The effect of surface modification by nitrogen plasma on photocatalytic degradation of polyvinyl chloride films

The solid-phase photocatalytic degradation of poly(vinyl chloride) (PVC) films was investigated under the ambient air in order to assess the feasibility of developing photodegradable polymers. Nitrogen plasma was used to modify PVC films to enhance the photocatalytic degradation of PVC with nano-sized anatase TiO₂. The plasma parameter varied in this study is discharge power from 30 to 120 W for a constant treatment time of 60 s and a constant gas pressure of 10 Pa. The photodegradation of the plasma-treated PVC-TiO₂ films was compared with that of pure PVC films and PVC-TiO₂ films performing weight loss monitoring, scanning electron microscopy (SEM) analysis, contact angle measurements, electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The wettability of the plasma-treated PVC is improved significantly. ESR revealed that the signal of radicals on the surface of the plasma-treated PVC film was enhanced after the treatment. Furthermore, the weight loss indicated that TiO₂ speeds up the photocatalytic degradation of PVC chains. The SEM image of the plasma-treated PVC-TiO₂ film showed a lot of crack on the film surface after irradiation. XPS indicated that the C and Cl atomic concentration reached minimum values on the surface of plasma-treated PVC-TiO₂ under identical photocatalytic condition. The experimental results reveal that plasma treatment can obviously enhance the photocatalytic degradation of PVC.     

Enhancement of photocatalytic degradation of polyethylene plastic with CuPc modified TiO2 photocatalyst under solar light irradiation

Solid-phase photocatalytic degradation of polyethylene (PE) plastic, one of the most common commercial plastic, over copper phthalocyanine (CuPc) modified TiO₂ (TiO₂/CuPc) photocatalyst was investigated in the ambient air under solar light irradiation. Higher PE weight loss rate, greater texture change; more amount of generated CO₂, which is the main product of the photocatalytic degradation of the composite PEC plastic can be achieved in the system of PE-(TiO₂/CuPc) in comparison with PE-TiO₂ system. The CuPc promoted charge separation of TiO₂ and enhanced the photocatalytic degradation of PE based on the analysis of surface photovoltage spectroscopy (SPS). During the photodegradation of PE plastic, the reactive oxygen species generated on TiO₂ or TiO₂/CuPc particle surfaces play important roles. The present study demonstrates that the combination of polymer plastic with TiO₂/CuPc composite photocatalyst in the form of thin film is a practical and useful way to photodegrade plastic contaminants under solar light irradiation.     

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.     

Low temperature preparation of anatase TiO2-activated carbon composite film

Anatase titania-activated carbon composite film was prepared by a simple method at low temperature (75 °C at most). The film was characterized by XRD, SEM and BET analysis. Results showed that the composite film was porous because it formed a nano-micro structure. The photocatalytic activity of the composite film was determined by degradation of 4-cholophenol (4-CP) under UV irradiation, and was compared to pure titania film and P25 film. It exhibited that the photocatalytic activity of composite film enhanced a lot. The recycle ability of the composite film was also investigated. The degradation ratio which was still higher than 85% after 5 cycles, decreased only 3% compared to the first cycle.     

Photocatalytic performance of ZnO:Fe array films under sunlight irradiation

ZnO:Fe array thin films were prepared by the hydrothermal method using the sol-gel grown film as a seed layer. The samples were characterized by X-ray diffraction (XRD), ultraviolet/visible absorption spectra (UV-vis) and scanning electron microscopy (SEM). The photocatalytic activities of the prepared samples were investigated for the photodegradation of methylene blue (MB) under sunlight irradiation. The results show that the lattice constant a and the cell volume of ZnO:Fe film increase due to the substitution of Fe for Zn. The absorption edge of Fe-doped ZnO displays a red shift with a significant absorption between 600 and 700 nm. The ZnO:Fe array film is composed of disk particles with uniformity and compactness. Doping Fe ions enhances the photodegradation rate of ZnO array film for MB. 1.5% Fe doped ZnO sample exhibits the highest activity under irradiation time of 4 h. Its degradation rate increases about 1.6 times compared to the undoped ZnO.     

Surface modification of polyethylene film by acrylamide graft and alcoholysis for improvement of antithrombogenicity

To improve antithrombogenicity of polyethylene (PE) films, the films pretreated by Ar plasma were radiated by ultraviolet light to initiate grafting polymerization with acrylamide (AAm) in absence of photo-initiator, then the AAm-grafted PE films (PE-g-AAm) were alcoholized with octadecyl alcohol. Effects of Ar plasma composite parameter (W/FM), pretreated time, AAm monomer concentration, and UV irradiation time on grafting rate were investigated systematically. AAm-grafted PE film and alcoholized PE film (PE-g-SAAm) were characterized by contact angle, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transfer infrared (ATR-FT-IR) spectroscopy and atomic force microscope (AFM), respectively. The results indicated that the moieties of AAm and stearyl were successively immobilized onto the PE surface. The platelet adhesion experiment showed that antithrombogenicity of the modified PE films was improved in comparison with PE films. The change in antithrombogenicity is attributed to the surface of the modified film in presence of tail-like structure which consists of polyacrylamide as spacer and stearyl as end groups.     

Synthesis and characterization of the efficient visible-light-induced photocatalyst AgBr and its photodegradation activity

AgBr photocatalysts were prepared with the 1-hexadecyl-3-methylimidazolium bromide ([C₁₆mim]Br) reactable ionic liquid at different temperatures by one-step hydrothermal method, in which the ionic liquid acted as a precursor and a template to control the size of AgBr crystal. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller (BET) surface area and diffuse reflectance spectroscopy (DRS). Methyl orange (MO) dye was chosen as a model pollutant to investigate the photocatalytic activity and the stability of the samples under visible light irradiation. The results indicated that the AgBr photocatalysts showed high efficiency in the degradation of MO under visible light irradiation. The kinetic property of the reaction followed the first-order reaction model. During the photocatalytic degradation reaction, AgBr was transformed to the Ag⁰/AgBr composite. However, the photocatalytic efficiency was still high and the photocatalytic activity was stable. The possible photocatalytic mechanism of the photocatalysts was also eventually proposed.     

Effect of N2 ion flux on the photocatalysis of nitrogen-doped titanium oxide films by electron-beam evaporation

Nitrogen-doped titanium oxide (TiO_xN_y) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N₂ flux modulated by the N₂ flow rate through an ion gun. The TiO_xN_y films have the absorption edge of TiO₂ red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO₂ can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO₂. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h⁻¹ and retaining 7° water contact angle on the surface under visible light illumination.     

Nitrogen doped TiO2 nanoparticles decorated on graphene sheets for photocatalysis applications

Nitrogen doped TiO₂ nanoparticles decorated on graphene sheets are successfully synthesized by a low-temperature hydrothermal method. The resulting GR-N/TiO₂ composites are characterized by X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-Ray photoelectron spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The optical properties are studied using UV–visible diffuse reflectance spectroscopy (DRS), which confirms that the spectral responses of the composite catalysts are extended to the visible-light region and show a significant reduction in band gap energy from 3.18 to 2.64 eV. Photoluminescence emission spectra verify that GR-N/TiO₂ composites possess better charge separation capability than pure TiO₂. The photocatalytic activity is tested by degradation of methyl orange (MO) dye under visible light irradiation. The results demonstrate that GR-N/TiO₂ composites can effectively photodegrade MO, showing an impressive photocatalytic enhancement over pure TiO₂. The dramatically enhanced activity of composite photocatalysts can be attributed to great adsorption of dyes, enhanced visible light absorption and efficient charge separation and transfer processes. This work may provide new insights into the design of novel composite photocatalysts system with efficient visible light activity.     

Characterization of N,C-codoped TiO2 films prepared by reactive DC magnetron sputtering

Titanium dioxide (TiO₂) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO₂ film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1s peak at 396.8 eV and a C 1s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO₂ film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO₂ catalysts.     

Investigation of photocatalytic reaction for thetitanium dioxide-phosphor composite

The present study examined the photocatalytic reaction of titanium dioxide (TiO₂)-coated, phosphor composite particles. Nanocrystalline TiO₂ layers were directly coated on the alkaline earth aluminate phosphor (CaAl₂O₄:Eu²⁺,Nd³⁺) particles by a sol-gel processing method and their photocatalytic reaction was analyzed according to the degradation of methylene blue aqueous solution under visible light irradiation. Compared with pure TiO₂, the TiO₂-coated phosphor powders showed a different photocatalytic mechanism and much faster photocatalytic reactivity under visible irradiation than that of pure TiO₂, which was almost negligible. The mechanism of the photocatalytic reactivity for the TiO₂-phosphor composite was discussed in terms of the energy band structure and phosphorescence. In addition, the TiO₂-coated phosphor powders were characterized by X-ray diffraction and transmission electron microscopy.     

A twice liquid arc discharge approach for synthesis of visible-light-active nanocrystalline Ag:ZnO photocatalyst

Ag:ZnO hybrid nanostructures were successfully prepared by a twice arc discharge method in liquid. The visible light photocatalytic activities were successfully demonstrated for the degradation of Rhodamine B (Rh. B), Methyl orange (MO), and Methylene blue (MB) as standard organic compounds under the irradiation of 90 W halogen light for 2 h. The Ag:ZnO nanostructures were characterized by X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and ultraviolet-visible absorption spectroscopy (UV-Vis). The results revealed that the Ag:ZnO nanostructures extended the light absorption spectrum toward the visible region and significantly enhanced the Rh. B photodegradation under visible light irradiation. 3 mM Ag:ZnO nanostructures exhibited highest photocatalytic efficiency. It has been confirmed that the Ag:ZnO nanostructures could be excited by visible light (E<3.3 eV). The significant enhancement in the Ag:ZnO nanostructures photocatalytic activity under visible light irradiation can be ascribed to the effect of physisorbed noble metal Ag by acting as electron traps in ZnO band gap. A mechanism for photocatalytic degradation of organic pollutant over Ag:ZnO photocatalyst was proposed based on our observations.     

The photocatalytic application and regeneration of anatase thin films with embedded commercial TiO2 particles deposited on glass microrods

Anatase thin films (<200 nm in thickness) embedding Degussa P25 TiO₂ were prepared by sol-gel method. TiO₂-anatase thin films were deposited on a fiberglass substrate and then ground to obtain glass microrods containing the composite films. The film structure was characterized using Raman spectroscopy, atomic absorption and UV-vis spectrophotometry, and atomic force microscopy. The photocatalytic activity of the composite films, calcined at 450 °C, and the regeneration of the activity under the same experimental conditions, were assessed using gas chromatography to study the photodegradation of phenol, an industrial pollutant, in water under 365 nm irradiation. The film with 15.0 wt.% of P25 TiO₂ was found to be more photoactive (54 ppm of degraded phenol at 6 h of illumination) than the other ones.     

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.     

Aerosol-assisted flow synthesis of WxTi1−xO2 solid solution spheres with enhanced photocatalytic activity

In this paper, W_xTi_1−xO₂ solid solutions (x = 0.000, 0.005, 0.010, 0.015, and 0.020) microspheres were synthesized with an aerosol-assisted flow synthesis method. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption, UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the as-prepared catalysts were measured by the degradation of rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). All the solid solutions exhibited higher photocatalytic activities than pure TiO₂ and the W_0.015Ti_0.985O₂ solid solution possessed the highest photocatalytic activity. The degradation constant of RhB on W_0.015Ti_0.985O₂ solid solution catalyst was about 15 times of that of the pure TiO₂ and 25 times of that of Degussa P25, respectively. This study provides an effective method to prepare visible light photocatalysts on a large scale.     

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.     

Preparation, characterization and photocatalytic activity of polycrystalline Bi2O3/SrTiO3 composite powders

Bi₂O₃/SrTiO₃ composite powders have been prepared and their photocatalytic activities were investigated by photooxidation of methanol. These powders were characterized by UV-Visible diffuse reflectance spectra, SEM and X-ray diffraction (XRD). The results revealed that all the Bi₂O₃/SrTiO₃ composite powders exhibited higher photocatalytic activity than pure SrTiO₃, Bi₂O₃ and TiO₂ (P25) under visible light irradiation (λ>440 nm). The effects of the Bi₂O₃ contents on the photocatalytic activities of the composite powders were examined, the photocatalytic activities increased with the content of Bi₂O₃ increasing to a maximum of 83% and then decreased under visible light irradiation. The effects of the calcination temperatures on the photocatalytic activities of the composite powders were also investigated.     

Efficient visible light-induced degradation of phenol on N-doped anatase TiO2 with large surface area and high crystallinity

The N-doped anatase TiO₂ photocatalysts were prepared via solvothermal and ethylenediamine reflux treatment, followed by the sequential calcination in air and NH₃/N₂ atmosphere. The resulting photocatalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and UV-vis diffuse reflectance spectra. The results revealed that the prepared N-doped anatase TiO₂ had characteristics of small crystallite size, large surface area, high crystallinity and visible light response. The prepared N-doped anatase TiO₂ photocatalysts showed much higher photocatalytic activity than N-doped Degussa P25 for the degradation of phenol under both ultraviolet and visible light irradiation, owing to more highly oxidizing hydroxyl radical which was the main oxidative species responsible for the degradation of phenol.     

Chitosan hydrogel films as a template for mild biosynthesis of CdS quantum dots with highly efficient photocatalytic activity

Cadmium sulfide (CdS) semiconducting quantum dots (QDs) were prepared using in situ synthesizing method in crosslinked chitosan hydrogel films under relative mild experimental conditions and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The experimental results confirmed that crosslinked chitosan hydrogel films provided a confined matrix for CdS QDs growth in uniform size through chelation and electrostation between cadmium ions and amino groups in chitosan chains. The CdS QDs/chitosan composite films exhibited a highly efficient photocatalytic activity for decolorization of methyl orange (MO) solution under visible light irradiation. The good linearity relationship between ln (C₀/C_i) and irradiation time (t) indicated that the decolorization of MO dye under present experimental conditions followed pseudo-first-order kinetics. These results suggested that CdS QDs/chitosan composite films were suitable material for potential application in decolorization of organic dye pollutants under visible light irradiation.     

Carbon quantum dots supported ZnO sphere based photocatalyst for dye degradation application

A Carbon quantum dots supported ZnO hollow Sphere (ZnO/C-dots) were synthesized through a solvothermal method using polyethylene glycol 400 (PEG 400) as a solvent. The phase and crystal structure of as-prepared ZnO/C-dots photocatalyst were characterized by powder X-ray diffraction (XRD). The surface morphology and size of the composite were analyzed using field emission scanning microscopy (FE-SEM). The optical properties of the as-prepared nanocomposites were examined using UV–visible (UV–Vis) spectrometer. The photocatalytic activity of pure ZnO and ZnO/C-dots nanocomposites were evaluated by the degradation of methylene blue (MB) under UV–Visible light irradiation. The ZnO/C-dots nanocomposites exhibited maximum photocatalytic MB dye degradation efficiency of 96% which is much higher that the pure ZnO (63%). The enhanced photocatalytic activity of ZnO/C-dots is due to the extended light absorption in the visible region and suppressed photoexcited electron-hole pair recombination rate. Moreover, the activity of photocatalyst after five cycles exhibits high stability, which is vital for the sustainable photocatalytic procedures. It is concluded that the prepared ZnO/C-dots composite have low cost, good stability and has a great potential application for Photocatalytic dye degradation.