可见光响应的铁掺杂二氧化钛的制备及其光催化性能研究

以硝酸铁、硫酸氧钛为出发原料,通过直接化学法合成了锐钛矿型的Fe掺杂的Ti O2纳米光催化剂;通过X射线衍射仪、傅里叶红外光谱仪、紫外-可见-近红外分光光度计、热差热重分析仪对样品的结构以及性能进行了表征。结果表明:Fe掺杂的纳米Ti O2光催化剂的紫外吸收光谱和纯Ti O2相比,吸收带边发生红移,光响应范围拓展到在可见光区域;Fe的掺杂可以提高Ti O2的光催化性能,其中1%的Fe-Ti O2对亚甲基蓝的光催化活性最高。在模拟可见光条件下,Fe-Ti O2表现出了较优的光催化性能,光照10 min后,降解率高达83.9%。     

Sulfanilic acid-modified P25 TiO2 nanoparticles with improved photocatalytic degradation on Congo red under visible light

Visible-light-induced titania/sulfanilic acid nano-composite photocatalysts were prepared and characterized by FTIR, XPS, UV-vis, XRD, and SEM. The results indicate that the formation of Ti-O-S bonds after the modification of P25 TiO₂ nanoparticles with sulfanilic acid ligands extends the photoresponse of the photocatalyst from the UV to the visible range. The photocatalytic activity of the nano-composite photocatalyst was examined by degrading Congo red under visible light, in which its effecting factors such as irradiation time, catalyst dosage, solution pH and the addition of H₂O₂, were investigated in detail. The possible mechanism of photocatalytic degradation under visible irradiation has been also presented.     

处理温度对锐钛型TiO2光催化活性的影响

高温处理锐钛型TiO2可使其转晶改变晶型比例,因此加热温度和加热时间是影响TiO2光催化活性的主要因素。通过该方法得到了可利用可见光的TiO2催化剂,并进行了可见光降解有机染料乙基紫的研究。结果表明,在TiO2和可见光共同作用下,乙基紫的光降解效果明显优于单独使用锐钛型、金红石型和按照转晶的比率混合的锐钛型和金红石型TiO2。     

可见光下改性纳米TiO2催化降解废水污染物的研究进展

通常TiO2可降解有机污染物,其最活泼晶型为锐钛矿相,但它却有较高带隙能,因此只能被紫外光激发;近年来,大量研究人员致力于对TiO2进行改性使其吸收波谱向可见光波长方向移动的研究,取得一定成效。文章综述了拓宽光谱响应光催化材料的类型、机理以及掺杂物用量、载体等对改性纳米TiO2可见光吸收范围及光催化剂活性的影响,展望了可见光响应光催化材料在降解废水污染物研究中的应用。     

Enhanced photocatalytic activity of Bi2WO6 doped with upconversion luminescence agent

In order to utilize visible light more effectively, a novel Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst was designed, in which Er³⁺:Y₃Al₅O₁₂ is a kind of upconversion luminescence agent and can emit ultraviolet light under visible light excitation. The photo-degradation of a typical model pollutant, phenol, demonstrated that Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst exhibited much enhanced photo-activity than bare Bi₂WO₆ under simulated solar light irradiation. Moreover, the Er³⁺:Y₃Al₅O₁₂/Bi₂WO₆ photocatalyst also showed photo-activity under visible light with wavelengths beyond the absorption edge of Bi₂WO₆, further testifying the upconversion effect of Er³⁺:Y₃Al₅O₁₂.     

Fullerene polymer film as a highly efficient photocatalyst for selective solar fuel production from CO2

C₆₀-based polymeric systems have been constantly anticipated for sustainable solar energy conversion. Reported, herein is a C₆₀ polymer film as visible light active photocatalyst for efficient and selective reduction of CO₂ for the first time. The C₆₀ polymer photocatalyst is synthesized via covalent coupling of C₆₀ monomer units consisting of tetra substituted C₆₀-pyrene conjugates through spacer groups. The synthesized C₆₀ polymer photocatalyst possesses an extended network of well-defined repeating monomer units with good stability and visible light-induced photocatalytic activity. The enhanced visible light harvesting ability of C₆₀ polymer photocatalyst reasonably yields it with higher catalytic ability than its monomer unit. The C₆₀ polymer film photocatalyst upon coupling with the biocatalyst carries out highly selective visible light driven reduction of CO₂ to HCOOH (239.46 μmol). The tandem way of incorporating C₆₀ into visible light active polymeric films for continuous use may be highly rewarding for their extended photocatalytic activity for solar fuel production from CO₂. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48536.     

Experimental analysis and optimization of the synthesizing property of nitrogen‐modified TiO2 visible‐light photocatalysts

BACKGROUND: The aim of this study was to investigate improvement of the photocatalytic activity of visible‐light driven nitrogen‐modified TiO₂ (N‐TiO₂) powder toward methyl blue (MB) and direct blue‐86 (DB‐86) dyes. The Taguchi method with an L₉ orthogonal array was applied to plan the synthesis parameters, i.e. nitrogen sources, nitrogen source concentrations, stirring time and calcined temperatures. 95% confirmation experiments were undertaken to verify the effectiveness of the Taguchi method. RESULTS: All N‐TiO₂ photocatalysts were shifted toward the visible light region with the optical band gap (Eg). Nitrogen source concentrations were significant parameters for the photocatalytic decolorization rate constants (k values). In comparison with pure TiO₂, the photodecolorization behavior of N‐TiO₂ toward DB‐86 was superior with a reaction rate constant of 1.68 × 10^?3 min^?1, and a 4 h photodecolorization efficiency of 34%. CONCLUSION: The Taguchi method was reported to alter the surface properties of commercial Degussa P25 TiO₂, which could then be used as a visible‐light driven photocatalyst. The visible‐light‐driven photocatalyst was investigated to determine material characteristics. Greater photodecolorization of MB and DB‐86 dye pollutants using optimally‐prepared N‐TiO₂ under visible light irradiation was successfully obtained. Copyright © 2011 Society of Chemical Industry     

Enhanced photocatalytic activity of TiO2/SiO2 by the influence of Cu-doping under reducing calcination atmosphere

Cu-doped titania photocatalyst supported on silica beads (Cu-TiO₂/SiO₂) were prepared under different Cu-ion concentration and under different calcination atmosphere. The properties and performance of Cu-TiO₂/SiO₂ were compared with undoped TiO₂/SiO₂ photocatalyst. The effect of Cu-doping and calcination atmosphere on photocatalytic degradation of phenol under both black light and visible light irradiation were investigated, where in both cases the degradation rate of phenol by Cu-doped catalyst prepared under reducing calcination atmosphere was found to be higher than the undoped catalyst or Cu-doped catalyst prepared under air atmosphere. This may be attributed to increase in visible light absorption and lengthening of photogenerated electron–hole pair recombination time. The photocatalytic beads were characterized by X-ray diffraction (XRD), UV-Vis absorption spectroscopy and SEM/EDAX analysis.     

Efficient photocatalytic degradation of organic dyes over titanium dioxide coating upconversion luminescence agent under visible and sunlight irradiation

In order to use the sunlight efficiently, a new titanium dioxide (TiO₂) photocatalyst with high catalytic activity under visible light irradiation was prepared with sol–gel technique. In this work, an upconversion luminescence agent, crystallized Er³⁺:Y₃Al₅O₁₂, was synthesized and its characters were determined. It is found that this crystallized Er³⁺:Y₃Al₅O₁₂ can emit three upconversion fluorescent peaks below 387 nm under the excitation of 488 nm visible light. Hence, this upconversion luminescence agent could transform visible light into ultraviolet light, which could satisfy the genuine requirement of TiO₂ photocatalyst. Additionally, the upconverison mechanisms were also discussed. Meanwhile, the prepared TiO₂ photocatalysts coating upconversion luminescence agent were characterized by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The photocatalytic activity of prepared TiO₂ powder was tested through the degradation of congo red in aqueous solution as a model compound under visible and sunlight irradiation. To affirm the complete mineralization, the ion chromatography and total organic carbon (TOC) were used to observe the mineralized anions and organic residues. The experimental results proved that the prepared TiO₂ photocatalyst coating crystallized Er³⁺:Y₃Al₅O₁₂ behaved much higher photocatalytic activity under visible light and sunlight irradiation, and was able to decompose the congo red in aqueous solution efficiently. Therefore, this method may be envisaged as a novel technology for treating dyes wastewater using solar energy, especially for textile industries in developing countries.     

Graphene modified Nd/TiO2 photocatalyst for methyl orange degradation under visible light irradiation

A novel nanoscale GR–Nd/TiO₂ composite photocatalyst was synthesized by the hydrothermal method. Its crystal structure, surface morphology, chemical composition and optical properties were studied using XRD, TEM, and XPS, DRS and PL spectroscopy. It was found that graphene and neodymium modification shifts the absorption edge of TiO₂ to visible-light region. The results of photoluminescence (PL) emission spectra show that GR–Nd/TiO₂ composites possess better charge separation capability than do Nd/TiO₂ and pure TiO₂. The photocatalytic activity of prepared samples was investigated by degradation of methyl orange (MO) dye under visible light irradiation. The results show that the GR–Nd/TiO₂ composite can effectively photodegrade MO, showing an impressive photocatalytic activity enhancement over that of pure TiO₂. The enhanced photocatalytic activity of the composite catalyst might be attributed to the large adsorptivity of dyes, extended light absorption range and efficient charge separation due to Nd doping and graphene incorporation.     

Degradation of phenol in industrial wastewater over the F–Fe/TiO_2 photocatalysts under visible light illumination

F–Fe/TiO_2 composite photocatalyst was synthesized by a facile one-step hydrothermal method and then characterized by XRD, XPS and UV–Vis DRS. The catalyst of F–Fe/TiO_2 exhibited the highest photodegradation rate for phenol as compared with pure TiO_2, F/TiO_2, Fe/TiO_2, F0.38–Fe0.13–TiO_2 and Fe(III)/F-TiO_2 under visible light irradiation. The simulated conditions of industrial phenolic wastewater including initial phenol concentration,visible light intensity, p H and different anions were investigated in the presence of F–Fe/TiO_2 photocatalyst. In addition, as expected, the F–Fe/TiO_2 photocatalyst displayed excellent stability, showing a potential industrial application for the treatment of phenolic wastewater.     

非金属掺杂改性二氧化钛光催化剂研究进展

采用掺杂金属离子或非金属离子可增强TiO2光催化材料可见光响应能力.金属离子掺杂往往牺牲其紫外光区催化能力,而采用非金属掺杂不仅能够增强其可见光响应能力,且保持紫外区光催化活性,非金属离子掺杂将是TiO2光催化改性的重要方法.综述了近年来采用非金属离子掺杂改性TiO2光催化剂的最新研究.     

TiO2 based nanopowder coatings over stainless steel plates for UV-C photocatalytic degradation of methylene blue

Immobilizing the photocatalyst in a water treatment process design is essential; however, the immobilization method may affect the photoactivity of the photocatalyst. In this work, photocatalyst powders were successfully coated on 316 L stainless steel plates by a novel brush coating method. Three combinations of photocatalyst mixtures (pure TiO₂ anatase, anatase doped with WO₃, or TiO₂ rutile) were and annealed at different temperatures between 460-540°C. The ~ 10 μm thick coatings demonstrated full plate coverage and strong adhesion and adequate durability. Surface roughness increased with annealing temperature. The doping and annealing process enabled band gap reduction to the visible light spectrum for all coatings, with the smallest band gap being 2.48 eV (1 eV = 1.6 × 10⁻¹⁹ J). Subsequent methylene blue degradation tests under UV-C showed that the coatings annealed in 460°C exhibited the best performance and with the highest degradation rate constant of 5.59 hours⁻¹.     

改性纳米二氧化钛可见光催化降解水体中五氯酚

采用共沉淀-浸渍法制备掺Fe的改性纳米TiO2光催化剂,以五氯酚(PCP)的光催化降解反应为模型,研究了不同光催化剂、不同光催化降解体系对水体中PCP降解效率。结果表明,适量Fe元素掺杂改性TiO2后,光催化剂为锐钛矿型,粒径变小,形貌规则,分散性能良好,且掺杂后可降低纳米TiO2光生电子-空穴对的复合几率,提升光催化剂对可见光子利用率。0.008%Fe-TiO2具有最佳的PCP可见光催化降解效率,降解率达90.3%,超声对光催化氧化降解水体PCP有良好协同作用。该降解反应体系简单、可直接利用可见光,成本低、便于推广。     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Dip to Drink: Solar Photocatalytic Reduction of Cr(VI) Using Fibrous Red Phosphorus Immobilized Quartz Sand as “Dip-Catalyst”

Cr(VI) is a highly toxic inorganic water pollutant and shows adverse effects on human health. Photocatalytic treatment is a green and efficient method to reduce the toxic Cr(VI) to non-toxic Cr(III). In general, photocatalysts are used in slurry form, which turns the post purification such as separation and re-use of the catalyst tedious. To overcome this limitation, in this article we describe the immobilization of visible light/sunlight active photocatalyst i.e. fibrous red phosphorus (FRP) on quartz sand (QS). FRP is a crystalline allotrope of red phosphorus with interesting structural features and optimum bandgap i.e.?~?1.9 eV with sunlight/visible light activity. FRP immobilized QS was used as a photocatalyst for the reduction of Cr(VI) at different initial concentrations of Cr(VI) and with different loads of photocatalyst. High rate of Cr(VI) photoreduction was observed with 100 mg of FRP immobilized QS with a rate constant of 0.052 min^?1. Immobilized photocatalyst was loaded in a tea bag and used as a “dip-photocatalyst” for the reduction of Cr(VI). In this process 80% of Cr(VI) reduction occurred in 60 min with a rate constant of 0.034 min^?1. After the photocatalytic process, dip catalyst was dried under ambient conditions and re-used for the 2nd and 3rd cycles. Such immobilization of catalyst and using it in a tea bag as a dip catalyst facilitates the hassle free separation, re-use of the photocatalyst and eliminates the necessity of post purification processes and makes the photocatalytic environmental remediation processes more cost effective.

     

硫掺杂纳米TiO2可见光催化剂的制备及光催化活性

用钛酸丙酯和硫脲为原料在煅烧条件下制备了硫掺杂纳米TiO2光催化剂,用XRD、XPS、TEM和UV-vis吸收光谱对催化剂进行了表征;分别以紫外光与太阳光为光源,甲基橙为目标降解物,评价了催化剂的光催化活性。结果表明,500℃煅烧的硫掺杂TiO2在紫外光区和可见光区的吸光度比纯TiO2提高了约0.23~0.46;经40~50 min降解,其在紫外光和太阳光下对甲基橙的降解率比纯TiO2分别提高了32%和69%。TEM结果表明,500℃煅烧的硫掺杂TiO2的粒径约为15~16 nm;XRD分析结果表明,硫掺杂能够促进TiO2从锐钛矿相向金红石相的转变,减小催化剂的晶粒粒径;XPS分析结果指出,硫原子的氧化态为+6,S6+部分取代了TiO2晶格中的Ti4+,形成了硫掺杂的TiO2光催化剂。     

以稻壳-TiO_2为原料化学活化制备TiO_2/SiO_2/AC光催化剂

以钛酸四丁酯[Ti(OBu)4]为钛源,采用溶胶-凝胶法将TiO2前驱体负载于稻壳表面,进一步以该复合物为原料,经炭化和KOH化学活化制得具有可见光激发活性的活性炭负载TiO2/SiO2光催化剂。以对亚甲基蓝的脱色率为依据探讨了钛酸四丁酯的用量及煅烧温度对催化剂光催化性能的影响。利用傅立叶变换红外光谱、扫描电镜及X射线衍射等测试手段对光催化剂的结构、表面形态及晶相结构进行了表征。结果表明,TiO2晶型为锐钛矿相结构,并且与SiO2作用形成了Ti—O—Si键。     

Visible light photocatalytic degradation of thiophene using Ag–TiO2/multi-walled carbon nanotubes nanocomposite

Ag–TiO₂ nanocatalyst, supported on multi-walled carbon nanotubes, was synthesized successfully via a modified sol–gel method, and the prepared photocatalyst was used to remediate aqueous thiophene environmentally by photocatalytic oxidation under visible light. The prepared Ag–TiO₂/multi-walled carbon nanotubes nanocomposite photocatalyst was characterized through X-ray diffraction, Brunauer–Emmett–Teller (BET), transmission electron microscopy, and UV–vis spectra (UV–vis). The results showed that both Ag and TiO₂ nanoparticles were well-dispersed over the MWCNTs and formed a uniform nanocomposite. Ag doping can eliminate the recombination of electron–hole pairs in the catalyst, and the presence of MWCNTs in the TiO₂ composite can change surface properties to achieve sensitivity to visible light. The optimum mass ratio of MWCNT:TiO₂:Ag was 0.02:1.0:0.05, which resulted in the photocatalyst's experimental performance in oxidizing about 100% of the thiophene in a 600 mg/L solution within 30 min and with 1.4 g L⁻¹ amount of catalyst used.     

制备条件对新颖负载型TiO_2光催化剂活性的影响

开发新颖玻璃弹簧填料型载体 ,采用浸渍 -烧结法制备纳米 Ti O2 负载型光催化剂 ,研究不同制备条件对其催化活性的影响。结果表明 ,该负载型催化剂较佳制备条件为 :P2 5 Ti O2 浸渍浆料浓度为 0 .5 % ,浸渍次数为 5次 ,焙烧温度为 40 0°C、时间为 3 h。该负载型光催化剂具有高的光照射表面积 /体积比、空隙率很大、床层压降低 ,以及在催化剂填充空间光辐射分布较均匀 ,导致有效的光催化反应体积成倍增加的优点。