Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

Synthesis and Studies of the Visible‐Light Photocatalytic Properties of Near‐Monodisperse Bi‐Doped TiO2 Nanospheres

Near‐monodisperse Bi‐doped anatase TiO₂ nanospheres with almost uniform diameters in the range of 117 to 87 nm were prepared simply by introducing different amounts of bismuth nitrate pentahydrate into the reaction system and subsequent calcinations. X‐ray diffraction, UV‐visible diffuse reflectance spectra, and X‐ray photoelectron spectroscopy confirm that the doped ions substitute some of the lattice titanium atoms, and furthermore, Bi³⁺ and Bi⁴⁺ ions coexist. All the Bi‐doped TiO₂ samples show much better photocatalytic activity than pure TiO₂ in the degradation of rhodamine B (RhB) under the irradiation of visible light (λ>420 nm), and, interestingly, it was found that the degradation mechanism is different from the conventional one, which has already been reported elsewhere. The detailed mechanism is discussed in this article.     

Preparation of Ce‐doped TiO2 Hollow Fibers and Their Photocatalytic Degradation Properties for Dye Compound

Cerium‐doped titanium dioxide (TiO₂) with a hollow fiber structure was successfully prepared using ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fiber as the template. The effects of cerium (Ce)‐doping on the crystallite sizes, crystal pattern, and optical property of the prepared catalysts were investigated by means of techniques such as scanning electron microscopy (SEM), X‐ray diffraction (XRD), BET surface area, and UV‐vis diffuse absorption spectroscopy. SEM observation showed that the prepared TiO₂ fibers possessed fibrous shape inherited from the cotton fiber and had a hollow structure. As confirmed by XRD and UV‐vis diffuse absorption spectroscopy examinations, Ce‐doping restrained the growth of grain size and extended the photoabsorption edge of TiO₂ hollow fiber into the visible light region. The present photocatalyst showed higher photocatalytic reactivity in photodegradation of highly concentrated methylene blue (MB) solutions than pure TiO₂ under UV and visible light, and the amount of Ce‐doped significantly affected the catalytic property. In the experiment condition, the photocatalytic activity of 0.5 mol% Ce‐doped TiO₂ fiber was optimal of all the prepared samples. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed. The material was easily removed by centrifugal separation. Therefore, using the template method and by doping with cerium, TiO₂ may hopefully become a low‐energy consuming, high activity and green environmentally friendly catalytic material.     

Template‐free Fabrication of Hierarchical Macro‐/mesoporous N‐doped TiO2/graphene Oxide Composites with Enhanced Visible‐light Photocatalytic Activity

Hierarchical macro‐/mesoporous N‐doped TiO₂/graphene oxide (N‐TiO₂/GO) composites were prepared without using templates by the simple dropwise addition mixed solution of tetrabutyl titanate and ethanol containg graphene oxide (GO) to the ammonia solution, and then calcined at 350 °C. The as‐prepared samples were characterized by scanning electron microscopy (SEM), Brunauer‐Emmett‐Teller (BET) surface area, X‐ray diffraction (XRD), Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and UV‐Vis absorption spectroscopy. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange in an aqueous solution under visible‐light irradiation. The results show that N‐TiO₂/GO composites exhibited enhanced photocatalytic activity. GO content exhibited an obvious influence on photocatalytic performance, and the optimal GO addition content was 1 wt%. The enhanced photocatalytic activity could be attributed to the synergetic effects of three factors including the improved visible light absorption, the hierarchical macro‐mesoporous structure, and the efficient charge separation by GO.     

One‐Pot Synthesis of Nitrogen‐doped TiO2 Nanowires with Enhanced Photocurrent Generation

A nitrogen‐doped TiO₂ (N‐TiO₂) nanowire film was synthesized via a one‐pot hydrothermal method using triethylamine as nitrogen source. The effect of the concentration of the triethylamine on the films was evaluated. In addition, the N‐TiO₂ nanowires were characterized using field‐emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and ultraviolet–visible spectroscopy. A 3.2× enhancement of the photocurrent for N‐TiO₂ (0.6) was achieved over the as‐prepared TiO₂ nanowire, under AM1.5G solar illumination. This was due to nitrogen doping, which could narrow the bandgap of titania to extend the adsorption of the catalyst to the visible light region.     

Samarium and Nitrogen Co‐Doped Bi2WO6 Photocatalysts: Synergistic Effect of Sm3+/Sm2+ Redox Centers and N‐Doped Level for Enhancing Visible‐Light Photocatalytic Activity

Samarium and nitrogen co‐doped Bi₂WO₆ nanosheets were successfully synthesized by using a hydrothermal method. The crystal structures, morphology, elemental compositions, and optical properties of the prepared samples were investigated. The incorporation of samarium and nitrogen ions into Bi₂WO₆ was proved by X‐ray diffraction, energy dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy. UV/Vis diffuse reflectance spectroscopy indicated that the samarium and nitrogen co‐doped Bi₂WO₆ possessed strong visible‐light absorption. Remarkably, the samarium and nitrogen co‐doped Bi₂WO₆ exhibited higher photocatalytic activity than single‐doped and pure Bi₂WO₆ under visible‐light irradiation. Radical trapping experiments indicated that holes (h⁺) and superoxide radicals ( ^. O₂^?) were the main active species. The results of photoluminescence spectroscopy and photocurrent measurements demonstrated that the recombination rate of the photogenerated electrons and holes pairs was greatly depressed. The enhanced activity was attributed to the synergistic effect of the in‐built Sm³⁺/Sm²⁺ redox pair centers and the N‐doped level. The mechanism of the excellent photocatalytic activity of Sm‐N‐Bi₂WO₆ is also discussed.     

Electrochemical Fabrication and Properties of Highly Ordered Fe‐Doped TiO2 Nanotubes

Highly‐ordered Fe‐doped TiO₂ nanotubes (TiO₂nts) were fabricated by anodization of co‐sputtered Ti–Fe thin films in a glycerol electrolyte containing NH₄F. The as‐sputtered Ti–Fe thin films correspond to a solid solution of Ti and Fe according to X‐ray diffraction. The Fe‐doped TiO₂nts were studied in terms of composition, morphology and structure. The characterization included scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, UV/Vis spectroscopy, X‐ray photoelectron spectroscopy and Mott–Schottky analysis. As a result of the Fe doping, an indirect bandgap of 3.0 eV was estimated using Tauc’s plot, and this substantial red‐shift extends its photoresponse to visible light. From the Mott–Schottky analysis, the flat‐band potential (E_fb) and the charge carrier concentration (N_D) were determined to be ?0.95 V vs Ag/AgCl and 5.0 ×10¹⁹ cm^?3 respectively for the Fe‐doped TiO₂nts, whilst for the undoped TiO₂nts, E_fb of ?0.85 V vs Ag/AgCl and N_D of 6.5×10¹⁹ cm^?3 were obtained.     

Improving the Photocatalytic Activity of Modified Anatase TiO2 with Different Concentrations of Aluminum under Visible Light: Mechanistic Survey

Visible light‐driven Al‐doped TiO₂ with different aluminum contents (2, 5 and 10 mol%) were synthesized via a facile sol–gel method. Fourier transform infrared (FTIR), UV‐visible diffuse reflectance, energy dispersive X‐ray (EDX) spectroscopy as well as X‐ray diffraction (XRD), X‐ray fluorescence (XRF) and scanning electron microscopy (SEM) methods were used for the characterization of the obtained nanoparticles. The photocatalytic performance of the samples was evaluated by the degradation of rhodamine B (RhB) under visible light irradiation. The yield of the degradation RhB was estimated to be 71%, 89%, 65% and 56%, for the bare TiO₂, 2%, 5% and 10% Al‐doped TiO₂, respectively. It was found that 2 mol% of Al‐doped TiO₂ shows the best photocatalytic performance. In low concentration of dopant, separation of photogenerated electron–hole pairs promoted, and subsequently, the degradation efficiency increased. It was proposed that the degradation of RhB by 2 mol% Al‐doped TiO₂ photocatalyst follows both N‐deethylation and chromophore cleavage mechanisms, while the N‐deethylation still predominated over cleavage of dye chromophore structure. The key role of hydroxyl radicals in RhB degradation was verified by the effects of scavengers. In addition, the photocatalyst can be reused for three runs without any significant loss of its catalytic activity.     

Synthesis and Modification of Zn‐doped TiO2 Nanoparticles for the Photocatalytic Degradation of Tetracycline

The synthesis of Zn‐doped TiO₂ nanoparticles by solgel method was investigated in this study, as well as its modification by H₂O₂. The catalyst was characterized by transmission electron microscopy, X‐ray diffraction, Brunauer–Emmett–Teller, UV–visible reflectance spectra and X‐ray photoelectron spectroscopy (XPS). The results indicated that doping Zn into TiO₂ nanoparticles could inhibit the transformation from anatase phase to rutile phase. Zn existed as the second valence oxidation state in the Zn‐doped TiO₂. Zn‐doped TiO₂ that was synthesized by 5% Zn doping at 450°C exhibited the best photocatalytic activity. Then, the H₂O₂ modification further enhanced the photocatalytic activity. Zn doping and H₂O₂ modifying narrowed the band gap and efficiently increased the optical absorption in visible region. The optimal degradation rate of tetracycline by Zn‐doped TiO₂ and H₂O₂ modified Zn‐doped TiO₂ was 85.27% and 88.14%. Peroxide groups were detected in XPS analysis of H₂O₂ modified Zn‐doped TiO₂, favoring the adsorption of visible light. Furthermore, Zn‐doped TiO₂ modified by H₂O₂ had relatively good reusability, exhibiting a potential practical application for tetracycline's photocatalytic degradation.     

Tungsten and nitrogen co‐doped TiO2 nanobelts with significant visible light photoactivity

Tungsten and nitrogen co‐doped TiO₂ nanobelts (W/N‐TNBs) have been successfully synthesized via 1‐step hydrothermal method. The structure, morphology, and composition of prepared samples were characterized by X‐ray diffraction, scanning electron microscopy, and X‐ray photoelectron spectroscopy, respectively. The prominent phase of all as‐prepared samples is anatase crystal. For samples with N doping, new energy states can be introduced on top of O 2p states which reduced the band gap by 1.1 eV. The reduced band gap leads to efficient visible light activity. The 3%‐W/N‐TNBs were found to exhibit the highest activity. The photocatalytic performance of 3%‐W/N‐TNBs under visible light is about 4.8 times than that of pure TiO₂ nanobelts, which emphasizes the synergistic effect of W and N co‐doping for effectively inhibiting the recombination of photogenerated electrons and holes. In addition, our results testify the different redox potentials of the photoelectrons at different final states.     

Photo Catalytic Degradation of Azo Dyes over Mn2+ Doped TiO2 Catalyst under UV/Solar Light:An Insight to the Route of Electron Transfer in the Mixed Phase of Anatase and Rutile

Mn²⁺ ion was doped into the TiO₂ matrix and its photocatalytic activity was evaluated for the degradation of a mono azo dye methyl orange (MO) and a di‐azo dye brilliant yellow (BY) under UV/solar light. X‐ray diffraction results revealed the phase transformation from anatase to rutile due to the inclusion of Mn²⁺ ion into the TiO₂ matrix. All the doped catalysts showed a red shift in the band gap to the visible region. The degradation reaction of the dyes was found to be dependent on its structure. It was found that mono azo dye degrades faster than di azo dye under UV/solar light. The rate constant under identical conditions calculated for the degradation of MO is 2.4 times (under UV light) and 4.5 times (under solar light) higher compared to BY. Among the photocatalysts studied, Mn²⁺(0.06 at.%)‐TiO₂ showed higher activity under both UV and solar light illumination. The synergestic effect in the bicrystalline framework of anatase and rutile effectively suppresses the charge carrier recombination and enhances the photocatalytic activity. The degradation reaction was followed by UV‐visible spectroscopy and the photoproducts formed were analyzed by GC‐MS techniques.     

Photodegradation of Rhodamine B on Sulfur Doped ZnO/TiO2 Nanocomposite Photocatalyst under Visible-light Irradiation

Sulfur doped ZnO/TiO₂ nanocomposite photocatalysts were synthesized by a facile sol‐gel method. The structure and properties of catalysts were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV‐vis diffusive reflectance spectroscopy (DRS) and N₂ desorption‐adsorption isotherm. The XRD study showed that TiO₂ was anatase phase and there was no obvious difference in crystal composition of various S‐ZnO/TiO₂. The XPS study showed that the Zn element exists as ZnO and S atoms form SO^2?₄. The prepared samples had mesoporosity revealed by N₂ desorption‐adsorption isotherm result. The degradation of Rhodamine B dye under visible light irradiation was chosen as probe reaction to evaluate the photocatalytic activity of the ZnO/TiO₂ nanocomposite. The commercial TiO₂ photocatalyst (Degussa P25) was taken as standard photocatalyst to contrast the prepared different photocatalyst in current work. The improvement of the photocatalytic activity of S‐ZnO/TiO₂ composite photocatalyst can be attributed to the suitable energetic positions between ZnO and TiO₂, the acidity site caused by sulfur doping and the enlargement of the specific area. S‐3.0ZnO/TiO₂ exhibited the highest photocatalytic activity under visible light irradiation after Zn amount was optimized, which was 2.6 times higher than P25.     

Preparation and Photocatalytic Activity of Mesoporous TiO2 Photocatalyst Co‐doped with Fe and H3PW12O40

The mesoporous titanium dioxide (MTiO₂) photocatalysts co‐doped with Fe and H₃PW₁₂O₄₀ were synthesized by template method using tetrabutyl titanate (Ti(OC₄H₉)₄), Fe(NO₃)k₃9H₂Oand H₃PW₁₂O₄₀ as precursors and Pluronic P123 as template. The as‐prepared photocatalyst was characterized by N₂ adsorption‐desorption measurements, X‐ray diffraction (XRD), scanning electron microscopy (SEM) and UV‐vis adsorption spectroscopy, and the photocatalytic activities of the prepared samples under UV and visible light were estimated by measuring the degradation rate of methyl blue (MB) (50 mg/L) in an aqueous solution. The characterizations indicated that the photocatalysts possessed a homogeneous pore diameter of ca. 10 nm with high surface area of ca. 150 m²/g. The results of MB photodecomposition showed that co‐doped mesoporous TiO₂ exhibited higher photocatalytic activities than un‐doped, single‐doped mesoporous TiO₂ under UV and visible light irradiation. It was shown that the co‐doped MTiO₂ could be activated by visible light and could thus be used as an effective catalyst in photo‐oxidation reactions. The synergistic effect of Fe and H₃PW₁₂O₄₀ co‐doping played an important role in improving the photocatalytic activity.     

Dye degradation studies of Mo‐doped TiO2 thin films developed by reactive sputtering

TiO₂ thin films with various Mo concentrations have been deposited on glass and n‐type silicon (100) substrates by this radio‐frequency (RF) reactive magnetron sputtering at 400°C substrate temperature. The crystal structure, surface morphology, composition, and elemental oxidation states of the films have been analyzed by using X‐ray diffraction, field emission scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy, respectively. Ultraviolet‐visible spectroscopy has been used to investigate the degradation, transmittance, and absorption properties of doped and undoped TiO₂ films. The photocatalytic degradation activity of the films was evaluated by using methylene blue under a light intensity of 100 mW cm⁻². The X‐ray diffraction patterns show the presence of anatase phase of TiO₂ in the developed films. X‐ray photoelectron spectroscopy studies have confirmed that Mo is present only as Mo⁶⁺ ions in all films. The Mo/TiO₂ band gap decreases from ~3.3 to 3.1 eV with increasing Mo dopant concentrations. Dye degradation of ~60% is observed in Mo/TiO₂ samples, which is much higher than that of pure TiO₂.     

Solvothermal Synthesis of M‐doped TiO2 Nanoparticles for Sonocatalysis of Methylene Blue and Methyl Orange (M = Cd,Ag, Fe,Ce, and Cu)

M‐doped TiO₂ nanoparticles were synthesized by a sol–gel‐assisted solvothermal method. X‐ray diffraction (XRD) , transmission electron microscopy (TEM) , and diffuse reflection spectroscopy (DRS) were used to characterize the as‐synthesized samples. The sonocatalytic performance of the specimens for methylene blue and methyl orange degradation was evaluated. XRD confirmed the formation of anatase as the unique phase in all samples. TEM showed that Cd, Cu, and Ce led to increased particle size in comparison to TiO₂ nanoparticles, whereas Fe and Ag had no considerable influence on this parameter. DRS confirmed the change in the absorption edge, and E _g values decreased in the range 4.6–1.2% by Cd, Ce, Fe, Cu, and Ag doping, respectively. Among the different dopants, only Cd and Ag improved the absorbance of UV –visible light, and only these samples induced sonodegradation of the dye models. It can be concluded that the improvement in the dye removal efficiency is not related to an increase in the crystallinity and/or a decrease in E _g, but only related to the increase in absorbance.     

Effect of Erbium on the Photocatalytic Activity of TiO2/Ag Nanocomposites under Visible Light Irradiation

Erbium co‐doped TiO₂/Ag catalysts are synthesized by using a simple, one‐step solvothermal method and characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, Raman analysis, X‐ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. The catalysts exhibit anatase crystal structures with increased visible light absorption compared with pure TiO₂. Enhanced photocatalytic activity is observed with Er co‐doped TiO₂/Ag nanocomposites for Rhodamine B degradation under visible light irradiation. The photocatalytic activity of 1 % Er co‐doped TiO₂/Ag is much higher than that of TiO₂/Ag, TiO₂/Er, pure TiO₂, and commercial Degussa P25. The kinetics of the degradation process are studied and the pseudo‐first‐order rate constant (k) and half‐life time (t_1/2) of the reaction are calculated. The enhanced activity might be accredited to the efficient separation of electron–hole pairs by silver and higher visible light absorption of TiO₂ induced by Er.     

Functionalization of cotton fabrics with rutile TiO<Subscript>2</Subscript> nanoparticles: Applications for superhydrophobic,UV-shielding and self-cleaning properties

The superhydrophobic cotton fabrics were prepared by combining the coating of titanium dioxide (TiO₂) with the subsequent dodecafluoroheptyl-propyl-trimethoxysilane (DFTMS) modification. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements revealed that the nanosized TiO₂ sphere consisted of granular rutile. The TiO₂ layer coated on the cotton altered both the surface roughness for enhancing the hydrophobicity and UV-shielding property. The cotton fabric samples showed excellent water repellency with a water contact angle as high as 162°. The UV-shielding was characterized by UV-vis spectrophotometry, and the results indicated that the fabrics could dramatically reduce the UV radiation. The photocatalytic progress showed that organic stains were successfully degraded by exposure of the stained fabric to UV radiation. Such multifunctional cotton fabrics may have potentials for commercial applications.     

Nitrogen‐doped graphene‐cerium oxide (NG‐CeO2) photocatalyst for the photodegradation of methylene blue in waste water

This study shows a facile approach for the preparation of CeO₂ nanoparticles decorated with porous nitrogen‐doped graphene (NG) nanosheets for effective photocatalytic degradation of methylene blue (MB). NG nanosheets were first synthesized using a hydrothermal method and then nitrogen‐doped graphene‐cerium oxide (NG‐CeO₂) was prepared through mixing of cerium nitrate with different concentrations of NG under ultrasonication followed by hydrothermal treatment. The synthesized nanocomposites were characterized using X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE‐SEM). The photocatalytic activity of the synthesized nanocomposites was analyzed against MB dye. Results showed that the nanocomposites of NG‐CeO₂ have an average particle size of 20 nm. The as‐prepared NG‐CeO₂ nanocomposites exhibited outstanding photocatalytic activity for dye degradation under visible light irradiation, which could be attributed to synergistic effects between the NG nanosheets and CeO₂. The quantum of photodegradation increases with the increase of the NG content in the nanocomposites.     

Bactericidal activity and UV-filtering property of TiO<Subscript>2</Subscript>-based photocatalysts coated on curtain fabrics

Synthesized and commercial titanium dioxide (TiO₂) were coated onto household curtain fabrics for anti-microbial and ultraviolet (UV) shielding functions. The coating was performed by inducing a deposition of the TiO₂ layer from the Ti precursor onto the fabric surface. A silane adhesive agent was employed to improve the adhesion between the coating and the fabric. Ag nanoparticles were also incorporated into some samples to further improve the anti-bacterial activity, which was evaluated by a standard qualitative test (AATCC 147). Efficiency for UV shielding was evaluated by measuring a UV–visible reflection of the coated fabrics both before and after subjecting it to several washing cycles. The results showed that the TiO₂-coated fabrics had potential as both anti-bacterial and UV shielding for the curtain industry.     

A new method for deposition nitrogen‐doped TiO2 nanofibers with mixed phases of anatase and rutile

A new method for deposition nitrogen‐doped TiO₂ nanofibers films was proposed. By using atmospheric pressure plasma jet generated by dual‐frequency power sources, the morphologies of these TiO₂ films were investigated by scanning electron microscopy. The structures of these films were characterized by X‐ray diffraction and Raman Shift Spectroscopy. The elemental composition of these films [Colour figure can be viewed at wileyonlinelibrary.com ] were characterized by means of X‐ray photoelectron spectroscopy. The optical absorption of these films were studied by UV‐vis absorbance spectra. These results indicated that the nitrogen‐doped nanofibers TiO₂ films have mixed phases of anatase and rutile. They also display narrow band gap. The I‐V characteristics curves exhibited good conductivity ability. Optical emission spectroscopy (OES) was measured to analyze the active group.