Visible-light responsive dye-modified TiO2 photocatalyst

A series of dye-modified TiO₂ photocatalysts were synthesized using dye Chrysoidine G (CG), tolylene-2,4-diisocyanate (TDI), and commercial TiO₂ (Degussa P25) as starting materials. TDI was used as a bridging molecule whose two -NCO groups reacted with Ti-OH of TiO₂ and -NH₂ groups of CG, respectively. As a result, special organic complexes were formed on the TiO₂ surface via stable π-conjugated chemical bonds between TiO₂ and dye molecules, confirmed by FT-IR, XPS, and UV-vis spectra. Due to the existence of π-conjugated surface organic complexes, the as-synthesized photocatalysts showed a great improvement in visible absorption (400-550 nm). Methylene blue, as a photodegradation target, was used to evaluate the photocatalytic performance, and the dye-modified TiO₂ exhibited much better activity under the visible light irradiation than bare TiO₂.     

Phase transformations in nanocrystalline TiO2 milled in different milling atmospheres

The structural evolution of nanocrystalline TiO₂ milled in different milling atmospheres was studied by X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy. Rietveld refinements of the XRD data showed that high-energy ball milling induced the transformations from anatase to srilankite and rutile at room temperature and ambient pressure. The milling atmospheres with different oxygen partial pressures had an influence on the transformation kinetics of anatase. When the nanocrystalline TiO₂ powders were, respectively, milled in oxygen, air and nitrogen atmospheres, the transformation rates of anatases in turn increased with a decrease in oxygen partial pressure of the milling atmosphere, due to the reducing concentration of oxygen vacancies in the milled TiO₂ lattice.     

Characterization of mesoporous nanocrystalline TiO2 photocatalysts synthesized via a sol-solvothermal process at a low temperature

Nanocrystalline TiO₂ samples with mesoporous structure were prepared via a solvothermal treatment of surfactant-stabilized TiO₂ sols. The samples were obtained from media of different acidities including nitric acid, deionized water, and ammonia (denoted as HT-1, HT-2 and HT-3, respectively). These samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂-sorption (BET surface area), micro-Raman spectroscopy, infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were tested by the self-photosensitized degradation of an azo dye, Mordant Yellow 10 (MY), in aqueous solution under visible light irradiation. The results reveal that all three samples have high surface area and are pure anatase phase. The sample prepared in nitric acid medium possesses the most ideal mesoporous structure and also exhibits a blue shift in the Raman spectrum. All three samples show much higher photocatalytic activity than the commercial P-25. The activity order of the three samples is HT-1>HT-2>HT-3.     

Preparation and photocatalytic degradability of TiO2/polyacrylamide composite

Based on the unique absorbent characters and three-dimensional network structure of polyacrylamide (PAM) superabsorbent polymer, a photocatalytic degradable TiO₂/PAM composite was synthesized by an aqueous solution polymerization method with N,N′-methylene bisacrylamide as crosslinker, potassium peroxydisulfate as initiator, acrylamide as monomer, and TiO₂ (P-25) as functional filler. The photocatalytic degradability of the composite was evaluated using methyl orange as photodegradation target, and the recovery and reproducibility of the composite was investigated. It was found that TiO₂/PAM composite had a good photocatalytic degradability, the composite also possessed a good reproducibility of photocatalytic degradability, which is possible to be used in practical process.     

Preparation and photocatalytic activity of Sb2S3/Bi2S3 doped TiO2 from complex precursor via gel-hydrothermal treatment

Sb₂S₃/Bi₂S₃ doped TiO₂ were prepared with the coordination compounds [M(S₂CNEt)₃] (M=Sb, Bi; S₂CNEt=pyrrolidinedithiocarbamate) as precursors via gel-hydrothermal techniques. The doped TiO₂ were characterized by XRD, SEM, XPS and UV-vis diffuse reflectance means. The photocatalyst based on doped TiO₂ for photodecolorization of 4-nitrophenol (4-NP) was examined. The optimal Bi₂S₃/Sb₂S₃ content, pH and different doped techniques have been investigated. Photocatalytic tests reveal that M₂S₃ doped TiO₂ via the gel-hydrothermal route performs better photocatalytic activity for photodegradation reaction of 4-nitrophenol (4-NP).     

Solid-phase photocatalytic degradation of polystyrene plastic with TiO2 as photocatalyst

Solid-phase photocatalytic degradation of polystyrene (PS) plastic with TiO₂ as photocatalyst was investigated in the ambient air under ultraviolet light irradiation. Higher weight loss rate, lower average molecular weight, increased carbonyl peak intensity, less volatile organics and more CO₂ emitted with irradiation in PS-TiO₂ composite sample compared to pure PS sample were observed. These facts indicated the higher photodegradation rate of PS-TiO₂ sample than that of PS sample, and emphasized the potential of the composite sample in bring about complete photodegradation of polystyrene plastic. It is implied that the degradation initially occurred over TiO₂ particles, followed by the diffusion reaction with the aid of reactive oxygen species generated on TiO₂ particle surface.     

TiO2 nanoparticles incorporated with CuInS2 clusters: preparation and photocatalytic activity for degradation of 4-nitrophenol

TiO₂ nanoparticles incorporated with CuInS₂ clusters were prepared in a solvothermal process and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersion X-ray analysis (EDX). Compared with pure TiO₂ nanoparticles, the TiO₂ nanoparticles incorporated with CuInS₂ clusters display higher photocatalytic activity with 99.9% of degradation ratio of 4-nitrophenol after 2 h irradiation. In order to investigate the effect of the CuInS₂ clusters on the photocatalytic activity of TiO₂ nanoparticles, diffuse reflectance UV–Vis spectra (DRS), photoluminescence (PL) spectra, and photocurrent action spectra were measured. The results indicate that the enhanced photocatalytic activity is probably due to the interface between TiO₂ and CuInS₂ as a trap of the photogenerated electrons to decrease the recombination of electrons and holes.     

A one-step solvothermal route for the synthesis of nanocrystalline anatase TiO2 doped with lanthanide ions

A one-step solvothermal synthesis is proposed for the preparation of nanocrystalline single-phase TiO₂ in the anatase form doped with lanthanide ions Eu³⁺, Er³⁺ and Sm³⁺. The structural properties of these products have been investigated by using X-ray powder diffraction, electron microscopy and Raman spectroscopy. Furthermore, the laser-excited luminescence spectra of the samples have been measured and analyzed. Following this route, the doping process turns out to be highly favorite and the resulting materials show an efficient luminescence in the visible region.     

TiO2纳米线的制备及其光电性能研究

利用在钛箔表面沉积一层TiO₂纳米粒子作为晶种，与NaOH反应，制备了一维物质TiO₂纳米线。并用XRD、SEM、TEM、HRTEM及EDS等分析手段对TiO₂纳米线的成分、形貌、结构进行表征。结果表明，采用该方法制得的TiO₂纳米线直径在20～50 nm左右、长度可达几微米。反应温度能显著影响所得纳米线的形貌。研究了TiO₂纳米线的光电化学性能。随反应温度的升高TiO₂纳米线光电转换效率增大。     

静电自组装制备纳米TiO2/SiO2光催化材料

采用静电自组装方法制备了纳米TiO2/SiO2光催化材料。采用巯丙基三甲氧基硅烷偶联剂对SiO2进行干法改性,采用双氧水/冰醋酸将偶联剂巯基基团氧化为磺酸基基团。在正负电荷的吸引下,带负电荷的SiO2与带正电荷的钛聚合阳离子自发地组装在一起,经一定温度热处理得到纳米TiO2/SiO2光催化材料。采用XRD、FTIR、PL、UV-Vis DRS、SEM和ICP等对材料进行了分析和表征。采用甲基橙溶液评价材料的光催化性能。结果表明:SiO2促使锐钛矿的形成,抑制锐钛矿向金红石的转变,减小TiO2的晶粒尺寸,使得TiO2光吸收波长发生蓝移。TiO2与SiO2通过Si-O-Ti键发生结合。采用静电自组装方法制备的材料中TiO2的含量高于传统方法,导致材料的光催化性能有所提高。     

Preparation, characterization, and infrared emissivity property of optically active polyurethane/TiO2/SiO2 multilayered microspheres

Optically active polyurethane/titania/silica (LPU/TiO₂/SiO₂) multilayered core–shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. LPU/TiO₂/SiO₂ was characterized by FT-IR, UV–vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), SEM and TEM, and the infrared emissivity value (8–14 μm) was investigated in addition. The results indicated that titania and polyurethane had been successfully coated onto the surfaces of silica microspheres. LPU/TiO₂/SiO₂ exhibited clearly multilayered core–shell construction. The infrared emissivity values reduced along with the increase of covering layers thus proved that the interfacial interactions had direct influence on the infrared emissivity. Besides, LPU/TiO₂/SiO₂ multilayered microspheres based on the optically active polyurethane took advantages of the orderly secondary structure and strengthened interfacial synergistic actions. Consequently, it possessed the lowest infrared emissivity value.     

Structural characterization and photocatalytic activity of hollow binary ZrO2/TiO2 oxide fibers

The formation of hollow binary ZrO₂/TiO₂ oxide fibers using mixed precursor solutions was achieved by activated carbon fibers templating technique combined with solvothermal process. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis, and infrared (IR) spectroscopy. The binary oxide system shows the anatase-type TiO₂ and tetragonal phase of ZrO₂, and the introduction of ZrO₂ notably inhibits the growth of TiO₂ nanocrystallites. Although calcined at 575 °C, all hollow ZrO₂/TiO₂ fibers exhibit higher surface areas (>113 m²/g) than pure TiO₂ hollow fibers. The Pyridine adsorption on ZrO₂/TiO₂ sample indicates the presence of stronger surface acid sites. Such properties bring about that the binary oxide system possesses higher efficiency and durable activity stability for photodegradation of gaseous ethylene and trichloromethane than P25 TiO₂. In addition, the macroscopic felt form for the resulting materials is more beneficial for practical applications than traditional catalysts forms.     

Preparation and photocatalytic activity of high-efficiency visible-light-responsive photocatalyst SnSx/TiO2

Visible-light-responsive composite photocatalysts SnS₂/TiO₂ and SnS/TiO₂ with different mass ratios were prepared by in-situ synthesis technology in solution with commercial TiO₂. The junction-based materials SnS_x (x=1, 2)/TiO₂ were found to have high visible-light photocatalytic performance and possess much better activity than the single-phase SnS_x or TiO₂. The greatly enhanced photocatalytic activity of the SnS_x/TiO₂ composites was mainly attributed to the matching band potentials and efficient charge transfer and separation at the tight-bonding interface between SnS_x and TiO₂. The fact was confirmed by the comparison of photocatalytic activities of the SnS₂/TiO₂ samples prepared by physical mixing method and in-situ synthesis technique.     

双介孔结构的纳米TiO2/I2复合材料的制备及其可见光催化性能

以钛酸丁酯为前驱体, 碘溶胶为碘源, 在室温下采用水解沉淀法制备了单质碘和纳米TiO₂复合的双介孔结构光催化剂(M-I₂-TiO₂). 采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I₂-TiO₂进行了表征. 以次甲基蓝(MB)溶液为模拟废水, 对M-I₂-TiO₂的光催化性能进行了评价, 研究了不同热处理温度对光催化活性的影响. 结果表明, M-I₂-TiO₂在可见光区有显著的吸收, 300 ℃热处理得到的样品比表面积高达227.6 m²/g, 600 ℃热处理所得样品的比表面积仍高达111.8 m²/g, 而400 ℃热处理所得样品具有最好的光催化降解性能. 双介孔结构纳米TiO₂/I₂复合材料的光催化降解性能显著高于相同方法制备的纯TiO₂和Degussa P-25商业产品. 催化剂经6次重复使用其光催化活性基本保持不变.     

低温下溶胶凝胶法制备TiO2纳米晶

从含过量水的溶胶出发,在室温下得到了TiO₂纳米晶。通过红外光谱,透射电子显微镜法和X射线粉末衍射法对含有过量水的溶胶体系中TiO₂纳米晶的室温形成机理进行了研究。与传统的溶胶凝胶法相比,在改良的溶胶凝胶体系中,在缩聚反应之前由于水过量使得钛的先驱体快速且充分的水解,从而生成[TiO₆]基团,随之形成TiO₂纳米晶。晶粒的尺寸为约3.5 nm,该法得到的TiO₂纳米晶比传统溶胶凝胶法得到的TiO₂纳米晶和商用光催化剂德固赛P25具有更好的光催化活性。     

电化学溶解钛金属直接水解法制备纳米TiO2

Metallic titanium was electrochemically dissoluted in absolute ethanol in the presence of Et4N•Br(as electro conductive additive),The electrolyte solution was then directly hydrolysized to obtain nanocrystalline TiO2.The powder obtained was calcined at 720℃ for 1 h.FT IR,Raman spectra,XRD and TEM were used to investigate the structure and particle size of the powder.Studies showed that the nanocrystalline TiO2 prepared by this method was of monocline structure with high textural stability and narrow size distribution of 10－20 nm,and its Raman spectra showed a shift of about 25 cm－1.The experiments also showed that the product yield could be improved by controlling the temperature under 50－60℃,selecting R4N•Br as conductive additive and preventing titanium anode from being passivated.The electrochemical dissolution of metal anode may be recommanded as a promising technique for the synthesis of nanomaterials.     

The release of TiO2 and SiO2 nanoparticles from nanocomposites

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO₂ or amorphous SiO₂ nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO₂ and TiO₂ nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.     

蛭石负载TiO2光催化剂的制备与性能

以新疆尉犁工业蛭石为载体,采用溶胶-凝胶法制备负载型二氧化钛光催化剂,利用XRD、TG、SEM、IR和低温N₂吸附－脱附对负载型二氧化钛进行表征,并以亚甲基蓝为目标降解物对其光催化性能进行研究。讨论了不同TiO₂负载量、反应温度和煅烧温度等因素对负载型二氧化钛光催化性能的影响,结果表明：TiO₂负载量为4.0wt%,反应温度为40 ℃,煅烧温度为400 ℃时,复合材料光催化效果最好,经60 W紫外灯照射20 min后,TiO₂/VMT复合材料对亚甲基蓝溶液的降解率为92.08%。     

Dependence of nitrogen doping on TiO2 precursor annealed under NH3 flow

N-doped TiO₂ photocatalysts were prepared by annealing two different precursors, P25 and a TiO₂ xerogel powder under NH₃/Ar flow at 500, 550, and 600 °C. The xerogel powder prepared by peptizing Ti(OH)₄ with HNO₃ was composed of nanoparticles and had large specific surface area. During the annealing process, the xerogel powder underwent increase in crystallinity, grain growth and phase transformation, whereas P25 did not show obvious changes. Compared with the N-doped TiO₂ photocatalysts from P25, the N-doped TiO₂ photocatalysts from the xerogel powder possessed higher concentrations of the substitutional nitrogen and exhibited more obvious absorption in the visible light region. The N-doped TiO₂ photocatalysts from the xerogel powder exhibited obvious visible-light activities for photodegrading methylene blue and the sample prepared at 500 °C achieved the best performance with a rate constant (k) about 0.44 h⁻¹, whereas those from P25 did not exhibit improved visible-light activities.     

Preparation and characterization of mesoporous TiO2-CeO2 nanopowders respond to visible wavelength

Mesoporous TiO₂-CeO₂ nanopowders responding to visible wavelength were synthesized by using a surfactant assisted sol-gel technique. They were obtained using metal alkoxide precursors modified with acetylacetone (ACA) and laurylamine hydrochloride (LAHC) as surfactant. The samples were characterized by XRD, nitrogen adsorption isotherm, SEM, TEM, and selected area electron diffraction (SAED), respectively. The 95 mol% TiO₂-5 mol% CeO₂ system yielded single anatase phase, however, further addition of the CeO₂ formed cubic CeO₂ structure while anatase TiO₂ decreased. Additions of 5 and 10 mol% CeO₂ increased the surface area, but those of 25, 50, and 75 mol% CeO₂ did not affect it very much. By using this mixed metal oxides system, TiO₂ can be modified to respond to the visible wavelength. The mixed metal oxides had catalytic activity (evaluating the formation rate of I₃⁻) about 2-3 times higher than pure CeO₂, while nanosize anatase type TiO₂ materials had no catalytic activity under visible light. The catalytic activity was almost proportional to the specific surface area. The formation rate of I₃⁻ was much improved by changing the calcination temperature and calcination period. Highest catalytic activity in this study was obtained for the 50 mol% TiO₂-50 mol% CeO₂ nanopowders calcined at 250 °C for 24 h.