Cu2O/Ag复合物的合成及SERS原位分析其可见光催化降解活性

A multifunctional Cu₂O/Ag micro-nanocomposite, which has the characteristics of high catalytic activities under the visible light and high surface-enhanced Raman scattering (SERS) activity, was fabricated via a facile method and employed for the in situ SERS monitoring of the photocatalytic degradation reaction of crystal violet. Through the variation of the AgNO₃ concentration, Ag content on the Cu₂O template can be controllably tuned, which has great influence on the SERS effect. The results indicate that Ag nanoparticles form on the Cu₂O nanoframes to obtain the Cu₂O/Ag nanocomposite, which can act as an excellent bifunctional platform for in situ monitoring of photocatalytic degradation of organic pollutions by SERS.     

Bifunctional photocatalysis of TiO2/Cu2O composite under visible light: Ti in organic pollutant degradation and water splitting

Photocatalytic experiment results under visible light demonstrate that both TiO₂ and Cu₂O have low activity for brilliant red X-3B degradation and neither can produce H₂ from water splitting. In comparison, TiO₂/Cu₂O composite can do the both efficiently. Further investigation shows that the formation of Ti³⁺ under visible light has great contribution. The mechanism of photocatalytic reaction is proposed based on energy band theory and experimental results. The photogenerated electrons from Cu₂O were captured by Ti⁴⁺ ions in TiO₂ and Ti⁴⁺ ions were further reduced to Ti³⁺ ions. Thus, the photogenerated electrons were stored in Ti³⁺ ions as the form of energy. These electrons trapped in Ti³⁺ can be released if a suitable electron acceptor is present. So, the electrons can be transferred to the interface between the composite and solution to participate in photocatalytic reaction. XPS spectra of TiO₂/Cu₂O composite before and after visible light irradiation were carried out and provided evidence for the presence of Ti³⁺. The image of high-resolution transmission electron microscopy demonstrates that TiO₂ combines with Cu₂O tightly. So, the photogenerated electrons can be transferred from Cu₂O to TiO₂.     

Photocatalytic performance of Cu2O and Ag/Cu2O composite octahedra prepared by a propanetriol-reduced process

Cu₂O and Ag/Cu₂O composite octahedra were synthesized via a hydrothermal reaction of CuAc₂ with urea in H₂O–propanetriol binary solution by adjusting the quantity of AgNO₃ at 180 °C for 10 h. The influence of reaction temperature and time on the morphology and phase of the products was investigated, and a possible growth mechanism of Cu₂O octahedron was also proposed. The photocatalytic activities of the as-prepared Cu₂O and Ag/Cu₂O octahedra for the degradation of methyl orange aqueous solution were studied. The results show that they are effective photocatalysts for the degradation of methyl orange, and the photocatalytic ability of Ag/Cu₂O composite is stronger than that of Cu₂O octahedra, which are expected to be useful in the treatment of wastewaters.     

Structural, photochemical and photocatalytic properties of zirconium oxide doped TiO2 nanocrystallites

Composite photocatalysts composed of TiO₂ and ZrO₂ have been prepared via the sol-gel method. The as-prepared nanocomposites are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectrometry and fluorescence emission spectra. The results shows that TiO₂/ZrO₂ nanocomposites are composed of mainly anatase titania and tetragonal ZrO₂. Incorporating TiO₂ particles with ZrO₂ plays an important role in promoting the formation of nanoparticles with an anatase structure and leads to decreased fluorescence emission intensity. Most of the TiO₂/ZrO₂ nanocomposites exhibited comparable photocatalytic activity compared with commercial TiO₂ for the degradation aqueous methyl orange (MO) under ultraviolet irradiation, while the composite with Zr/Ti mass ratio of 15.2% shows the highest photocatalytic performances. Furthermore, the as-prepared nanocomposites can be reused with little photocatalytic activity loss. Without any further treatment besides rinsing, the photocatalytic activity of TiO₂/ZrO₂ (15.2%) composites is still higher than after five-cycle utilization.     

Photo(electro)catalytic Activity of Cu-Modified TiO2 Nanorod Array Thin Films under Visible Light Irradiation

In the present study, a two-step method was applied to synthesise Cu²⁺-modified TiO₂ nanorod array thin films for photocatalytic processes. TiO₂ nanorod array thin films were synthesised by a hydrothermal method and then modified with an ultrasonic-assisted sequential cation adsorption method. The samples were characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and inductively coupled plasma mass spectroscopy (ICP-MS) analysis. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry and Mott–Schottky analysis; photocatalytic activities were tested by methylene blue degradation under visible light. The photocurrent density of the TiO₂/FTO sample modified with 50 mM Cu²⁺ solution was 26 times higher than that of the unmodified TiO₂/FTO sample. Additionally, methylene blue degradation efficiency under visible light was increased 40% with respect to the efficiency of the unmodified sample. The mechanism of the photocatalytic activity enhancement of Cu²⁺-modified TiO₂ nanorod films was discussed.     

The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes

CdS/TiO₂ nanocomposites were prepared via a simple wet chemical method, and characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their ability to degrade Acid Rhodamine B was investigated under visible light irradiation. The results indicate that CdS/TiO₂ nanocomposite with a mass ratio of 4:1(TiO₂:CdS) showed high photocatalytic activity and the CdS loaded on TiO₂ nanotube surface exhibited a hexagonal phase. The dispersion of CdS on TiO₂ nanotube surface had an important effect on the degradation efficiency of pollutant, which provides a strategy for practical industry application.     

Synthesis and characterization of Ag/BiVO4 composite photocatalyst

Ag/BiVO₄ composite photocatalysts were hydrothermal synthesized and characterized by XRD, SEM, XPS and DRS techniques. Their photocatalytic activities were determined by oxidative decomposition of methyl orange in aqueous solution under visible light irradiation. It revealed that the doped Ag species greatly improved the visible light absorption abilities and morphologies of the composites, and thus lead to enhanced photocatalytic activities compared with that of the pure BiVO₄.     

Photocatalytic properties of porous C-doped TiO2 and Ag/C-doped TiO2 nanomaterials by eggshell membrane templating

Porous organic carbon-doped titania (C-TiO₂) nanomaterials and their composites with Ag nanoparticles (Ag/C-TiO₂) were synthesized by an eggshell membrane templating method, and their structural and photocatalytic properties were systematically characterized. These nanomaterials, exhibiting a macroscopic morphology of a thin film, are composed of interwoven tubes, and the tube wall consists of nanocrystals. The doped organic carbon was composed of the active carbon and carbonate species, which could form a layer around the surface of TiO₂ nanoparticles, while the silver was incorporated into Ag/C-TiO₂ composites as separated Ag nanoparticles. The degradation of methylene blue under visible light irradiation was employed to evaluate the photocatalytic activity of these as-prepared TiO₂-based materials. Both C-TiO₂ and Ag/C-TiO₂ nanomaterials showed higher photocatalytic activity than pure TiO₂ material–commercial Degussa P25. These results can be accounted for the coupling effect of the incorporation of carbon species and Ag nanoparticles.     

Synergetic Photocatalytic Nanostructures Based on Au/TiO2/Reduced Graphene Oxide for Efficient Degradation of Organic Pollutants

Recently, there is crucial interest in the design and fabrication of nanocatalysts for efficient decomposition of organic pollutants in wastewater using visible light. This work reports the assembling fabrication of synergetic photocatalytic Au/TiO₂/RGO nanostructures by utilizing the reduced graphene oxide (RGO) as substrate material and efficient separator for electrons and holes. The Au/TiO₂ nanostructures with a ≈7 nm TiO₂ particles size are dispersed uniformly on RGO nanosheets. UV–vis diffuse reflectance spectroscopy verifies that Au/TiO₂/RGO nanocomposites show strong absorption of visible light. The degradation efficiency after 1 h for hydroquinone under visible light and UV light is ≈77% and ≈90%, respectively. Under visible light, the calculated apparent rates (k ) of the Au/TiO₂/RGO nanocomposites are 0.0112 and 0.0174 min^?1 for decomposition of methylene blue and hydroquinone. That are five times greater than that of bare TiO₂. The high photocatalytic activity is mainly attributed to the synergy between RGO and Au/TiO₂ nanostructure. The strategy of composite nanostructures assembling on RGO is ensured to have a great practicable potential for the designing of high efficient multielement composite nanoparticles catalysts.     

Structure and optical properties of Ag/CeO2 nanocomposites

Silver/ceria (Ag/CeO₂) nanocomposites were prepared from Ce(NO₃)₃?6H₂O, AgNO₃, and NH₄OH with different molar ratios through a hydrothermal process, and then were completed by carrying out the precursors calcining at 750 °C for 2 h under air atmosphere. Below 1 % of Ag concentration in Ag/CeO₂ nanocomposites, the Ag crystalline structure does not appear. XRD and TEM results show evidence of two different effects (the agglomeration and the barrier effects) governing the process of crystal growth. HR-TEM image and EDX elemental analysis of the Ag/CeO₂ nanocomposite confirmed that isolated Ag nanocrystals are dispersed in the CeO₂ matrix. The red shifts are attributed to the quantum confinement effect and the valence change of the Ce⁺ ions. Ag nanoparticles can help to improve the absorption of visible light, enhancing the absorption intensity of Ag/CeO₂ nanocomposite. These results are of great significance for the control of microstructure, crystallinity, and applications for the development of nanocomposite materials.     

Urchin-like CdS/ZrO2 nanocomposite prepared by microwave-assisted hydrothermal combined with ion-exchange and its multimode photocatalytic activity

A series of urchin-like CdS/ZrO₂ nanocomposites with different mole ratios of Cd/Zr were prepared by a two-step method combining the microwave-assisted hydrothermal and ion exchange methods. The products were characterized by X-ray diffraction, ultraviolet–visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and N₂ adsorption–desorption measurements. The results of the study revealed that the CdS/ZrO₂ nanocomposites had mixed phases of tetragonal ZrO₂ and hexagonal CdS. Moreover, the samples prepared by the microwave-assisted hydrothermal method possessed the urchin-like structure with a surface composed of protrude-like nanoparticles in large quantities. The absorption in the visible region changed slightly with increasing mole ratio of Cd/Zr. Moreover, compared to the nanocomposites prepared by the conventional heating, the nanocomposites prepared by the microwave-assisted hydrothermal synthesis showed significantly different Brunauer–Emmett–Teller values, and the urchin-like CdS/ZrO₂ structures were obtained. The photocatalytic degradation of methyl orange under ultraviolet (UV) light irradiation indicated that the photocatalytic activity of the CdS/ZrO₂ nanocomposite with CdS/ZrO₂ molar ratio of 30 % was higher than those of CdS, ZrO₂, and other different ratios of CdS/ZrO₂ nanocomposites. Moreover, under UV light, visible light, and microwave-assisted multimode photocatalytic degradation, the urchin-like CdS/ZrO₂ nanocomposites significantly affected the photodegradation of various dyes. To understand the possible reaction mechanism of the photocatalysis by the CdS/ZrO₂ nanocomposites, a series of controlled experiments were performed, and the stability and reusability of the CdS/ZrO₂ nanocomposites were further investigated by the photocatalytic reaction.     

Fast and selective Cu2O nanorod growth into anodic alumina templates via electrodeposition

The fast and selective growth of cuprous oxide (Cu₂O) nanorods into anodic aluminum oxide (AAO) templates is achieved under optimized alkaline conditions via electrochemical deposition. The growth rate of Cu₂O nanorods at room temperature reached 360 nm/min, the fastest rate reported to date. The synthesis of Cu₂O nanorods by applying a constant current by using Cu₂O nanotubes as a transition state is extensively discussed; a Pt pottery-shaped layer played a key role as a seed layer for the fast Cu₂O growth. We report here the existence of regions of nanostructured Cu₂O based on our studies and previous relevant works, which include potential-pH curves for Cu²⁺-lactate solutions.     

Evaluating the electric property of different crystal faces and enhancing the Raman scattering of Cu2O microcrystal by depositing Ag on the surface

The surface electric property of Cu₂O microcrystal affects the interaction of facets with substance in the aqueous solution, and hence plays a key role in determining the photocatalytic activity. In this paper, the capability of Cu₂O microcrystals with exclusive {111}, {110} or both lattice surfaces in reducing Ag⁺ to Ag⁰ were investigated. Ag particles selectively deposited on {111} surfaces of Cu₂O, while not on {110} surfaces. The different behaviors of the two surfaces are mainly attributed to their different electric properties: negatively-charged {111} surfaces absorb Ag⁺ ions while positively-charged {110} surfaces repel them. Raman scattering of Cu₂O {111} surfaces was enhanced by the photo-deposition of Ag particles.     

Study on the photocatalytic activity of K2La2Ti3O10 doped with zinc(Zn)

The layered perovskite type oxides, K₂La₂Ti₃O₁₀ and zinc(Zn)-doped K₂La₂Ti₃O₁₀ were prepared by sol-gel method and were characterized by power X-ray diffraction, UV-vis diffuse reflectance and X-ray photoelectron spectroscopy. The photocatalytic activity for water splitting of the catalyst powders was investigated with I⁻ as electron donor under ultraviolet and visible light irradiation respectively. The electronic structure of the powders has been analyzed by the first principles calculation, which reveals the photo responses in the visible region and the improvement of the photocatalytic activity of K₂La₂Ti₃O₁₀. Conclusions were made that zinc(Zn)-doped K₂La₂Ti₃O₁₀ exhibited higher reactivity for hydrogen production. When I⁻ was used as electron donor, the optimum doping concentration of zinc(Zn) was found to be 0.015:1 (n_Zn:n_Ti). The average hydrogen production rates were 126.6 μmol/(gcat h) under ultraviolet irradiation and 55.5 μmol/(gcat h) under visible light irradiation which were raised by 131% and 251% compared with undoped K₂La₂Ti₃O₁₀ photocatalyst, respectively.     

Design and fabrication of a TiO2/nano-silicon composite visible light photocatalyst

Nano-silicon (nc-Si) was utilized as the charges generator to promote the photocatalytic and super-hydrophilic reactivity of TiO₂ film under visible light irradiation. The photocatalytic ability of TiO₂/nc-Si composite photocatalyst was evaluated by a set of experiments to photodecompose 100 ppm methylene blue (MB) in aqueous solution. And the super-hydrophilic property was characterized by measuring the water droplet contacts angle, under visible light irradiation in atmospheric air and at room temperature. Under 100 mW/cm² visible light irradiation, the droplet contact angles were reduced to 0° within 4 h with nc-Si charge generator. Additionally, the rate constant of MB photo-degradation was promoted 6.6 times.     

Shape evolution, photoluminescence and degradation properties of novel Cu2O micro/nanostructures

Three kinds of novel cuprous oxide (Cu₂O) micro/nanostructures are synthesized via a facile template-free hydrothermal method. Two factors are critical for the growth process of typical samples: the concentration of copper ions (Cu(II)) and the addition of Polyvinylpyrrolidone (PVP) as surfactant. It is found that the application of ethanol as solvent speeds up the reduction rate of Cu(II), and it promotes the aggregating of Cu₂O nanocrystals at the preliminary stage to form irregular spherical structures. Photoluminescence (PL) properties of the three kinds of samples and their photocatalytic activities for degradation of Methyl Orange (MO) are also measured. The sample with higher concentration of copper vacancy (V _Cu) defects has better photocatalytic ability, indicating that besides the morphology of Cu₂O nano/microcrystals, the defects in crystalline structures can also influence their electrical characteristics, and thus change their photocatalytic activity. This provides a potential method to improve the photocatalytic performances of Cu₂O crystals.     

铈和磷钨酸共掺杂纳米二氧化钛中空纤维的制备及其光催化活性

以棉花纤维为模板,以钛酸四正丁酯、硝酸铈铵和磷钨酸为原料采用模板法制备了一系列铈和磷钨酸共掺杂的、具有中空纤维结构的TiO₂光催化材料, 利用扫描电子显微镜、X射线衍射、BET和紫外-可见光谱等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征. 以苯酚溶液的光催化降解为模型反应,考察了不同掺杂量的样品在紫外和可见光下的光催化性能. 结果表明,用模板法制备的TiO₂纤维材料具有中空结构,共掺杂的TiO₂纤维在紫外和可见光条件下较纯TiO₂纤维和单掺杂TiO₂纤维对苯酚溶液具有更好的光催化降解效果, 且铈和磷钨酸的掺杂量显著影响该纤维材料的催化性能;当铈掺杂量为0.3mol%和磷钨酸掺杂量为2mol%,在500 oC焙烧2 h所得中空纤维材料的催化性能最佳,4 h即可使苯酚溶液的降解率达98.5%;重复使用4次仍可使苯酚溶液的降解率保持在87%以上,且该催化剂材料易于离心分离去除.     

Combination of ultrasound-treated 2D g-C3N4 with Ag/black TiO2 nanostructure for improved photocatalysis

Herein, nanosheets of g-C₃N₄ (CN), prepared using a green ultrasonication process under various conditions, were combined with Ag/black TiO₂ nanocomposites (AgBT) to create two-dimensional (2D) CN/Ag/black TiO₂ tri-composites (CNAgBT). The thickness of the CN sheets varied with the ultrasonication conditions. The CNAgBT sample prepared using ultrasound-treated CN exhibited the highest average photocatalytic efficiencies for the degradation of two model pollutants, followed in decreasing order by AgBT, black TiO₂ (BT), sheet CN, bulk CN, and TiO₂. The order of pollutant degradation efficiencies by the photocatalysts was consistent with that of the charge carrier separation efficiencies. The degradation efficiency of the CNAgBT increased as the CN-to-AgBT ratio increased from 0.05 to 0.1, but decreased gradually for higher ratios between 0.15 and 0.20, indicating a lower optimal CN-to-AgBT ratio. A plausible photocatalytic degradation mechanism for the CNAgBT nanocomposites was proposed. Additionally, CNAgBT with a CN-to-AgBT ratio of 0.1 displayed a higher hydrogen generation rate with a maximum value of 21.5 mmol g⁻¹ over 5 h than those of the AgBT and BT. Overall, the CNAgBT prepared using ultrasonication-treated CNs showed enhanced photocatalytic performance for both pollutant degradation and hydrogen generation.     

Efficient one-pot synthesis of Ag nanoparticles loaded on N-doped multiphase TiO2 hollow nanorod arrays with enhanced photocatalytic activity

The simultaneous Ag loaded and N-doped TiO₂ hollow nanorod arrays with various contents of silver (Ag/N-THNAs) were successfully synthesized on glass substrates by one-pot liquid phase deposition (LPD) method using ZnO nanorod arrays as template. The catalysts were characterized by Raman spectrum, field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscope (HRTEM), ultraviolet-vis (UV-vis) absorption spectrum and X-ray photoelectron spectroscopy (XPS). The results suggest that AgNO₃ additive in the precursor solutions not only can promote the anatase-to-rutile phase transition, but also influence the amount of N doping in the samples. The photocatalytic activity of all the samples was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The sample exhibited the highest photocatalytic activity under UV light illumination when the AgNO₃ concentration in the precursor solution was 0.03 M, due to Ag nanoparticles acting as electron sinks; When the AgNO₃ concentration was 0.07 M, the sample performed best under visible light illumination, attributed to the synergetic effects of Ag loading, N doping, and the multiphase structure (anatase/rutile).     

Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities

Novel Pd/InVO₄-TiO₂ thin films with visible light photocatalytic activity were synthesized from the Pd and InVO₂ co-doped TiO₂ sol via sol-gel method. The photocatalytic activities of Pd/InVO₄-TiO₂ thin films were investigated based on the oxidative decomposition of methyl orange in aqueous solution. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results indicate that the Pd/InVO₄-TiO₂ thin films are compact, uniform and consist of sphere nanoparticles with diameters about 80-100 nm. The UV-vis spectra show that the Pd/InVO₄-TiO₂ thin films extend the light absorption spectrum toward the visible region. XPS results reveal that doped Pd exist in the form of metallic palladium. The photocatalytic experiments demonstrate that Pd doping can effectively enhance the photocatalytic activities of InVO₄-TiO₂ thin films in decomposition of aqueous methyl orange under visible light irradiation. It has been confirmed that Pd/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV) due to the existence of the Pd and InVO₄ doped in the films.