Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2

A visible-light-active TiO₂ photocatalyst was prepared through carbon doping by using glucose as carbon source. Different from the previous carbon-doped TiO₂ prepared at high temperature, our preparation was performed by a hydrothermal method at temperature as low as 160 °C. The resulting photocatalyst was characterized by XRD, XPS, TEM, nitrogen adsorption, and UV–vis diffuse reflectance spectroscopy. The characterizations found that the photocatalyst possessed a homogeneous pore diameter about 8 nm and a high surface area of 126 m²/g. Comparing to undoped TiO₂, the carbon-doped TiO₂ showed obvious absorption in the 400–450 nm range with a red shift in the band gap transition. It was found that the resulting carbon-doped TiO₂ exhibits significantly higher photocatalytic activity than the undoped counterpart and Degussa P25 on the degradation of rhodamine B (RhB) in water under visible light irradiation (λ > 420 nm). This method can be easily scaled up for industrial production of visible-light driven photocatalyst for pollutants removal because of its convenience and energy-saving.     

Preparations and photocatalytic properties of magnetically separable nitrogen-doped TiO2 supported on nickel ferrite

A magnetically separable nitrogen-doped photocatalyst TiO_2−xN_x/SiO₂/NiFe₂O₄ (TSN) with a typical ferromagnetic hysteresis was prepared by a simple process: the magnetic SiO₂/NiFe₂O₄ (SN) dispersion prepared by a liquid catalytic phase transformation method and the visible-light-active photocatalyst TiO_2−xN_x were mixed, sonificated, dried, and calcined at 400 °C. The prepared photocatalyst is photoactive under visible light irradiation and easy to be separated from a slurry-type photoreactor under the application of an external magnetic field, being one of promising photocatalysts for wastewater treatment. Transmission electron microscope (TEM) and X-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that the magnetic SiO₂/NiFe₂O₄ (SN) nanoparticles adhere to the surface of TiO_2−xN_x congeries. The magnetic photocatalyst TSN shows high catalytic activity for the degradation of methyl orange in water under UV and visible light irradiation (λ > 400 nm). SiO₂ coating round the surface of NiFe₂O₄ nanoparticles prevents effectively the injection of charges from TiO₂ particles to NiFe₂O₄, which gives rise to the increase in photocatalytic activity. Moreover, the recycled TSN exhibits a good repeatability of the photocatalytic activity.     

Preparation and performances of mesoporous TiO2 film photocatalyst supported on stainless steel

Mesoporous TiO₂ film photocatalysts supported on stainless steel substrates were prepared using the sol–gel method with Ti(OC₄H₉)₄ as a precursor and poly ethylene glycol (PEG) as a structure-directing agent. Mesoporous TiO₂ film with a pore diameter of about 15 nm was obtained with the addition of PEG (molecular WEIGHT =400). The pore diameter of TiO₂film was varied with molecular weight of PEG additive. The structure-directing process was also discussed. Mesoscopically ordered inorganic/polymer composites were believed to form during the process. Compared to conventional TiO₂ film photocatalyst, the mesoporous TiO₂ film showed a good performance for the photo degradation of rhodamine B (RB) solution irradiated with UV light of 365 nm. The photo degradation constant of rhodamine B for mesoporous TiO₂ film photocatalyst can arrive at 22 times of that for conventional TiO₂ film photocatalyst. Also an excellent performance for the degradation of gaseous formaldehyde with mesoporous film photocatalyst was obtained. The photo degradation rate of gaseous formaldehyde for mesoporous TiO₂ film photocatalyst can arrive at six times of that for conventional TiO₂ film photocatalyst.     

Visible light photocatalysis on praseodymium(III)-nitrate-modified TiO2 prepared by an ultrasound method

Nanocrystalline TiO₂ incorporated with praseodymium(III) nitrate has been prepared by an ultrasound method in a sol–gel process. The prepared sample is characterized by X-ray diffraction (XRD), nitrogen adsorption (BET surface area), UV–vis diffuse reflectance spectroscopy (UV–Vis DRS) and X-ray photoelectron spectroscopy (XPS). The prepared material consists of TiO₂ nanocrystalline with 5 nm size incorporated with highly dispersed Pr(NO₃)₃. Visible light absorptions at 444, 469, 482 and 590 nm are observed in the prepared sample. These bands are attributed to the 4f transitions ³H₄ → ³P₂, ³H₄ → ³P₁, ³H₄ → ³P₀ and ³H₄ → ¹D₂ of praseodymium(III) ions, respectively. This sample Pr(NO₃)₃-TiO₂, as a novel visible light photocatalyst, shows high activity and stability in the decomposing rhodamine-B (RhB) and 4-chlorophenol (4-CP) under visible light irradiation. Results examined by electron spin resonance spectroscopy (ESR) reveal that the irradiation (>420 nm) of the photocatalyst dispersed in RhB aqueous solution induces the generation of highly active hydroxyl radicals (OH), leading to the cleavage of the whole conjugated chromophore structure of RhB. A mechanism based on local excitation of praseodymium(III) nitrate chromophore and interfacial charge transfer from the chromophore to TiO₂ is proposed to explain the formation of active hydroxyl radicals in the photocatalytic system under visible light irradiation.     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

Visible-light photocatalytic activity of TiO2/ZnS nanocomposites prepared by homogeneous hydrolysis

Photocatalytic active TiO₂/ZnS composites were prepared by homogeneous hydrolysis of mixture of titanium oxo-sulphate and zinc sulphate in aqueous solutions with thioacetamide. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission microscopy (HRTEM) and electron diffraction (ED). The nitrogen adsorption–desorption was used for surface area (BET) and porosity determination. Diffuse reflectance UV/VIS spectra for evaluation of photophysical properties were recorded in the diffuse reflectance mode (R100) and transformed to an absorption spectra through the Kubelka–Munk function. The method of UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies of the prepared TiO₂/ZnS nanocomposites. The photoactivity of the prepared TiO₂/ZnS nanocomposites was assessed by the photocatalytic decomposition of Orange II dye in an aqueous slurry under irradiation of 255 nm, 365 nm and 400 nm wavelength. Under the same conditions, the photocatalytic activity of the commercially available photocatalyst (Degussa P25), the pure anatase TiO₂ and sphalerite ZnS were also examined. The composite sample having the highest catalytic activity was obtained by hydrolysis of mixture solutions 0.63 M TiOSO₄ and 0.08 M ZnSO₄ · 7H₂O.     

Effect of silver on the photocatalytic degradation of humic acid

In this study, humic acid was mineralized and degraded photocatalytically in presence of bare TiO₂ and silver loaded TiO₂ (0.5–5.0 at.% Ag). X-ray diffraction (XRD) and inductive coupled plasma (ICP) analysis confirm the complete photodeposition of silver over TiO₂ by photodeposition method. X-ray photoemission spectroscopy (XPS) studies confirmed the presence of Ag⁰ in all Ag–TiO₂ samples and the absence of Ag⁺ ions. Silver loading over TiO₂ improved the rate of mineralization and degradation of humic acid with a maximum loading of 1.0 at.% Ag. Ninety percent carbon from humic acid was mineralized to CO₂ only after 60 min by using bare TiO₂ as a photocatalyst. However, this conversion was possible within 40 min by using 1.0 at.% Ag-loaded TiO₂. This observation verifies that coating of metals like silver over TiO₂ acts as an electron sink and can improve the redox reaction by preventing electron–hole recombination reaction. The optimum 1.0 at.% Ag loading in the current work is indicative that the blocking of the TiO₂ surface active sites by silver also plays an important role in the photocatalytic mineralization and degradation of humic acid. As the silver loading is increased, less number of active site are available over the surface of photocatalyst TiO₂ for redox reaction. This finding was supported by the TEM analysis of the photocatalyst samples.     

Photocatalytic reduction of water by TaON under visible light irradiation

Some noble metals have been studied as H₂ evolution promoters for TaON, a visible light driven oxynitride photocatalyst. H₂ evolution on TaON photocatalyst under visible light irradiation (420 nm≤λ≤500 nm) in an aqueous methanol solution was found to be remarkably enhanced by adding Ru as a noble metal co-catalyst.     

On the activation of Pt/Al2O3 catalysts in HC-SCR by sintering: determination of redox-active sites using Multitrack

A highly dispersed Pt/Al₂O₃ catalyst was used for the selective catalytic reduction of NO_x using propene (HC-SCR). Contact with the reaction gas mixture led to a significant activation of the catalyst at temperatures above 523 K. According to CO chemisorption data and HRTEM analysis, Pt particles on the activated catalyst had sintered. The redox behavior of the fresh and sintered catalysts was investigated using Multitrack, a TAP-like pulse reactor. If Pt particles on the catalyst are highly dispersed (average size below 2 nm), only a small part (10%) of the total number of Pt surface sites as determined by CO chemisorption (Pt_surf) participates in H₂/O₂ redox cycles (Pt_surf,redox) in Multitrack conditions. For a sintered catalyst, with an average particle size of 2.7 nm, the number of Pt_surf and Pt_surf,redox sites are in good agreement. Similar results were obtained for both catalysts using NO as the oxidant. The low number of Pt_surf,redox sites on highly dispersed Pt/Al₂O₃ is explained by the presence of a kinetically more stable—probably ionic—form of Pt---O bonds on all surface sites of the smaller Pt particles, including corner, edge and terrace sites. When the average particle size shifts to 2.7 nm, the kinetic stability of all Pt---O bonds is collectively decreased, enabling the participation of all Pt surface sites in the redox cycles.

A linear correlation between the NO_x conversion in HC-SCR, and the amount of Pt_surf,redox was found. This suggests that redox-active Pt sites are necessary for catalytic activity. In addition, the correlation could be significantly improved by assuming that Pt_surf,terrace sites of the particles larger than 2.7 nm are mainly responsible for HC-SCR activity in steady state conditions. Implications of these results for the pathway of HC-SCR over Pt catalysts are discussed.     

Hydrogen evolution by water splitting using novel composite zeolite-based photocatalyst

Novel zeolite-based material showing photocatalytic properties in the visible light have been synthesized by incorporating TiO₂, heteropolyacid (HPA) and transition metal, namely cobalt. This material shows high efficiency for water splitting under visible light irradiation. Hydrogen generation to the tune of 2171 μmol/h/g of TiO₂ has been achieved for the composite photocatalyst synthesized as compared to H₂ evolution rate to the tune of 131.6 μmol/h/g of TiO₂ for Degussa P25. This suggests that the TiO₂ which gets effectively dispersed and stabilized on the surface of zeolite works synergistically with cobalt and heteropolyacid to make the material active in visible light for evolution of hydrogen from water. TiO₂ is the photocatalyst, HPA functions as the dye sensitiser as well as redox system; zeolite functions as support matrix and as electron acceptor in synergy with cobalt. The probable mechanism for improved hydrogen evolution rate using such composite photocatalyst has been discussed.     

Rapid preparation of Bi2WO6 photocatalyst with nanosheet morphology via microwave-assisted solvothermal synthesis

Nanocrystalline Bi₂WO₆ photocatalyst with nanosheet morphology was successfully synthesized by a microwave-solvothermal process. The prepared samples were characterized by X-ray diffraction technique (XRD), BET surface area analysis, Uv–vis diffuse reflectance spectrum (Uv–vis DRS), field emission scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). In comparison with a conventional hydrothermal process, the microwave-solvothermal process presented many advantages in a shorter reaction time, higher surface area and more oxygen vacancies for the preparation of Bi₂WO₆ samples. The absorption edge of the samples is at ca. 445 nm, corresponding to band gap energy of about 2.8 eV. The morphology of nanosheets with nanocrystals was also observed. For the decomposition of Rhodamine B (RhB) under visible light irradiation (λ > 420 nm), nanocrystalline Bi₂WO₆ samples obtained by microwave-solvothermal process showed higher photocatalytic activity than that of the sample obtained by conventional hydrothermal process.     

The preparation of coupled WO3/TiO2 photocatalyst by ball milling

The coupled photocatalyst WO₃/TiO₂ is prepared by ball milling by doping WO₃ into TiO₂ and using H₂O solution as disperser. The coupled photocatalyst WO₃/TiO₂ is characterized by UV–VIS diffuse reflection spectrum, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Transmission electron microscopy (TEM). The results show that the optimum percentage of WO₃ doped is 3% and that the photocatalytic activity of the coupled WO₃/TiO₂ photocatalyst is much higher than that of TiO₂ and WO₃–TiO₂ with no ball milling. Compared with TiO₂, the photoexcited wavelength range of the WO₃/TiO₂ photocatalyst red-shifts about 50 nm, and the light absorption intensity is also improved. The crystal phase of TiO₂ is not changed and new crystal phases are not found during the process of ball milling. WO₃ and TiO₂ coupled highly, forming the WO₃/TiO₂ photocatalyst. The increased photocatalytic activity of the coupled photocatalyst may be attributed to the enhance charge separation efficiency and the extend wavelength range of photoexcitation.     

Preparation of novel TiP2O7 carbon composite using ion-exchanged resin (C467) and evaluation for photocatalytic decomposition of 2-propanol

TiP₂O₇ carbon composite photocatalyst was successfully prepared by using ion-exchanged resin (C467) containing amino phosphate by metal ion-exchanged carbothermal reduction (MIER-CTR) method using TiCl₃ and TiCl₄. During the carbonization process in nitrogen, the pre-oxidation (300–350 °C) in air is essential for producing homogeneously dispersed TiP₂O₇ on the carbon matrix. In the absence of pre-oxidation, the resin was melted. The carbonization temperature 500 °C was found to be suitable for producing single phase TiP₂O₇ with higher yields. Powder X-ray diffraction (XRD) and Raman spectroscopic results suggest the formation of TiP₂O₇, while X-ray diffraction results reveal that the crystallite size was less than 35 nm. UV-Vis studies show that the band gap of TiP₂O₇ was 3.32 eV. The TiP₂O₇ carbon composite catalyst was applied for the photocatalytic decomposition of 2-propanol at 30 °C using a mercury lamp (365 nm).     

Photocatalytic activities of AgSbO3 under visible light irradiation

A novel visible light sensitive photocatalyst, AgSbO₃ was prepared by a conventional solid-state reaction method. This oxide belonging to a cubic-pyrochlore structure can absorb visible light with wavelength up to about 480 nm. From the band structure calculation, we found that the top of the valence band consists of the hybridized Ag 4d and O 2p orbitals and the bottom of the conduction band mainly consists of the Ag 5s and the Sb 5s orbitals. Photocatalytic activities were evaluated using O₂ evolution from an aqueous silver nitrate solution and decomposition of gaseous 2-propanol under visible light irradiation. We found that AgSbO₃ shows a higher O₂ evolution activity than WO₃ and 2-propanol can be mineralized by the AgSbO₃ photocatalysis under visible light irradiation.     

Photocatalytic syngas synthesis from CO2 and H2O using ultrafine CeO2-decorated layered double hydroxide nanosheets under visible-light up to 600 nm

The rational design of photocatalyst that can effectively reduce CO₂ under visible light(l>400 nm),and simultaneously precise control of the products syngas(CO/H2)ratio is highly desirable for the Fischer-Tropsch reaction.In this work,we synthesized a series of CeO₂-decorated layered double hydroxides(LDHs,Ce-x)samples for photocatalytic CO₂ reduction.It was found that the selectivity and productivity of CO and H₂ from photoreduction of CO₂ in conjunction with Ru-complex as photosensitizer performed an obvious“volcano-like”trend,with the highest point at Ce-0.15 and the CO/H₂ ratio can be widely tunable from 1/7.7 to 1/1.3.Furthermore,compared with LDH,Ce-0.15 also drove photocatalytic CO₂ to syngas under 600 nm irradiation.It implied that an optimum amount of CeO₂ modifying LDH promoted the photoreduction of CO₂ to syngas.This report gives the way to fully utilize the rare earth elements and provides a promising route to enhance the photo-response ability and charge injection efficiency of LDH-based photocatalysts in the synthesis of syngas with a tunable ratio under visible light irradiation.     

N-doping TiO2 thin film prepared by heat treatment in electric field

A visible-light-active TiO_2−xN_x photocatalyst was synthesized in electric field. The N-doping TiO₂ film had a thickness of about 70–80 nm. The results of the photocatalytic experiments showed that the vis-activity rose largely. XPS and XRD analysis implied that the doping N substituted the oxygen-deficient in TiO₂ film. The Einstein shift in optical absorption spectrum of the N-doped film was also observed by the UV–VIS with a cut wave length of about 550 nm. Based on the experiment, it could be concluded that the N doping is effective to narrow the gap and enhance the photocatalysis.     

Microstructure, kinetics and mechanisms of CO2 catalytic decomposition over freshly reduced nano-crystallite CuFe2O4 at 400–600 °C

The decomposition of CO₂ was investigated as a process of both industrial and environmental importance. Copper ferrite was obtained by the thermal decomposition of acetate precursors. CuFe₂O₄ were isothermally reduced in H₂ flow at 400–600 °C, the isothermal reduction profiles obtained in this study show that a topochemical mode of reduction is done by which the reduction process proceeds. The nano-wires metallic phase of iron (106 nm) and copper (56 nm), produced from the complete reduction of CuFe₂O₄, were subjected to the direct reoxidation in CO₂ flow at 400–600 °C. The reoxidation process was found to be controlled by both the reduction and reoxidation temperatures. CO₂ decomposes to carbon nano-tubes during the reoxidation of the freshly reduced CuFe₂O₄. The prepared, completely reduced and reoxidized CuFe₂O₄ compacts, were characterized by XRD, SEM, TEM and reflected light microscope. For the reoxidation process, it is found that at the initial stages the reaction is controlled by the interfacial chemical reaction mechanism with some contribution to the gaseous diffusion mechanism. On the other hand at the intermediate and final stages the mechanism by which the reoxidation process proceeds was found to be the solid-state diffusion.     

FeWO4/WO3复合物的溶胶-凝胶合成及降解纺织染料废水研究

采用溶胶-凝胶法以尿素作为燃料一步合成具有高光催化活性的特殊异质结结构的钨酸铁/三氧化钨（FeWO₄/WO₃）复合光催化剂。X射线粉末衍射和傅里叶红外光谱分析表明,FeWO₄/WO₃复合光催化剂不含其他任何杂质,仅出现了FeWO₄和WO₃两相的衍射峰。FeWO₄/WO₃复合光催化剂由FeWO₄的菱形大颗粒和球形的WO₃小颗粒组成,二者以（111）（020）晶面耦合形成异质结。与WO₃相比,FeWO₄/WO₃复合光催化剂的光谱响应范围被拓展,且具有更高的光吸收系数,可响应可见光。对不同染料浓度、催化剂含量、pH和染料种类对FeWO₄/WO₃复合光催化剂的光催化活性影响的实验研究表明,染料浓度、催化剂含量和pH分别为50 mg/L、1.5 g/L和7时,FeWO₄/WO₃复合光催化剂在降解分散橙纺织染料时降解率达到97%。FeWO₄/WO₃复合光催化剂在降解分散黑、分散蓝、分散黄和分散橙时具有选择性。通过光催化机理分析发现,FeWO₄/WO₃复合光催化剂形成的特殊异质结结构可加速体系电荷载流子的转移和分离,进而使得FeWO₄/WO₃复合光催化剂的光催化活性得到提高。     

Effects of divalent metal ion (Mg, Zn and Be) doping on photocatalytic activity of ruthenium oxide-loaded gallium nitride for water splitting

The effects of divalent metal ion doping on the photocatalytic activity of GaN powder for overall water splitting were studied. The doping of Zn²⁺, Mg²⁺ and Be²⁺ to GaN converted it to be a remarkably active and stable photocatalyst in the presence of RuO₂ as a co-catalyst. Both H₂ and O₂ were produced from the initial stage of UV light illumination, and the ratio of H₂ to O₂ attained at the stoichiometric ratio of 2.0 at stationary conditions. Main absorption of undoped GaN was at around 390 nm, and a slight shift to longer wavelength occurred with the divalent metal ion-doped GaN. Undoped GaN showed photoluminescence peak due to band gap transition, whereas Zn²⁺ and Mg²⁺-doped GaN generated a broad photoluminescence peak having a center at around 450 nm and a tail extending to 600 nm. In RuO₂-dispersed Mg²⁺-doped GaN, with increasing content of Mg in starting materials used for preparation, the activity increased, whereas photoluminescence intensity decreased. The role of divalent metal ion dopants is concluded to produce p-type GaN, which is able to increase the concentration and mobility of holes.     

Hydrothermal synthesis of titanium dioxides from peroxotitanate solution using different amine group-containing organics and their photocatalytic activity

Nanosized TiO₂ particles were prepared by hydrothermal method of the amorphous powders which were precipitated in an aqueous peroxotitanate solution using different amine group-containing organics. The physical properties of prepared nanosized TiO₂ particles were investigated. We also examined the activity of TiO₂ particles as a photocatalyst for the decomposition of orange II. The TiO₂ particles calcined at 400 °C were shown to have a stable anatase phase which has no organic compounds. The particles size of titania particles decreased from 15 to 10 nm as the carbon chain length increased. The titania nanoparticles were shown to have a polygonal shape prepared using NH₄OH and tetramethylammonium hydroxide (TMAOH) as additives, however, the micrographs showed the spherical and narrow size distribution prepared using tetraethyl-ammonium hydroxide (TEAOH) and tetrabutylammonium hydroxide (TBAOH). The titania particles prepared using TEAOH as an amine group-containing organic showed the highest activity on the photocatalytic decomposition of orange II. In addition, the titania particles calcined at 500 °C showed the highest activity on the photocatalytic decomposition of orange II.