Investigation of Br–N Co-doped TiO<Subscript>2</Subscript> photocatalysts: preparation and photocatalytic activities under visible light

Bromine (Br) and nitrogen (N) co-doped TiO₂ ((Br–N–TiO₂) photocatalysts were prepared by a sol–gel method. The catalysts were characterized by X-ray Diffraction (XRD), N₂ adsorption and desorption isotherms, X-ray Photoelectron Spectra (XPS), UV-Vis Diffraction Spectra and Electron Spin Response (ESR) Spectra. Experiments on photodegradation of Methylene Blue (MB) and Sulfosalicylic Acid (SSA) under visible light were carried out to evaluate the photocatalytic activities of the catalysts. Chemical Oxygen Demand (COD) analysis was also conducted to evaluate the mineralization degrees of the catalysts in MB photodegradation. Enhanced photocatalytic activities were observed for the Br–N–TiO₂ catalysts in the experiments of MB and SSA photodegradation. A possible mechanism was proposed to explain the improved photocatalytic activities of the Br–N–TiO₂ catalysts.     

Preparation and photocatalytic activity of B,Ce Co-doped TiO2 hollow fibers photocatalyst

A series of B, Ce co-doped TiO₂ (B, Ce-TiO₂) photocatalytic materials with a hollow fiber structure were successfully prepared by template method using boric acid, ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500°C in an N₂ atmosphere for 2 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, and UV-visible spectroscopy (UV-Vis) were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photocatalytic performance of the samples was studied by photodegradation phenol in water under UV light irradiation. The results showed that the TiO₂ fiber materials have hollow structures, and the fiber structure materials showed better photocatalytic properties for the degradation of phenol than pure TiO₂ under UV light. In the experiment condition, the photocatalytic activity of B, Ce co-doped TiO₂ fibers was optimal of all the prepared samples. In addition, the possibility of cyclic usage of B, Ce co-doped TiO₂ fiber photocatalyst was also confirmed, the photocatalytic activity of TiO₂ fibers remained above 90% of that of the fresh sample after being used four times. The material was easily removed by centrifugal separation from the medium. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.     

可见光响应的镍硅共掺杂二氧化钛及其光催化性能

为了更好地利用太阳光和提高二氧化钛的光催化性能,以钛酸四正丁酯、正硅酸乙酯、六水合硝酸镍为原料,在高压釜中140℃非水溶剂热反应,所得材料经400℃焙烧制得镍硅共掺杂的二氧化钛光催化剂.所得材料用X射线衍射、氮吸附、透射电镜、X射线光电子能谱、傅里叶变换红外光谱、紫外漫反射等测试手段分析,结果显示所有样品均为锐钛矿型二氧化钛,Si和Ni均掺杂到TiO2体相中,样品具有较大的比表面积,其最大达303.3m2·g-1.在可见光照射下,以降解罗丹明-B为探针反应研究其可见光催化性能,与未掺杂和镍掺杂的二氧化钛相比较,共掺杂的二氧化钛具有更高的可见光催化性能,当Ni/Ti和Si/Ti的物质的量的比分别为0.01和0.20时,可见光催化性能最好.可见光催化性能的提高归因于镍和硅的协同作用.     

生物质C-N-P自掺杂TiO_2的合成及其对亚甲基兰的光催化降解活性

采用溶胶-超声辐照技术同步合成了生物质C-N-P自掺杂TiO_2复合催化剂,通过X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(FESEM)、紫外-可见漫反射光谱(UV-Vis-DRS)及光致发光光谱(PL)对样品进行了表征.以亚甲基兰(MB)为目标污染物,研究了C-N-P共掺杂TiO_2的可见光光催化性能.实验结果表明,在可见光照射下,光催化反应时间为2 h时,C-N-P共掺杂TiO_2复合催化剂对亚甲基兰的降解效率最高可达9 8.5%;相比纯TiO_2,C-N-P共掺杂TiO_2复合催化剂的比表面积增大,吸收边带红移,禁带宽度减小,相变温度升高,光生载流子复合率降低.     

F and Fe co-doped TiO2 with enhanced visible light photocatalytic activity

Four different sols, pure TiO₂, F doped TiO₂, Fe doped TiO₂, and F–Fe co-doped TiO₂ sols, were prepared by peroxidation at low temperature. The crystal structure, morphology, light adsorption, and photocatalytic properties of the pure and doped TiO₂ were examined by X-ray diffraction, transmission electron microscopy, and ultraviolet–visible spectrophotometry. The relationship between the average size, crystal type, range of visible light absorption, and photocatalytic activity and content and type of doped ions were investigated. The results showed that the average size of the F–Fe co-doped TiO₂ composed of both the anatase and rutile phases was the same as that of pure TiO₂. Furthermore, the visible light photocatalytic activity of the F–Fe co-doped TiO₂ was significantly improved over pure TiO₂, F-doped TiO₂, and Fe-doped TiO₂ due to the large red shift in the light adsorption edge.     

载钛羟基磷灰石光催化降解内分泌干扰物双酚A

对载钛羟基磷灰石（TiHAP）进行了透射电镜、X射线衍射、紫外-可见光谱和Zeta电位表征,并应用液相色谱-质谱技术对比了TiHAP和P25 TiO₂对环境内分泌干扰物双酚A（BPA）的吸附和光催化降解性能,探讨了富里酸和Fe³⁺对TiHAP薄膜光催化性能的影响。结果表明,TiHAP和TiO₂粉体对BPA的吸附符合Langmuir吸附等温方程,且前者吸附性能更大。TiHAP薄膜光催化降解BPA的性能优于TiO₂薄膜;富里酸和Fe³⁺对TiHAP和TiO₂薄膜光催化性能的影响趋势不同,从能带结构、电子转移和吸光性等角度分析了性能不同的原因。本结果可以为应用TiHAP降解环境内分泌干扰物提供依据。     

原位碳、氮共掺杂二氧化钛空心球的制备与可见光光催化性能

在H₂O₂-HF 的乙醇-水混合溶液中, 通过水热处理碳氮化钛(TiCN)制备了碳、氮共掺杂TiO₂ 空心球(CNTH). 用X 射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X 射线光电子能谱(XPS)和紫外-可见(UV-Vis)吸收光谱表征了所制备的样品. 在可见光(λ≥400 nm)照射下, 通过降解甲基蓝检测了碳、氮共掺杂TiO₂空心球的光催化活性. 结果表明, 源于TiCN中的部分碳和氮原子原位掺入了TiO₂的晶格中, 部分碳掺入TiO₂点阵的间隙中. 该材料在整个可见光区展示了增强的可见光吸收, 其带边明显红移. 光催化研究表明在强可见光吸收和独特的空心球结构的协同作用下, 碳、氮共掺杂TiO₂空心球展示了比P25更高的可见光光催化活性.     

Photocatalytic degradation of dimethyl phthalate ester using novel hydrophobic TiO2 pillared montmorillonite photocatalyst

TiO₂ pillared montmorillonites were prepared by introducing Ti⁴⁺ into a layer of montmorillonite modified with or without cetyltrimethylammonium bromide. The components and texture of the prepared composites were characterized by thermogravimetric analysis, X-ray powder diffraction and scanning electron misroscopy. The adsorption and photocatalytic degradation performance of a model environmental endocrine disruptor, dimethyl phthalate ester, were investigated using this newly prepared hydrophobic TiO₂ pillared montmorillonite photocatalyst. The adsorption of dimethyl phthalate ester from water varied from 9% to 28% on the prepared hydrophobic photocatalyst. Although the experimental results showed that the photocatalytic activity of the hydrophobic photocatalyst was slightly lower than that of hydrophilic one, electron spin resonance verified that hydroxyl radicals were also generated in hydrophobic TiO₂ pillared montmorillonite photocatalyst under UV irradiation. To elucidate the decomposition mechanism of dimethyl phthalate ester, 12 main photocatalytic intermediates were identified during the photocatalytic degradation process, and a plausible degradation mechanism was also proposed.     

Sol–gel preparation and characterization of Ag and Mg co-doped nano TiO<Subscript>2</Subscript>: efficient photocatalytic degradation of C.I. Acid Red 27

In this study, we successfully prepared pure, mono-doped, and Ag, Mg co-doped TiO₂ nanoparticles using the sol–gel method, with titanium tetraisopropoxide as the Ti source. The prepared samples were characterized by X-ray powder diffraction (XRD), specific surface area and porosity (BET and BJH) measurement, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, photoluminescence, and energy dispersive X-ray spectroscopy techniques. The XRD data showed that the prepared nanoparticles had the same crystals structures as the pure TiO₂. Also, DRS results indicated that the band gap of co-doped photocatalyst was smaller than that of the monometallic and undoped TiO₂ and that there was a shift in the absorption band towards the visible light region. Furthermore, the photocatalytic activity of the prepared catalysts was evaluated by the degradation of C.I. Acid Red 27 in aqueous solution under visible light irradiation. The results showed that Ag (0.08 mol%), Mg (0.2 mol%) co-doped TiO₂ had the highest photoactivity among all samples under visible light. It was concluded that co-doping of the Ag and Mg can significantly improve the photocatalytic activity of the prepared photocatalysts, due to the efficient inhibition of the recombination of photogenerated electron–hole pairs. The optimum calcination temperature and time were 450 °C and 3 h, respectively.     

Preparation of magnetically supported chromium and sulfur co-doped TiO2 and use for photocatalysis under visible light

Novel magnetic chromium and sulfur co-doped TiO₂ photocatalysts (M-Cr/S/TiO₂) have been prepared by a sol?Cgel process, using magnetic hollow fly ash microspheres as support material. The crystal phase of M-Cr/S/TiO₂ was characterized by X-ray diffraction, UV?Cvisible absorption spectroscopy, and transmission electron microscopy. The photocatalytic activity of the photocatalysts was examined by photodegradation of methyl orange in aqueous solution under visible light irradiation. The results showed that chromium and sulfur co-doped catalysts (Cr/S/TiO₂) containing 0.60?% (atomic ratio) chromium and 1.2?% (atomic ratio) sulfur calcined at 450?°C for 2?h had high catalytic efficiency under visible irradiation. It is worth mentioning that the floating M-Cr/S/TiO₂ catalyst had greater photocatalytic activity than Cr/S/TiO₂ powder. Therefore, M-Cr/S/TiO₂ is a promising, high-performing, visible-light-driven photocatalyst.     

Synthesis and photocatalytic activity of nanocrystalline TiO2 co-doped with nitrogen and cobalt(II)

Nitrogen-modified cobalt-doped TiO₂ materials were successfully prepared via a modified sol–gel method. The structure and properties of the catalysts were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM, ultraviolet–visible light diffuse reflectance spectra (UV–Vis DRS), N₂ adsorption–desorption isotherms, and energy-dispersive X-ray spectroscopy. The XRD patterns of the pure and co-doped TiO₂ samples indicate that the predominant phase was anatase. The average grain size obtained from TEM was approximately 10 nm. The Brunauer–Emmett–Teller analysis results indicate that the specific surface area was 77.7 m² g^?1. The UV–Vis DRS results for the co-doped sample reveal an absorption edge that had been red-shifted to 500 nm. The photocatalytic activities of the samples were evaluated through photodegradation of papermaking wastewater under UV and visible light irradiation. Compared with the cobalt-doped TiO₂ sample and Degussa P25, the 3 mol% N-doped mesoporous N/Co-TiO₂ photocatalyst exhibited the highest photocatalytic activity, which can be ascribed to the synergistic effect of the N and Co co-doping.     

Preparation of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles by mechanical alloying and annealing for sensitizing C-modified TiO<Subscript>2</Subscript> and acquirement of efficient photocatalyst

ZnFe₂O₄ nanoparticles sensitized by C-modified TiO₂ hybrids (ZnFe₂O₄–TiO₂/C) were successfully prepared by a feasible method. The ZnFe₂O₄ nanoparticles were prepared by mechanical alloying and annealing. The residual organic compounds in the synthetic process of TiO₂ were selected as the carbon source. The as-prepared composites were characterized by X-ray diffraction, Raman spectroscopy, X-ray fluorescence, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible light diffuse reflectance spectroscopy (UV–Vis) and N₂ adsorption–desorption analysis. The photocatalytic activity of the photocatalysts was measured by degradation of methyl orange under ultraviolet (UV) light and simulated solar irradiation, respectively. The results show that the carbon did not enter the TiO₂ lattice but adhered to the surface of TiO₂. The photocatalytic activity of the as-prepared C-modified TiO₂ (TiO₂/C) improved both under UV and simulated solar light irradiation, but the improvement was not dramatic. Introduction of ZnFe₂O₄ into the TiO₂/C could enhance the absorption spectrum range. The ZnFe₂O₄–TiO₂/C hybrids exhibited a higher photocatalytic activity both than that of the pure TiO₂ and TiO₂/C under either UV or simulated solar light irradiation. The complex synergistic effect plays an important role in improving the photocatalytic performance of ZnFe₂O₄–TiO₂/C composites. The optimum photocatalytic performance was obtained from the ZnFe₂O₄(0.8 wt%)–TiO₂/C sample.     

Synthesis and photocatalytic activity of co-doped mesoporous TiO2 on Brij98/CTAB composite surfactant template

Using composite surfactant templates, polyoxyethylene (20) oleyl ether (Brij98) and cetyl trimethyl ammonium bromide (CTAB), as structure-directing agents, N and La co-doped mesoporous TiO₂ complex photocatalysts were synthesized successfully. The micromorphology of co-doped mesoporous TiO₂ samples was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FT-IR), energy-dispersive X-ray spectrometer (EDS) and N₂ adsorption-desorption measurements. The results indicated that the complex photocatalyst prepared with a molar ratio of Brij98:CTAB=1:1 showed a uniform pore size of ca. 7 nm and a high specific surface area (S_BET) of 279.0 m² g⁻¹, and exhibited the highest photocatalytic activity for degradation of papermaking wastewater under ultra-violet light irradiation. The chemical oxygen demand (CODc_r) percent degradation was about 73% in 12 h and chroma percent degradation was 100% in 8 h.     

Metal–metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO₂ (Ce–TiO_2?xN_x) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N₂ adsorption and desorption methods, photoluminescence and ultraviolet–visible (UV–vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in ?3 state in Ce–TiO_2?xN_x. The modified surface of TiO₂ provides highly active sites for the dyes at the periphery of the Ce–O–Ti interface and also inhibits Ce particles from sintering. UV–visible DRS studies show that the metal–metal charge transfer (MMCT) of Ti/Ce assembly (Ti⁴⁺/Ce³⁺ → Ti³⁺/Ce⁴⁺) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron–hole pair separation between the two interfaces Ce–TiO_2?xN_x and Ce₂O₃. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO₂, Ce–TiO_2?xN_x and commercial Degussa P25 was determined. The higher visible light activity of Ce–TiO_2?xN_x was due to the participation of MMCT and interfacial charge transfer mechanism.     

Surface morphology and active sites of TiO<Subscript>2</Subscript> for photoassisted catalysis

The main aim of this work is to discriminate the closely related adsorption and catalytic degradation processes that occur during a photocatalytic reaction. Very high-surface-area TiO₂ and Pd-doped TiO₂ were synthesized by microwave-assisted hydrothermal synthesis and used for degradation of methylene blue as a model pollutant dye. Thorough structural, morphological, and surface analyses of the synthesized catalysts were conducted to investigate key material properties that influence adsorption and catalytic performance. The adsorption capacity of the catalysts was determined by fitting adsorption data using the Langmuir isotherm model, and the photocatalytic activity of the synthesized samples was evaluated by periodically measuring the concentration of methylene blue as it was photocatalytically degraded under ultraviolet (UV) light. The results indicated that noble-metal incorporation compromised adsorption but favored catalytic performance.     

Morphology and photocatalytic activity of TiO2 Aerogels

In this paper we describe a methodology to form a data base that will allow us to investigate the correlation between the morphology of Ti?₂ aerogels and their photocatalytic activity with respect to photodecomposition of a water soluble organic compound. We start with a qualitative theoretical argument in which we show that any functionality that involves optimization of different length scale should require some kind of ramified structure. For photocatalytic activity we need to optimize substrate and light absorptions with diffusion of products and reactants. We proceed to describe the techniques that we use to analyze and parametrize the morphology of the aerogels, using nitrogen adsorption and Small Angle Neutron Scattering. The photocatalytic activity is monitored through the photodecomposition of salicylic acid. We compare the adsorption and photodegradation of salicylic acid on the aerogels to many other forms of TiO₂ and report that under our experimental conditions the photocatalytic activity of the aerogels is superior.     

Synthesis and photocatalytic properties of core–shell TiO~2@ZnIn_2S_4 photocatalyst

A novel core–shell TiO2@ZnIn2S4composite has been synthesized successfully by a simple and flexible hydrothermal route using TiO2as precursors.The as-synthesized samples were characterized by X-ray diffraction,UV–vis diffuse reflectance spectra and transmission electron microscopy.The photocatalytic properties of samples were tested by degradation of aqueous methylene blue（MB）under visible light irradiation.It was found that the as-synthesized TiO2@ZnIn2S4photocatalyst was more effcient than TiO2and ZnIn2S4in the photocatalytic degradation of MB.Moreover,TEM images confrmed the TiO2@ZnIn2S4nanoparticles possessed a well-proportioned core–shell morphology.     

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.     

Direct synthesis of Nd3+ doped mesoporous TiO2 and investigation of its photocatalytic performance

Nd³⁺ doped mesoporous TiO₂ samples with different molar ratio of Nd/Ti were synthesized by a sol?Cgel method. The textural and optical properties of the samples were systematical characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption?Cdesorption isotherms, Fourier transform infrared spectroscopy and UV?CVisible absorbance spectroscopy. It was revealed that Nd³⁺ doping inhibited the phase transformation from anatase to rutile after calcination, and the mesoporous structure of doped samples was still retained with the increase of Nd/Ti molar ratio. The surface area of the samples varied from 137 to 210 m²g^?1 and the average pore size of them ranged between 5.7 and 8.2?nm. The photocatalytic activities of all the samples were evaluated by degradation methyl orange (MO) in aqueous solution as a model reaction under UV light irradiation. The results showed that the doped samples demonstrated a higher photocatalytic activity than the mesoporous TiO₂, and the 3?mol% Nd³⁺ doped mesoporous TiO₂ exhibited the best photocatalytic performance. Meanwhile, a promotion effect of the H₂O₂ added was verified in the degradation of MO.     

High temperature stability and photocatalytic activity of nanocrystalline anatase powders with Zr and Si co-dopants

TiO₂ nanopowders doped by Si and Zr were prepared by sol–gel method. The effects of Si and Zr doping on the structural, optical, and photo-catalytic properties of titania nanopowders have been studied by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a significant effect on anatase phase stability, crystallinity, and particle size of TiO₂. Titania rutile phase formation in ternary system (Ti–Si–Zr) was inhibited by Zr⁴⁺ and Si⁴⁺ co-doped TiO₂ in high temperatures (500–900 °C) and 36 mol% anatase composition is retained even after calcination at 1,000 °C. The photocatalyst activity was evaluated by photocatalytic degradation kinetics of aqueous methylen orange under visible radiation. The results show that the photocatalytic activity of the 20 %Si and 15 %Zr co-doped TiO₂ nanopowders have a larger degradation efficiency than pure TiO₂ under visible light.