Synthesis and characterization of bamboo-like CdS/TiO<Subscript>2</Subscript> nanotubes composites with enhanced visible-light photocatalytic activity

In order to efficiently use the visible light in the photocatalytic reaction, a novel bamboo-like CdS/TiO₂ nanotubes composite was prepared by a facile chemical reduction method, in which CdS nanoparticles located in the TiO₂ nanotubes. The composition and structure of this nanocomposite were characterized by TEM, HRTEM, XRD, XPS, FTIR and UV-vis spectroscopy. This CdS/TiO₂ nanotubes composite exhibited much higher visible-light photocatalytic activity for the degradation of methylene blue than pure TiO₂ nanotubes and CdS nanoparticles, and the highest photodegradation efficiency after 6 h irradiation can reach 84.5%. It is inferred that the unique structure of CdS/TiO₂ nanotubes composites acts an important role for the improvement of their photocatalytic activity.     

Efficient visible-light-induced photocatalytic degradation of MO on the Cr-nanocrystalline titania-S

In order to improve visible light photocatalytic activities of the nanometer TiO₂, a novel and efficient Cr,S-codoped TiO₂ (Cr-TiO₂-S) photocatalyst was prepared by precipitation-doping method. The crystalline structure, morphology, particle size, and chemical structure of Cr-TiO₂-S were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) techniques, respectively. Results indicate that the doping of Cr and S, cause absorption edge shifts to the visible light region (λ > 420 nm) compare to the pure TiO₂, reduces average size of the TiO₂ crystallites, enhances desired lattice distortion of Ti, promotes separation of photo-induced electron and hole pair, and thus improves pollutant decomposition under visible light irradiation. The photocatalytic activities of Cr-TiO₂-S nanoparticles were evaluated using the photodegradation of methyl orange (MO) as probe reaction under the irradiation of UV and visible light and it was observed that the Cr-TiO₂-S photocatalyst shows higher visible photocatalytic activity than the pure TiO₂. The optimal Cr-TiO₂-S concentration to obtain the highest photocatalytic activity was 5 mol% for both of Cr and S.     

Preparation of N-doped TiO<Subscript>2</Subscript> photocatalyst by atmospheric pressure plasma process for VOCs decomposition under UV and visible light sources

The nitrogen doped (N-doped) titanium dioxide (TiO₂) photocatalyst was prepared by the atmospheric-pressure plasma-enhanced nanoparticles synthesis (APPENS) process operated under normal temperature, i.e. the dielectric barrier discharge plasma process. The N₂ carrier gas is dissociated in the AC powered nonthermal plasma environment and subsequently doped into the TiO₂ photocatalyst that was capable of being induced by visible light sources. The APPENS process for producing N-doped TiO₂ showed a higher film deposition rate in the range of 60–94 nm/min while consuming less power (<100 W) as compared to other plasma processes reported in literatures. And the photocatalytic activity of the N-doped TiO₂ photocatalyst was higher than the commercial ST01 and P25 photocatalysts in terms of toluene removals in a continuous flow reactor. The XPS measurement data indicated that the active N doping states exhibited N 1s binding energies were centered at 400 and 402 eV instead of the TiN binding at 396 eV commonly observed in the literature. The light absorption in the visible light range for N-doped TiO₂ was also confirmed by a clear red shift of the UV-visible spectra.     

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.     

Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.     

Effect of ZnS layers on optical properties of prepared CdS/TiO<Subscript>2</Subscript> nanotube arrays for photocatalyst

The TiO₂ nanotube arrays (TiO₂ NTAs) prepared by re-oxidation were chosen as basement. The NTAs prepared through re-oxidation show smoother surface and more uniform tube mouth on large scale compared with the first as-grown one. We use successive ionic layer adsorption and reaction method to deposit quantum dots (ZnS and CdS) onto the sample successively. The findings reveal that two kinds of quantum dots (～10 nm) distribute regularly and the nanotube mouth is open. From the UV–Vis absorption spectrum of samples, the red shift occurs after the sedimentation of the two quantum dots, which proves that the double modification can expand the absorption to 650 nm. Among all specimens, the sample produced by co-deposition has the highest speed of catalytic efficiency of 90.7% compared with bare TiO₂ NTAs (52.9%) and just CdS QDs sensitized sample (65.8%). In the test of photocatalysis durability, the decay percentages of CdS/TiO₂ NTAs and ZnS/CdS/TiO₂ NTAs were 35.8 and 48.4%, respectively, which means that the ZnS passivation layer plays a crucial role in enhancing photocatalytic activities.     

Preparation and visible light photocatalytic activity of mesoporous N, S-codoped TiO2(B) nanobelts

The mesoporous N, S-codoped TiO₂(B) nanobelts are synthesized via hydrothermal synthesis and post-treatment, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption measurements (BET), X-ray photoelectron spectra (XPS), and UV-vis diffuse reflectance spectra (DRS). The results show that the prepared samples are mesoporous structured and exhibit stronger absorption in the visible light region with red shift in the absorption edge. The photocatalytic activity of N, S-codoped mesoporous TiO₂(B) nanobelts is evaluated by the photocatalytic photodegradation of potassium ethyl xanthate (KEX) under visible light irradiation. It is found that the photocatalytic activity of the prepared samples increases with increasing the molar ratio of thiourea to Ti (R). At R = 3, the photocatalytic activity of the N, S-codoped TiO₂(B) sample TBLTS-3 reaches a maximum value. With further increasing R, the photocatalytic activity of the sample decreases. The high photocatalytic activity of N, S-codoped TiO₂(B) nanobelts can be attributed to the balance between strong absorption in visible light region and low recombination rate of electron/hole pairs.     

Multiwalled carbon nanotubes decorated with nitrogen, palladium co-doped TiO2 (MWCNT/N, Pd co-doped TiO2) for visible light photocatalytic degradation of Eosin Yellow in water

Multiwalled carbon nanotube (MWCNT/N), Pd co-doped TiO₂ nanocomposites were prepared by calcining the hydrolysis products of the reaction of titanium isopropoxide, Ti(OC₃H₇)₄ containing multiwalled carbon nanotubes with aqueous ammonia. The prepared samples were characterised by Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, diffuse reflectance UV?CVis spectrophotometry (DRUV?CVis), XRD, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). DRUV?CVis analysis confirmed the red shift in the absorption edge at lower MWCNT percentages. SEM and TEM images showed the complete coverage of the MWCNTs with clusters of anatase TiO₂ at low MWCNT percentages. Higher MWCNT levels led to their aggregation and consequently poor coverage by N, Pd co-doped TiO₂. The photocatalytic activities of the nanocomposites were monitored by photodegradation of Eosin Yellow under simulated solar and visible light irradiation (???>?450?nm). Irradiation with simulated solar radiation gave higher dye-degradation rates compared to visible radiation. The optimum MWCNT weight percentage in the composites was found to be 0.5. High degradation-rate constants of 3.42?×?10^?2 and 5.18?×?10^?3?min^?1 were realised for the 0.5% MWCNT/N, Pd co-doped TiO₂ composite, using simulated solar light and visible light, respectively.     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

A novel Cr₂O₃/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr₂O₃ on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr₂O₃ nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV–visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr₂O₃. The 2.5Cr₂O₃/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H₂ evolution for Cr₂O₃/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr³⁺ and a probably photocatalytic mechanism was proposed.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with lanthanum and iodine

The novel visible-light-activated La/I/TiO₂ nanocomposition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by X-ray powder diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG-DSC) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of La/I/TiO₂ was evaluated by studying photodegradation of reactive blue 19 as a probe reaction under simulated sunlight irradiation. Photocatalytic experiment results showed that the maximum specific photocatalytic activity of the La/I/TiO₂ photocatalyst appeared when the molar ratio of La/Ti was 2.0 at%, calcined at 350 °C for 2 h, due to the sample with good crystallization, high BET surface area and small crystal size. Under simulated sunlight irradiation, the degradation of reactive blue 19 aqueous solution reached 98.6% in 80 min, which showed La/I/TiO₂ photocatalyst to be much higher photocatalytic activity compared to standard Degussa P25 photocatalyst. The higher visible light activity is due to the codoping of lanthanum and iodine.     

Photodeposition of ultrathin MoS<Subscript>2</Subscript> nanosheets onto cubic CdS for efficient photocatalytic H<Subscript>2</Subscript> evolution

In this work, the photocatalyst composed of ultrathin MoS₂ nanosheets onto the surface of cubic CdS nanoparticles with an average diameter of 7~10 nm has been successfully fabricated through a facile and mild photodeposition route. The ultrathin MoS₂ nanosheets as a cocatalyst were demonstrated to greatly boost photocatalytic H₂ evolution over cubic CdS upon visible light irradiation. It was clearly revealed that both the cubic CdS substrate and structure of ultrathin MoS₂ nanosheets play critical roles in the observed efficient H₂ evolution. The cubic CdS offers a strong adherence for ultrathin MoS₂ nanosheets to form a well contact interface, across which the photogenerated charge transfer and charge separation are achieved. The ultrathin MoS₂ nanosheets introduce a high density of unsaturated active S atoms for H₂ evolution.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

Photoinduced Degradation of the Optical Properties of Colloidal Ag<Subscript>2</Subscript>S and CdS Quantum Dots Passivated by Thioglycolic Acid

The results of studying degradation of the optical properties of colloidal Ag₂S and CdS quantum dots (QDs) 2.6–3.2 nm in size passivated by thioglycolic acid (TGA) are presented. The photoluminescence intensity of colloidal Ag₂S QDs has been found to decrease under laser irradiation at a wavelength of 445 nm, beginning with the effective power of 10 mW. The observed effect is interpreted as a photochemical reaction of formation of new nonradiative-recombination channels in Ag₂S QDs upon excitation. It is established for colloidal CdS QDs passivated by TGA that a decrease in the optical density in the entire absorption spectrum and the luminescence intensity is accompanied by precipitation of the colloidal particles in a cell and related to photodegradation of the passivating shell.     

Curcumin-sensitized TiO2 for enhanced photodegradation of dyes under visible light

Curcumin was coated on P25 TiO₂ by using impregnation method from freshly prepared curcumin solution. The resulting products (Cur–TiO₂–P25) was studied by several techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier-transformed infrared spectroscopy, specific surface area by the Brunauer–Emmett–Teller method, and UV–Vis diffused reflectance spectroscopy. Experimental results revealed that impregnation of curcumin at 0.5, 3, 5, and 7 wt% did not affect the native phase of anatase and rutile in P25 significantly, however, it caused red shift of absorption onset in all curcumin-coated samples. The Cur–TiO₂–P25 showed enhanced adsorption efficiency and increased photocatalytic activity under visible light with optimal result at 5 wt% curcumin content. Commercial anatase and rutile coated with curcumin (Cur–TiO₂–an and Cur–TiO₂–ru) were also prepared by the same method for the use in comparative studies of photodegradation of dyes. Cur–TiO₂–an and Cur–TiO₂–ru were also characterized with some selected equipment above but not as extensively as the Cur–TiO₂–P25. Curcumin coating helped improve photocatalytic efficiencies of P25 and anatase but not for rutile. The mechanism of photocatalytic reaction was proposed that under visible light irradiation, curcumin molecule could act as dye sensitizing agent that injected electron into the conduction band of TiO₂ leading to photodegradation of dyes.     

Sunlight photocatalytic activity of CdS modified TiO2 loaded on activated carbon fibers

To improve the photocatalytic application performances of TiO₂, in this work, firstly CdS modified Degussa P25 TiO₂ (CdS/TiO₂) composites were prepared by two methods, sol-gel method and precipitation method. Next they, sol-gel-CdS/TiO₂ (sg-CdS/TiO₂) and precipitation-CdS/TiO₂ (pp-CdS/TiO₂), were loaded on activated carbon fibers (ACFs) by dip-coating method using the sodium carboxymethyl cellulose as adhesives. The composites were characterized by XRD, UV-vis absorbance spectra, SEM, EDS and BET. The photocatalytic activities under sunlight were investigated by the degradation of methylene blue. The results showed that CdS/TiO₂ composites were mainly composed of anatase-TiO₂ and little CdS cubic phases. The absorption wavelengths of sg-CdS/TiO₂ and pp-CdS/TiO₂ composites were extended to 590 nm and 740 nm, respectively. The absorption edge had a pronounced ‘red shift’. From EDS analysis, the elemental contents of CdS/TiO₂ were mainly Ti and O and a small quantity of S and Cd. CdS/TiO₂ loaded on ACFs were in the form of small clusters, but not very uniform; compared with the original ACFs, the surface area and pore volume of CdS/TiO₂/ACFs decreased slightly, respectively, while the average pore diameter was not changed. The photodegradation rate of methylene blue under sunlight with CdS/TiO₂/ACFs composites was markedly higher than that of P25-TiO₂/ACFs, and the effect of pp-CdS/TiO₂/ACFs composites was better than that of sg-CdS/TiO₂/ACFs, when irradiated for 180 min, and the photodegradation rate of methylene blue reached to 90.1%. The photodegradation kinetics of the methylene blue fitted with the Langmuir-Hinshelwood equation. The apparent reaction rate constants of sg-CdS/TiO₂/ACFs and pp-CdS/TiO₂ were 0.0105 min⁻¹ and 0.0146 min⁻¹, respectively, which were about 1.3-1.7 times as large as that of P25-TiO₂/ACFs.     

Hydrothermal synthesis,characterization and optical absorption property of nanoscale WS2/TiO2 composites

Nanosized tungsten disulfide (WS₂) sensitized titanium dioxide (TiO₂) was successfully prepared via a simple yet facile hydrothermal process. The nanocomposite exhibited a wide and intensive absorption in the visible light region of 400–700 nm, and may have a potential application as a visible photocatalyst. In addition, the sensitization mechanism of the nano-WS₂ was proposed to elaborate the wide visible light absorption of the WS₂/TiO₂ nanocomposites.     

Diatom-templated TiO2 with enhanced photocatalytic activity: biomimetics of photonic crystals

The siliceous frustules with sophisticated optical structure endow diatoms with superior solar light-harvesting abilities for effective photosynthesis. The preserved frustules of diatom (Cocconeis placentula) cells, as biophotonic crystals, were thus employed as both hard templates and silicon resources to synthesize TiO₂ photocatalyst. Characterizations by a combination of physicochemical techniques proved that the bio-inspired sample is TiO₂-coated SiO₂ with biogenic C self-doped in. It was found that the synthesized composites exhibited similar morphologies to the original diatom templates. In comparison with commercial Degussa P25 TiO₂, the C-doped TiO₂/SiO₂ catalyst exhibited more light absorption in the visible region and higher photocatalytic efficiency for photodegradation of rhodamine B under visible light due to the biomorphic hierarchical structures, TiO₂ coating and C-doping.     

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.     

Investigation on a novel ZnO/TiO2–B photocatalyst with enhanced visible photocatalytic activity

A new type of composite photocatalysts (ZnO/TiO₂–B) with Zinc oxide nanoparticles dispersed on boron doped titanium dioxide was prepared via a sol–gel method. The as-prepared powders were characterized by HRTEM, XRD, XPS, UV–vis DRS, and PL techniques. The results reveal that B³⁺ ions are doped into the TiO₂ lattice in interstitial mode, while ZnO nanoparticles are dispersed on the surface of TiO₂. The absorption of photocatalysts was extended into visible light region and the photogenerated electrons and holes were separated efficiently. Hence, ZnO/TiO₂–B composite photocatalyst exhibits much better photocatalytic activity than those of pure TiO₂ and TiO₂–B on photodegradation of 4-chlorophenol under visible light irradiation.