocomposites have been synthesized by hydrothermal treatment of inorganic salts and thermal exfoliated graphene sheets. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show that cobalt ferrite nanoparticles with sizes of 10-40 nm are well dispersed on graphene sheets. OH⁻ was recognized as a tie to integrate the inorganic salts with the graphene sheets, which made reaction started and developed on the surface of graphene sheets and formed cobalt ferrite nanoparticles on graphene sheets. The adsorption kinetics investigation revealed that the adsorption of methyl orange from aqueous solution over the as-prepared CoFe₂O₄-FGS nanocomposites followed pseudo-second-order kinetic model and the adsorption capacity was examined as high as 71.54 mg g⁻¹. The combination of the superior adsorption of FGS and the magnetic properties of CoFe₂O₄ nanoparticles can be used as a powerful separation tool to deal with water pollution.     

The preparation and characterization of La doped TiO2 nanoparticles and their photocatalytic activity

In this paper, pure and La doped TiO₂ nanoparticles with different La content were prepared by a sol-gel process using Ti (OC₄H₉)₄ as raw material, and also were characterized by XRD, TG-DTA, TEM, XPS, DRS and Photoluminescence (PL) spectra. We mainly investigated the effects of calcining temperature and La content on the properties and the photocatalytic activity for degrading phenol of as-prepared TiO₂ samples, and also discussed the relationships between PL spectra and photocatalytic activity as well as the mechanisms of La doping on TiO₂ phase transformation. The results showed that La³⁺ did not enter into the crystal lattices of TiO₂ and was uniformly dispersed onto TiO₂ as the form of La₂O₃ particles with small size, which possibly made La dopant have a great inhibition on TiO₂ phase transformation; La dopant did not give rise to a new PL signal, but it could improve the intensity of PL spectra with a appropriate La content, which was possibly attributed to the increase in the content of surface oxygen vacancies and defects after doping La; La doped TiO₂ nanoparticles calcined at 600°C exhibited higher photocatalytic activity, indicating that 600°C was an appropriate calcination temperature. The order of photocatalytic activity of La doped TiO₂ samples with different La content was as following: 1>1.5>3>0.5>5>0 mol%, which was the same as the order of their PL intensity, namely, the stronger the PL intensity, the higher the photocatalytic activity, demonstrating that there were certain relationships between PL spectra and photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions.     

金@氧缺陷二氧化钛核壳纳米颗粒的制备及光催化产氢

通过水解TiCl_3在金纳米颗粒外表生长TiO_2,然后在Ar/H2气氛中高温煅烧成功地合成了核壳形貌的Au@H-TiO_2缺陷结构。采用XRD、TEM、XPS、UV-Vis测试方法对产物的物相结构、形貌及光吸收能力做了系统的分析。与不存在缺陷态的TiO_2和Au@A-TiO_2相比,Au@H-TiO_2表现出最高的产氢速率,这可以归因于其电荷分离效率的提高和电荷转移阻抗的降低,瞬态光电流测试以及电化学阻抗数据证实了这一结论。这些性能的改进可能与Au@H-TiO_2中的Ti~(3+)自掺杂和Au修饰有关。     

Nanocomposites of poly(l-lactide) and surface-grafted TiO2 nanoparticles: Synthesis and characterization

A new method of surface modification of TiO₂ nanoparticles by surface-grafting l-lactic acid oligomer was developed. The surface-grafting reaction was evaluated by Fourier transformation infrared (FTIR) and thermal gravimetric analysis (TGA). The results showed that l-lactic acid oligomer could be easily grafted onto the TiO₂ nanoparticles surface in the presence of stannous octanoate and the highest amount of grafted polymer was about 8.5% in weight. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) results showed that grafted TiO₂ (g-TiO₂) in chloroform or PLLA matrix approximated to uniform, while unmodified TiO₂ nanoparticles tended to aggregate. The tensile strength of this material was greatly improved by the addition of g-TiO₂ nanoparticles in poly(l-lactide) (PLLA) matrix. The tensile strength of the g-TiO₂/PLLA nanocomposite containing 5 wt.% of g-TiO₂ was 72 MPa, which was 23.1% higher than that of pure PLLA. Even though the incorporation of the TiO₂ nanoparticles into PLLA led to the deterioration of its elongation at break, the g-TiO₂/PLLA nanocomposite also exhibited better ductility than that of TiO₂/PLLA nanocomposite.     

Hierarchical chlorine-doped rutile TiO2 spherical clusters of nanorods: Large-scale synthesis and high photocatalytic activity

In this study, we report the synthesis of hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods photocatalyst on a large scale via a soft interface approach. This catalyst showed much higher photocatalytic activity than the famous commercial titania (Degussa P25) under visible light (λ>420 nm). The resulting sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy, ¹H solid magic-angle spinning nuclear magnetic resonance (MAS-NMR) and photoluminescence spectroscopy. On the basis of characterization results, we found that the doping of chlorine resulted in red shift of absorption and higher surface acidity as well as crystal defects in the photocatalyst, which were the reasons for high photocatalytic activity of chlorine-doped TiO₂ under visible light (λ>420 nm). These hierarchical chlorine-doped rutile TiO₂ spherical clusters of nanorods are very attractive in the fields of environmental pollutants removal and solar cell because of their easy separation and high activity.     

Tuning the aspect ratio of hydrothermally grown ZnO by choice of precursor

Variable aspect ratio (length/diameter), one dimensional ZnO nanostructures are synthesized by reacting Zn²⁺ precursor derived from Zn·Ac₂, Zn·Cl₂ and Zn·(NO₃)₂ under hydrothermal treatment. The growth mechanism illustrating the formation of self-assembling from individual ZnO nanoparticles to rod-like form is explained briefly. XRD reveals that the ZnO obtained from various zinc salts are pure, wurtzite structure, with crystalline hexagonal phase. The qualitative analysis of ZnO formation and morphology of ZnO nanoparticles are estimated from FESEM and TEM micrographs. Strong UV absorption corresponding to the recombination of electron-hole pair is observed and the blue shift absorption obeys the size confinement effect. The extent of absorption relatively varies when the morphology is changed from nano-bundles to individual rod-like ZnO. When electrons are excited at wavelength of 240 nm, a strong near band edge (NBE) emission and surface defects emission are observed in the PL spectra. The broader emission situated in the blue-green region of the visible spectrum, originating from surface oxygen defects, is not observed in ZnO derived from Zn·Ac₂.