Efficient and Robust Cu/TiO2 Nanorod Photocatalysts for Simultaneous Removal of Cr(VI) and Methylene Blue under Solar Light

Because of its large bandgap, TiO₂ can function only under UV light. TiO₂ surface modification with noble metal nanoparticles can extend the light absorption from UV to visible light region and enhance the photocatalytic quantum yield. In this work, TiO₂ nanorods (Cu/TiO₂) modified by copper nanoparticles were prepared by a one‐step solvothermal method at low cost. The resultant Cu/TiO₂ nanorods show excellent synergistic effect in the oxidation of methylene blue (MB) and the reduction of aqueous Cr(VI) under solar light irradiation. Mechanistic investigation suggests that the Cr(VI) species could effectively scavenge the electrons from MB in the presence of the as‐prepared photocatalyst, leading to the simultaneous removal of both pollutants. Being economically viable, environmentally sustainable, and highly efficient, the proposed photocatalyst holds promise for technologies involving simultaneous organic degradation and heavy metal removal in wastewater treatment.     

Reconsideration to the deactivation of TiO2 catalyst during simultaneous photocatalytic reduction of Cr(VI) and oxidation of salicylic acid

Photocatalytic reduction/oxidation and deactivation of TiO₂ photocatalyst was investigated in the systems composed of Cr(VI) and salicylic acid. The selection of analysis method of Cr(IV) was very important to the monitoring of the photocatalytic process. It was found that as previously reported, serious deactivation of TiO₂ catalyst in the simultaneous photo-reduction of Cr(VI) and oxidation of salicylic acid was incorrectly observed if the Cr(VI) level was analyzed by directly monitoring the absorbance at characteristic 348 nm band of Cr(VI), because it seriously suffers from the interferences of the intermediates generated from the degradation of salicylic acid. By using an appropriate method to determine the Cr(VI) concentration, it was observed that all the added Cr(VI) could be reduced, not showing marked deactivation of the photocatalyst. A long time photocatalytic reduction of Cr(VI) under UV illumination induced the deposition of Cr(III) species on the surface of TiO₂ particles, which could cause a mild deactivation of the photocatalyst. However, the accompanied oxidation of salicylic acid was demonstrated to depress the deactivation effect of the deposited Cr(III) species on the photocatalytic activity of the TiO₂ photocatalyst.     

Ion engineering techniques for the preparation of the highly effective TiO<Subscript>2</Subscript> photocatalysts operating under visible light irradiation

The successful application of ion engineering techniques for the development of TiO₂ photocatalysts operating under visible and/or solar light irradiations has been summarized in this review article. First, we have physically doped various transition metal ions within a TiO₂ lattice on an atomic level by using an advanced metal ion implantation method. The metal ion implanted TiO₂ could efficiently work as a photocatalyst under visible light irradiation. Some field tests under solar light irradiation clearly revealed that the Cr or V ions implanted TiO₂ samples showed 2–3 times higher photocatalytic reactivity than the un-implanted TiO₂. Second, we have developed the visible light responsive TiO₂ thin film photocatalyst by a single process using an RF-magnetron sputtering (RF-MS) deposition method. The vis-type TiO₂ thin films showed high photocatalytic reactivity for various reactions such as reduction of NOx, degradation of organic compounds, and splitting of H₂O under visible and/or solar light irradiations.     

Effect of dopant concentration on photocatalytic activity of TiO2 film doped by Mn non-uniformly

The thin films of TiO₂ doped by Mn non-uniformly were prepared by sol-gel method under process control. In our preceding study, we investigated in detail, the effect of doping mode on the photocatalytic activity of TiO₂ films showing that Mn non-uniform doping can greatly enhance the activity. In this study we looked at the effect of doping concentration on the photocatalytic activity of the TiO₂ films. In this paper, the thin films were characterized by UV-vis spectrophotometer and electrochemical workstation. The activity of the photocatalyst was also evaluated by photocatalytic degradation rate of aqueous methyl orange under UV radiation. The results illustrate that the TiO₂ thin film doped by Mn non-uniformly at the optimal dopant concentration (0.7 at %) is of the highest activity, and on the contrary, the activity of those doped uniformly is decreased. As a comparison, in 80 min, the degradation rate of methyl orange is 62 %, 12 % and 34 % for Mn non-uniform doping film (0.7 at %), the uniform doping film (0.7 at %) and pure titanium dioxide film, respectively. We have seen that, for the doping and the pure TiO₂ films, the stronger signals of open circuit potential and transient photocurrent, the better photocatalytic activity. We also discusse the effect of dopant concentration on the photocatalytic activity of the TiO₂ films in terms of effective separation of the photon-generated carriers in the semiconductor.     

不同复合体系对含钛高炉渣光催化还原Cr(VI)的影响

采用煅烧的硫酸盐掺杂的含钛高炉渣(sulfate-modified titanium-bearing blast furnace slag, STBBFS)作为光催化剂, 研究了Cr(VI)-柠檬酸[Cr(VI)-CA]复合体系和Cr(VI)-柠檬酸-硝酸铁[Cr(VI)-CA-FN]复合体系对 STBBFS催化剂光催化活性的影响. 结果表明: 酸性条件下, 不同复合体系对STBBFS催化剂光催化活性的促进作用按Cr(VI)-CA-FN复合体系＞Cr(VI)-CA复合体系＞Cr(VI)单一体系增强. Cr(VI)-CA复合体系在pH＝2.5, 反应50 min后STBBFS催化剂光催化活性为0.426 mg&#8226;min―1&#8226;g―1时将溶液中的Cr(VI)全部还原; 而Cr(VI)-CA-FN复合体系在pH＝2.5, 反应16 min后STBBFS催化剂光催化活性为1.2425 mg&#8226;min―1&#8226;g―1时将溶液中的Cr(VI)全部还原. 两种复合体系中, Cr(VI)离子的光催化还原过程都遵循L-H动力学规律, 虽然加入CA和FN后, 降低了吸附对光催化还原Cr(VI)的影响, 但是Cr(VI)吸附至催化剂表面仍然是整个反应过程的关键.     

Preparation of TiO<Subscript>2</Subscript> nanofibers immobilized on quartz substrate by electrospinning for photocatalytic degradation of ranitidine

The photocatalytic activity of TiO₂ nanofibers immobilized on quartz substrates was investigated by evaluating the decomposition of organic pollutants. TiO₂ nanofibers were synthesized by electrospinning the Ti-precursor/polymer mixture solution, followed by hot-pressing for enhancing the adhesion of TiO₂-nanofiber films to the substrates. TiO₂ started to crystalize in the anatase form at 500 °C and reached the optimal photocatalytic anatase/rutile phase ratio of 70:30 at a calcination temperature of 600 °C. The TiO₂-nanofiber film was demonstrated to be an efficient photocatalyst by ranitidine decomposition under UV illumination and was proven to have a comparable photocatalytic activity with the well-known Degussa P25 nanoparticulate photocatalyst and excellent recyclability during 10 cycles of photocatalytic operation, indicating no loss of TiO₂ nanofibers during photocatalytic operations.     

Understanding the synergistic effects,optical and electronic properties of ternary Fe/C/S‐doped TiO2 anatase within the DFT + U approach

Although TiO₂ is an efficient photocatalyst, its large band gap limits its photocatalytic activity only to the ultraviolet region. An experimentally synthesized ternary Fe/C/S‐doped TiO₂ anatase showed improved visible light photocatalytic activity. However, a theoretical study of the underlying mechanism of the enhanced photocatalytic activity and the interaction of ternary Fe/C/S‐doped TiO₂ has not yet been investigated. In this study, the defect formation energy, electronic structure and optical property of TiO₂ doped with Fe, C, and S are investigated in detail using the density functional theory + U method. The calculated band gap (3.21 eV) of TiO₂ anatase agree well with the experimental band gap (3.20 eV). The defect formation energy shows that the co‐ and ternary‐doped systems are thermodynamically favorable under oxygen‐rich condition. Compared to the undoped TiO₂, the absorption edge of the mono‐, co‐, and ternary‐doped TiO₂ is significantly enhanced in the visible light region. We have shown that ternary doping with C, S, and Fe induces a clean band structure without any impurity states. Moreover, the ternary Fe/C/S‐doped TiO₂ exhibit an enhanced photocatalytic activity, a smaller band gap and negative formation energy compared to the mono‐ and co‐doped systems. Moreover, the band edges of Fe/C/S‐doped TiO₂ align well with the redox potentials of water, which shows that the ternary Fe/C/S‐doped TiO₂ is promising photocatalysts to split water into hydrogen and oxygen. These findings rationalize the available experimental results and can assist the design of TiO₂‐based photocatalyst materials.     

TiO2/EDTA-rich carbon composites: Synthesis,characterization and visible-light-driven photocatalytic reduction of Cr(VI)

TiO₂/EDTA-rich carbon composites exhibits excellent photoreduction of Cr(VI) activity via ligand-to-metal charge transfer process.     

Characterization of Titanium Dioxide Doped with Nitrogen and Sulfur and its Photocatalytic Appraisal for Degradation of Phenol and Methylene Blue

The degradation of organic dyes in the presence of modified TiO₂ is still under intensive investigation. We report here an evaluation of the photocatalytic activity of nitrogen‐ (N‐) and sulfur‐ (S‐) doped TiO₂ for the degradation of phenol and methylene blue (MB). N‐doped TiO₂ (N–TiO₂), S‐doped TiO₂ (S–TiO₂), and N–S‐doped TiO₂ (N–S–TiO₂) were prepared using the sol–gel method. The photocatalytic activity was evaluated in a batch reactor using phenol and MB as models of pollutants. In addition, this investigation was performed using a household lamp as the visible light source. Properties of the synthesized materials in terms of Brunauer–Emmett–Teller (BET) surface analysis, field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and photocatalytic ability were examined. Our study shows that N–S–TiO₂ exhibits better photocatalytic degradation ability for all the considered dyes compared to the other doped TiO₂ materials. In conclusion, we have successfully prepared and evaluated the photocatalytic activity of N‐ and S‐doped TiO₂ for the degradation of phenol and MB using an ordinary household lamp.     

Pure and modified TiO2 photocatalysts and their environmental applications

Semiconductor photocatalysis is a process that harnesses light energy in chemical conversions. In particular, its applications to environmental remediation have been intensively investigated. The characteristics of TiO₂, the most popular photocatalyst, is briefly described and selected studies on the degradation/conversion of various recalcitrant pollutants using pure and modified TiO₂ photocatalysts, which were carried out in this group, are reviewed. Photocatalytic reactions are multi-phasic and take place at interfaces of not only water/TiO₂ and air/TiO₂ but also solid/TiO₂. Examples of photocatalytic reactions of various organic and inorganic substrates that are converted through the photocatalytic oxidation or reduction are introduced. TiO₂ has been modified in various ways to improve its photocatalytic activity. Surface modifications of TiO₂ that include surface platinization, surface fluorination, and surface charge alteration are discussed and their applications to pollutants degradation are also described in detail.     

Samarium-doped mesoporous TiO2 nanoparticles with improved photocatalytic performance for elimination of gaseous organic pollutants

Mesoporous TiO₂ doped with different amounts of Sm were prepared via a sol-gel route with Pluronic P123 as template. The materials were characterized by X-ray diffraction, transmission electron microscopy, and N₂ sorption experiments, etc. The photocatalytic activity of the mesoporous TiO₂ was tested in elimination of gaseous methanol and acetone. The Sm doped mesoporous TiO₂ have higher activity than those of the commercial photocatalyst (Degussa, P25) and Sm doped TiO₂ counterparts without mesopore structure under ultraviolet light irradiation. A possible mechanism was proposed to account for the high photocatalytic activity of the Sm doped mesoporous TiO₂. The superior activity of the Sm doped mesoporous TiO₂ may be attributed to the synergic effect of the high surface area, mesopore structure and doped Sm species.     

Preparation of photocatalytic nano-ZnO/TiO2 film and application for determination of chemical oxygen demand

A composite nano-ZnO/TiO₂ film as photocatalyst was fabricated with vacuum vaporized and sol-gel methods. The nano-ZnO/TiO₂ film improved the separate efficiency of the charge and extended the range of spectrum, which showed a higher efficiency of photocatalytic than the pure nano-TiO₂ and nano-ZnO film. The photocatalytic mechanism of nano-ZnO/TiO₂ film was discussed, too. A new method for determination of low chemical oxidation demand (COD) value in ground water based on nano-ZnO/TiO₂ film using the photocatalytic oxidation technology was founded. This method was originated from the direct determination of the Mn(VII) concentration change resulting from photocatalytic oxidation of organic compounds on the nano-ZnO/TiO₂ film, and the COD values were calculated from the absorbance of Mn(VII). Under the optimal operation conditions, the detection limit of 0.1 mg l⁻¹, COD values with the linear range of 0.3-10.0 mg l⁻¹ were achieved. The results were in good agreement with those from the conventional COD methods.     

Photocatalytic activity of polyaniline/Fe-doped TiO2 composites by in situ polymerization method

This study was focused on the photocatalytic activity of polyaniline (Pani)/iron doped titanium dioxide (Fe–TiO₂) composites for the degradation of methylene blue as a model dye. TiO₂ nanoparticles were doped with iron ions (Fe) using the wet impregnation method and the doped nanoparticles were further combined with Pani via an in situ polymerization method. For comparison purposes, Pani composites were also synthesized in the presence undoped TiO₂. The photocatalyst and the composites were characterized by standard analytical techniques such as FTIR, XRD, SEM, EDX and UV–Vis spectroscopies. Fe–TiO₂ and its composites exhibited enhanced photocatalytic activity under ultraviolet light irradiation. Improved photocatalytic activity of Fe–TiO₂ was attributed to the dopant Fe ions hindering the recombination of the photoinduced charge carriers. Pani/Fe–TiO₂ composite with 30?wt.% of TiO₂ nanoparticles achieved 28% dye removal and the discoloration rate of methylene blue for the sample was 0.0025?min^?1. FTIR, XRD, SEM, EDX and UV–Vis spectroscopies supported the idea that Fe ions integrated into TiO₂ crystal structure and Pani composites were successfully synthesized in the presence of the photocatalyst nanoparticles. The novelty of this study was to investigate the photocatalytic activity of Pani composites, containing iron doped TiO₂ and to compare their results with that of Pani/TiO₂.     

Preparation and characterization of nitrogen-doped TiO2 photocatalyst in different acid environments

Nitrogen-doped TiO₂ powders were successfully prepared by a wet method, i.e., a micro-emulsion-hydrothermal method, in different acid environments. Several characterization techniques, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra, were combined to determine the crystal phase, concentration and chemical states of the nitrogen doped in TiO₂. The high photocatalytic activity of the nitrogen-doped TiO₂ was evaluated through the decomposition of rhodanmine B under visible light irradiation. It was suggested that the doped nitrogen formed oxynitride (NO) and produced impurity states at higher above the valence band of TiO₂. Therefore, the nitrogen doping could enhance the response of photocatalyst to the visible light and improve the photocatalytic activity because of the narrowing of band gap of TiO₂.     

A study on the degradation of methamidophos in the presence of nano-TiO<Subscript>2</Subscript> catalyst doped with Re

A new Re-doped nano-TiO₂ photocatalyst was synthesized by immersion method. The novel doped nano-TiO₂ photocatalyst utilizing visible light was firstly prepared. The doped nano-TiO₂ powder was charactered by XRD, FTIR, UV-Vis, and its photocatalytic activity was tested through the photocatalytic degradation of methamidophos as a model compound under ultraviolet irradiating and in sunlight, respectively. In order to compare the photocatalytic activities, the same experiment was carried out for undoped nano-TiO₂. The degradation ratio of methamidophos in the presence of doped nano-TiO₂ reached 64.40% under sunlight for 12 h, which was 2.64% in the presence of undoped nano-TiO₂. The degradation ratio of methamidophos in the presence of doped nanoTiO₂ reached 90.39% under UV irradiationat 2.5 h, which was 51.29% in the presence of undoped nano-TiO₂. All the results show that the doped TiO₂ is a promising photocatalyst using sunlight for treating the organophosphorous pesticide wastewater. The article is published in the original.     

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.     

Development of TiO<Subscript>2</Subscript> photocatalysts suitable for practical use and their applications in environmental cleanup

Recently, environmental disruption is proceeding on a global scale through the consumption of huge amounts of fossil fuels and the emission of various chemical substances. However, these substances resist bio-treatment. TiO₂ generates electrons and holes by irradiation with light. Most organic micro-pollutants, including dioxins, are decomposed into carbon dioxide and water by the effect of the holes with high oxidative potential. By using such a photocatalytic reaction, various applications are feasible for environmental cleanup. In general, TiO₂ powder has been utilized as photocatalyst, although TiO₂ powder photocatalyst has several disadvantages: (1) it is difficult to handle, (2) photocatalytic reaction is slow and it takes a lot of time for treatment and (3) it is difficult to apply to plastics and textiles, because the photocatalyst decomposes them. We have developed a photocatalyst suitable for practical use and have developed high-activity photocatalysts such as TiO₂ photocatalytic transparent film, photocatalytic silica-gel, apatite-coated TiO₂ photocatalyst usable for plastics and textiles, photocatalytic paper, photocatalytic blue charcoal and photocatalytic oxygen scavenger. The application of these high-activity photocatalysts has been studied in deodorization, anti-bacterial, self-cleaning, anti-stain, water treatment, air purification such as photocatalytic decomposition of dioxins and VOC, and NO _x removal. Now various photocatalytic articles using these new photocatalyst materials are on the market in Japan. Photocatalytic technology can create many valuable products for environmental use all over the world.     

Electrospun TiO2 nanofibers coated with polydopamine for enhanced sunlight-driven photocatalytic degradation of cationic dyes

Controlled polydopamine (PDA)-coated TiO₂ composite nanofibers (NFs) were successfully fabricated via a facile electrospinning process and exposing TiO₂ NFs into a slightly alkaline dopamine solution. Chemical composition, structural morphology, and photocatalytic degradation property of as-prepared TiO₂ NFs and PDA-coated TiO₂ composite NFs were characterized by Fourier transfer infrared, X-ray photoelectron spectra, transmission electron microscopy, UV-vis diffuse reflectance spectra, and photocatalytic degradation experiments. The results indicated that the core-shell TiO₂@PDA composite NFs were successfully prepared and the thickness of PDA shell was highly controlled within several nanometers. And obtained TiO₂@PDA composite NFs exhibited improved photocatalytic performance after PDA coating, which is attributed to the photosensitization of PDA shell. Moreover, with increased pH values of initial solution, both absorption capacity in the dark and photocatalytic performance of TiO₂@PDA composite NFs showed significant improvement. Additionally, the obtained composite NFs showed different degrees of enhancement in photocatalytic performance based on different dyes, which is related to the “bait” effect of PDA shell. Comparing with anionic dyes, TiO₂@PDA composite NFs tended to adsorb and degrade more cationic dye molecules. It is anticipated that the fabricated composite NFs with controlled core-shell structure have great potential to be applied for organic pollutants removal, especially cationic dyes.     

The Influence of Defects on Mo‐Doped TiO2 by First‐Principles Studies

TiO₂ doped with transition metals shows improved photocatalytic efficiency. Herein the electronic and optical properties of Mo‐doped TiO₂ with defects are investigated by DFT calculations. For both rutile and anatase phases of TiO₂, the bandgap decreases continuously with increasing Mo doping level. The 4d electrons of Mo introduce localized states into the forbidden band of TiO₂, and this shifts the absorption edge into the visible‐light region and enhances the photocatalytic activity. Since defects are universally distributed in TiO₂ or doped TiO₂, the effect of oxygen deficiency due to oxygen vacancies or interstitial Mo atoms is systemically studied. Oxygen vacancies associated with the Mo dopant atoms or interstitial Mo will reduce the spin polarization and magnetic moment of Mo‐doped TiO₂. Moreover, oxygen deficiency has a negative impact on the improved photocatalytic activity of Mo‐doped TiO₂. The current results indicate that substitutional Mo, interstitial Mo, and oxygen vacancy have different impacts on the electronic/optical properties of TiO₂ and are suited to different applications.     

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.