Visible light absorption ability and photocatalytic oxidation activity of various interstitial N-doped TiO2 prepared from different nitrogen dopants

Nitrogen-doped TiO₂ was developed to enable photocatalytic reactions using the visible range of the solar spectrum. This work reports on the synthesis, characterisation and kinetic study of interstitial N-doped TiO₂ prepared by the sol–gel method using three different types of nitrogen dopants: diethanolamine, triethylamine and urea. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV–visible spectroscopy were used to analyse the titania. Different interstitial N-doped TiO₂ properties, such as absorption ability in the UV–visible light region, redshift in adsorption edge, good crystallisation and composition ratio of titania structures (anatase and rutile) could be obtained from different nitrogen dopants. Amongst investigated nitrogen precursors, diethanolamine provided the highest visible light absorption ability of interstitial N-doped TiO₂ with the smallest energy bandgap and the smallest anatase crystal size, resulting in the highest efficiency in 2-chlorophenol degradation. The photocatalytic activity of all N-doped TiO₂ can be arranged in the following order: TiO₂/diethanolamine > TiO₂/triethylamine > TiO₂/urea > un-doped TiO₂. The initial rate of 2-chlorophenol degradation using the interstitial N-doped TiO₂ with diethanolamine was 0.59 mg/L-min and the kinetic constant was 2.34 × 10⁻² min⁻¹ with a half-life of 98 min. In all cases, hydroquinone was detected as a major intermediate in the degradation of 2-chlorophenol.     

TiO2 supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

TiO₂ nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N₂-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO₂/SBA-15 composite was prepared by loading TiO₂ nanoparticles on uniform rod-like SBA-15 of 1 μm length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.     

Photocatalytic degradation of RhB over MgFe2O4/TiO2 composite materials

MgFe₂O₄/TiO₂ (MFO/TiO₂) composite photocatalysts were successfully synthesized using a mixing-annealing method. The synthesized composites exhibited significantly higher photocatalytic activity than a naked semiconductor in the photodegradation of Rhodamine B. Under UV and visible light irradiation, the optimal percentages of doped MgFe₂O₄ (MFO) were 2 wt.% and 3 wt.%, respectively. The effects of calcination temperature on photocatalytic activity were also investigated. The origin of the high level of activity was discussed based on the results of X-ray diffraction, UV-vis diffuse reflection spectroscopy, scanning electron microscopy, transmission electron microscopy, and nitrogen physical adsorption. The enhanced activity of the catalysts was mainly attributed to the synergetic effect between the two semiconductors, the band potential of which matched suitably.     

Preparation of novel CdS-graphene/TiO2 composites with high photocatalytic activity for methylene blue dye under visible light

In this study, CdS combined graphene/TiO₂ (CdS-graphene/TiO₂) composites were prepared by a sol–gel method to improve on the photocatalytic performance of TiO₂. These composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM). The photocatalytic activities were examined by the degradation of methylene blue (MB) under visible light irradiation. The photodegradation rate of MB under visible light irradiation reached 90·1% during 150 min. The kinetics of MB degradation were plotted alongside the values calculated from the Langmuir–Hinshelwood equation. 0·1 CGT sample showed the best photocatalytic activity, which was attributed to a cooperative reaction between the increase of photo-absorption effect by graphene and photocatalytic effect by CdS.     

Photocatalytic properties of Au/TiO2 thin films prepared by RF magnetron co-sputtering

Au/TiO₂ thin films with various Au doping contents were deposited on quartz substrates by radio frequency (RF) magnetron co-sputtering. The as-deposited Au/TiO₂ films were characterized by energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), XRD, and UV-vis techniques. Au doping and UV treatment enhanced the photocatalytic efficiency of TiO₂ thin films. The optimal RF power of the Au target and UV treatment time were 5 W and 1 h, respectively. The enhanced photoactivity of Au(5 W)/TiO₂ thin films with UV treatment is found to result from the increased hydroxyl concentration.     

Study of the deposition parameters and Fe-dopant effect in the photocatalytic activity of TiO2 films prepared by dc reactive magnetron sputtering

The reactive magnetron sputtering method was used to prepare pure and Fe-doped titanium dioxide thin films. The films were deposited onto microscope glass slides and polycarbonate plates at different total pressure and Fe-doping concentrations. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-visible spectroscopy (UV). For glass substrates a polycrystalline TiO₂ structure was verified with X-ray diffraction, which showed typical characteristic anatase reflections. An iron phase appeared in the highly Fe-doped samples. The absorption edges of the Fe-doped TiO₂ films shifted to visible region with increasing concentration of iron. For the polycarbonate substrate an amorphous TiO₂ structure was revealed for all deposition conditions. The effects of different Fe-doping and total pressure levels on the photocatalytic activity were obtained by the degradation rates of Rhodamine-B (RoB) dye under UV light irradiation. For the deposition conditions considered in this study the highest photodegradation rates were achieved for films deposited on the polymer substrates. Of these overall highest rates was achieved for deposition at 0.4 Pa and without doping. However, for both substrates, films prepared at the particular total pressure of 0.5 Pa and a low iron concentration showed better photocatalytic activity than the pure TiO₂ films prepared under the same deposition parameters. On the contrary, the photocatalytic degradation rates of RoB on the highly Fe-doped TiO₂ films decreased strongly.     

Photocatalytic performance of TiO2 films produced with combination of oxygen-plasma and rapid thermal annealing

In this work, a combination of oxygen plasma and rapid thermal annealing was suggested in order to oxidize the surface of titanium into TiO₂. A plasma was formed by employing pure oxygen at 150 W, 300 W, and 400 W under a pressure of 7.5 to 8.5 Pa for 5 to 10 min. The TiO₂ was then subjected to rapid thermal annealing (RTA) at a temperature of 400 to 500 °C for 1 min. From the attained results, an RF power of 300 W for 5 min was observed to be sufficient to produce an optimal photocatalytic TiO₂ film. Optimal conditions were confirmed by additional experiments involving humic acid (HA) degradation of the TiO₂ films. When compared to a traditional TiO₂ film, a TiO₂ film prepared with an oxygen-plasma treatment and RTA system exhibited improved photocatalytic capability for HA photodegradation in an aqueous solution. Therefore, this process proposed in this work can be an excellent alternative to the traditional method for fabricating photocatalytic TiO₂ films.     

Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

碳纳米管修饰LaFeO3/TiO2复合材料的光催化性能与机理

采用超声辅助溶胶凝胶法制备了LaFeO₃颗粒,进一步以碳纳米管(CNTs)为基底和钛酸丁酯为前体,通过一步水热法煅烧合成CNTs/TiO₂/LaFeO₃(CTF)三元异质结光催化复合材料。通过扫描电子显微镜(SEM)、X射线衍射分析(XRD)、氮气吸附-解吸等温线(BET)、紫外-可见分光光度计(UV-Vis)、光致发光光谱(PL)等表征手段对材料的形貌与特征结构、比表面积和孔径结构以及光学特征进行了分析,并在紫外光下通过降解活性黑五(RB5)测试样品的光催化性能。结果表明,以CNTs作为载体,能够有效提升LaFeO₃/TiO₂复合材料的光催化性能。当CNTs在复合材料中的质量占比为5%时,150 W汞灯照射下RB5的50 min去除率可达99.5%。CNTs一方面通过增加复合材料的比较面积为催化反应的进行提供了更多的活性位点,更为重要的是,CNTs作为光生载流子传输的通道加快了电荷分离效率,提升了复合材料的降解能力和催化反应动力学进程。     

Hydrothermal synthesis and characterization of TiO2 nanorod arrays on glass substrates

Large-scale, well-aligned single crystalline TiO₂ nanorod arrays were prepared on the pre-treated glass substrate by a hydrothermal approach. The as-prepared TiO₂ nanorod arrays were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. X-ray diffraction results show that the main phase of TiO₂ is rutile. Scanning electron microscopy and transmission electron microscopy results demonstrate that the large-scale TiO₂ nanorod arrays grown on the pre-treated glass substrate are well-aligned single crystal and grow along [0 0 1] direction. The average diameter and length of the nanorods are approximately 21 and 400 nm, respectively. The photocatalytic activity of TiO₂ nanorod arrays was investigated by measuring the photodegradation rate of methyl blue aqueous solution under UV irradiation (254 nm). And the results indicate that TiO₂ nanorod arrays exhibit relatively higher photocatalytic activity.     

Mesoporous Au/TiO2 composites preparation,characterization, and photocatalytic properties

In this work, mesoporous Au/TiO₂ composites have been synthesized and tested on photodegradation of methylene blue dye solution. Mesoporous TiO₂ prepared at 450 °C using triblock polymer F127 as structure-directing agent was applied as substrate, while various HAuCl₄ concentrations were used for Au loading through deposition-precipitation method using urea as precipitator and hydrogen reducing process. The influences of Au loading on the microstructures of mesoporous TiO₂ including degree of dispersion, particle size, surface area, light absorption, and band gap were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), diffuse reflection infrared Fourier transformed spectroscopy (DRIFT), N₂ adsorption–desorption isotherm analysis (BET), and UV–Vis diffuse reflectance spectra. With Au loading, the size of TiO₂ nanoparticles in Au/TiO₂ composites is similar as that of TiO₂ substrate. However, the degree of dispersion was greatly improved. Furthermore, an obvious surface plasmon resonance centered at 570 nm was found in UV–Vis diffuse reflectance spectra for Au/TiO₂ composites. Au loading also induced an obvious red shift of light absorption from UV region to visible region and strengthened both UV and visible light absorption in contrast to substrate. Photodegradation results verified that photocatalytic activity of mesoporous TiO₂ was improved by Au loading. 0.25%Au/TiO₂ composite showed the highest activity, which may be ascribed to its high surface hydroxyl content and the formed Schottky junction after Au loading. These results suggested that noble metal modification is a promising way to synthesize photocatalysts with both high activity and visible light sensitivity.     

Facile synthesis of Ag nanoparticles supported on TiO2 inverse opal with enhanced visible-light photocatalytic activity

TiO₂ inverse opal films loaded with silver nanoparticles (ATIO) were synthesized on glass substrates. TiO₂ inverse opal (TIO) films were prepared via a sol-gel process using self-assembly of SiO₂ colloidal crystal template and a facile wet chemical route featuring an AgNO₃ precursor solution to fabricate silver nanoparticles on the TIO films. The inverse opal structure and Ag deposition physically and chemically modify titania, respectively. The catalysts were characterized by Raman spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), UV-vis absorption spectra, X-ray photoelectron spectroscopy and photoluminescence spectroscopy. The HRTEM results show that Ag nanoparticles measuring 5-10 nm were evenly distributed on TIO. Both the UV- and visible-light photocatalytic activities of the samples were evaluated by analyzing the degradation of methylene blue (MB) in aqueous solution. The results reveal that the apparent reaction rate constant (k_app) of MB degradation of the sample ATIO under UV-light irradiation is approximately 1.5 times that of the conventional Ag-loaded TiO₂ film (ATF) without an ordered porous structure at an AgNO₃ concentration of 5 mM in the precursor solution. At an AgNO₃ concentration of 10 mM, the sample exhibits a k_app value approximately 4.2 times that of ATF under visible-light irradiation. This enhanced visible-light photocatalytic performance can be attributed to the synergistic effect of optimized Ag nanoparticle deposition and an ordered macroporous TIO structure. Repeated cycling tests revealed that the samples showed stable photocatalytic activity, even after six repeated cycles.     

Preparation of Fe-doped TiO2 nanotube arrays and their photocatalytic activities under visible light

Fe-doped TiO₂ nanotube arrays have been prepared by the template-based liquid phase deposition method. Their morphologies, structures and optical properties were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and UV-vis absorption spectroscopy. Their photocatalytic activities were evaluated by the degradation of methylene blue under visible light. The UV-vis absorption spectra of the Fe-doped TiO₂ nanotube arrays showed a red shift and an enhancement of the absorption in the visible region compared to the undoped sample. The Fe-doped TiO₂ nanotube arrays exhibited good photocatalytic activities under visible light irradiation, and the optimum dopant amount was found to be 5.9 at% in our experiments.     

Flame-made single phase Zn2TiO4 nanoparticles

Using zinc naphthenate and titanium tetra isopropoxide (1:1 mol.%) dissolved in ethanol as precursors, single phase Zn₂TiO₄ nanoparticles were synthesized by the flame spray pyrolysis technique. The Zn₂TiO₄ nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. The average diameter of Zn₂TiO₄ spherical particles was in the range of 5 to 10 nm under 5/5 (precursor/oxygen) flame conditions. All peaks can be confirmed to correspond to the cubic structure of Zn₂TiO₄ (JCPDS No. 25-1164). The SEM result showed the presence of agglomerated nanospheres with an average diameter of 10-20 nm. The crystallite sizes of spherical particles were found to be in the range of 5-18 nm from the TEM image. An average BET equivalent particle diameter (d_BET) was calculated using the density of Zn₂TiO₄.     

Preparation,characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles

Holmium-doped TiO₂ nanoparticles with high photocatalytic activities were prepared by sol–gel method and characterized by X-ray diffraction, transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy, and surface area measurement by nitrogen adsorption in this study. Experimental results indicated holmium doping could increase the surface area of TiO₂ nanoparticles, and inhibit the growth of crystalline size and the anatase-to-rutile phase transformation. The results of photodegrading methyl orange showed holmium doping improved the photocatalytic activity of TiO₂, and the reasons could be attributed to the synergetic effects of large surface areas, small crystallite size, lattice distortion and more charge imbalance of holmium-doped TiO₂. In our experiment, the optimal doped amount was 0.3 mol.% for the maximum photocatalytic degradation ratio when holmium-doped TiO₂ was calcined at 500 °C, and the optimal calcined temperature was 600 °C when the doped amount was 0.5 mol.%.     

Solar photocatalytic degradation of isoproturon over TiO2/H-MOR composite systems

The photocatalytic degradation and mineralization of isoproturon herbicide was investigated in aqueous solution containing TiO₂ over H-mordenite (H-MOR) photocatalysts under solar light. The catalysts are characterized by X-ray diffraction (XRD), UV–Vis diffused reflectance spectra (UV–Vis DRS), Fourier transform-infra red spectra (FT-IR) and scanning electron microscopy (SEM) techniques. The effect of TiO₂, H-MOR support and different wt% of TiO₂ over the support on the photocatalytic degradation and influence of parameters such as TiO₂ loading, catalyst amount, pH and initial concentration of isoproturon on degradation are evaluated. 15 wt% TiO₂/H-MOR composite is found to be optimum. The degradation reaction follows pseudo-first order kinetics and is discussed in terms of Langmuir–Hinshelwood (L–H) kinetic model. The extent of isoproturon mineralization studied with chemical oxygen demand (COD) and total organic carbon (TOC) measurements and 80% mineralization occurred in 5 h. A plausible mechanism is proposed based on the intermediates identified by liquid chromatography–mass spectroscopy (LC–MS).     

Photochemical synthesis and characterization of Ag/TiO2 nanotube composites

TiO₂ nanotubes were fabricated by a hydrothermal method. Silver nanoparticles with diameters around 3–5 nm were loaded onto the surface of TiO₂ nanotubes via a deposition approach followed by a photochemical reduction process under ultraviolet irradiation. Transmission electron microscopy (TEM), N₂ adsorption measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-vis diffuse reflectance spectroscopy (UV-vis), and fluorescence spectroscopy (FL) were applied to characterize the as-prepared Ag/TiO₂ nanotube composites. The photocatalytic activity of the as-prepared materials was investigated by photodegrading of methyl orange. The results showed that silver particles were in zero oxidation state and highly dispersed on the surface of TiO₂ nanotubes when the concentration of Ag⁺ was low. The presence of metallic silver can help the electron-hole separation by attracting photoelectrons. The Ag/TiO₂ nanotube composites with a suitable amount of silver showed a further improvement on the photocatalytic activity for degradation of methyl orange in water.     

Novel photocatalytic TiO2 coatings produced by HVOF thermal spraying process

Titanium dioxide coatings were deposited by high velocity oxy-fuel spraying (HVOF) using agglomerated nano-powders. Different spraying parameters were used to determine their influences on the crystallite structure and photocatalytic performance of the coatings. The as-sprayed TiO₂ coatings were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Photocatalytic efficiency of the elaborated samples was evaluated from the conversion rate of ethanol. A high anatase content of 80% by volume was achieved for the coating deposited by a 120 ml/min fuel flow rate. The results show that the as-sprayed TiO₂ HVOF coatings were highly photocatalytically reactive for the degradation of ethanol.     

Removal of fluoride from aqueous solution by polypyrrole/Fe3O4 magnetic nanocomposite

Highly efficient visible light TiO₂ photocatalyst was prepared by the sol-gel method at lower temperature (≤300 °C), and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and differential scanning calorimetry-thermogravimetric analysis (DSC-TGA). The effects of the heat treatment temperature and time of the as-prepared TiO₂ on its visible light photocatalytic activity were investigated by monitoring the degradation of methyl orange solution under visible light irradiation (wavelength ≥ 400 nm). Results show that the as-prepared TiO₂ nanoparticles possess an anatase phase and mesoporous structure with carbon self-doping and visible photosensitive organic groups. The visible light photocatalytic activity of the as-prepared TiO₂ is greatly higher than those of the commercial TiO₂ (P-25) and other visible photocatalysts reported in literature (such as PPy/TiO₂, P3HT/TiO₂, PANI/TiO₂, N-TiO₂ and Fe³⁺-TiO₂) and its photocatalytic stability is excellent. The reasons for improving the visible light photocatalytic activity of the as-prepared TiO₂ can be explained by carbon self-doping and a large amount of visible photosensitive groups existing in the as-prepared TiO₂. The apparent optical thickness (τ_app), local volumetric rate of photo absorption (LVRPA) and kinetic constant (k_T) of the photodegradation system were calculated.     

Facile synthesis of nano-TiO2/stellerite composite with efficient photocatalytic degradation of phenol

In this paper, we report a kind of nano-TiO₂/stellerite composite with enhanced photoactivity, which was synthesized by a typical homogeneous precipitation method followed by a calcination crystallization process using natural stellerite as support. The as-prepared composites were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption, high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The results showed that TiO₂ loading amounts and calcination temperatures had significant influence on the adsorption and photocatalytic degradation properties of phenol. Moreover, it was indicated that the TiO₂ nanoparticles (NPs) with smaller grain size (around 12.0?nm) and narrower size distributions were uniformly deposited on the surface of stellerite as a layer of film. Compared with commercial P25, the received composite exhibited more superior photocatalytic degradation performance towards phenol. The enhanced photocatalytic degradation performance should result from the better dispersibility of TiO₂ NPs and higher separation efficiency of photogenerated electron-hole pairs. This work may set foundation for the practical application of this new composite photocatalyst in the field of wastewater treatment.