黑色二氧化钛的研究与发展论文

photocatalysis and related surface phenomena(二氧化钛光催化及相关表面现象)作者: Fujishima, Akira; Zhang, Xintong; Tryk, Donald SCIENCE REPORTS 卷: 63 期: 12 页: 515-582 出版年: DEC 15 photocatalysis of naproxen: Effect of the water matrix, anions and diclofenac on degradation rates.(萘普生的TiO2光催化：水基质的作用，对阴离子和双氯芬酸的降解率)作者: Kanakaraju, Devagi; Motti, Cherie A; Glass, Beverley D; 等.Chemosphere 卷: 139 页: 579-88 出版年: 2015-Nov (Epub 2015 Sep 01) photocatalysis: A historical overview and future prospects.(二氧化钛光催化：一个历史的概述和未来前景)作者: Hashimoto, K; Irie, H; Fujishima, AJAPANESE JOURNAL OF APPLIED PHYSICS PART 1-REGULAR PAPERS BRIEF COMMUNICATIONS & REVIEW PAPERS 卷: 44 期: 12 页: 8269-8285 出版年: DEC surface science perspective on TiO2 photocatalysis(二氧化钛光催化的表面科学研究)作者: Henderson, Michael SCIENCE REPORTS 卷: 66 期: 6-7 页: 185-297 出版年: JUN 15 2011

纳米二氧化钛是具有屏蔽紫外线功能和产生颜色效应的一种透明物质。由于它透明性和防紫外线功能的高度统一，使得它一经问世，便在防晒护肤、塑料薄膜制品、木器保护、透明耐用面漆、精细陶瓷等多方面获得了广泛应用。特别是在80年代末期，这种能产生诱人的“随角异色”效应的效应颜料被成功地用于豪华型高级轿车面漆之后，引起了世界范围的普遍关注，发达国家如美、日、欧等国对此研究工作十分活跃，相继投入了大量人力、物力，并制订了长远规划，在国际市场竞争激烈迄今，他们已取得许多令人惊异的成果，并已形成高技术纳米材料产业，生产这种附加值极高的高功能精细无机材料，收到良好的经济效益和社会效益，纳米氧化物材料也正成为中国产业界关注的热点。随着纳米材料研究的深入，纳米组装体系、人工组装合成的纳米结构的材料体系越来越受到人们的关注，这意味着纳米材料的研究已可以按照人们的意愿设计、组装、创造新的体系，更有目的地使该体系具有人们所希望的特性，技术上的飞跃，为纳米材料的应用进一步打开市场的大门，在广泛的领域形成了一大批高技术产品。如信息与通讯方面的磁性存储器、光学存储器、液晶显示、光学方面的功能性薄膜；电子方面的原件开发，能源方面的太阳能电源，热敏绝缘体，测量与控制技术方面的传感器；陶瓷方面的结构陶瓷，功能陶瓷以及其他方面的抗老化橡胶、功能油漆、光催化降解剂、保洁抗菌材料、超高磁能衡土水磁体等。在纳米材料的市场增长中，o维-3维结构技术，超精度加工技术，超薄膜生产技术，横向结构技术所制造的产品最具市场增长潜力。有关研究还表明，在今后10年中，纳米材料的市场应用开发的速度还会加快，因为工业国家纳米材料领域的专利自1993年以来一直以每年20%以上的速度递增。资料表明，西方工业国家在纳米材料及相关领域的科研经费投入每年达75亿美元左右。国际上在此领域竞争日趋激烈。

发1篇 氮氟掺杂二氧化钛光催化微囊藻毒素 （如有需要可以帮翻译一部分 此类文章在线翻译一般不准) 还有部分无法发出，把邮箱留下，我发给你。题目：Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water正文：1. IntroductionThe development of nanotechnology for the synthesis ofnanomaterials is providing unprecedented opportunities to dealwith emerging environmental problems associated with watercontamination along with worldwide energy-related concerns [1].Currently, advanced oxidation technologies (AOTs) and nanotechnologies(AONs) have been extensively investigated for thedestruction of toxic and recalcitrant organic compounds andinactivation of microorganisms in water and air [2–12]. Titaniumdioxide (TiO2), a well-known semiconductor with photocatalyticproperties, is a widely used AON for water and air remediation [6–10]. It has proven to be highly effective in the nonselectivedegradation of organic contaminants due to high decompositionand mineralization rates. However, conventional TiO2 requiresultraviolet (UV) radiation (l < 400 nm) to overcome its wide bandgap energy ( eV for anatase phase) for photocatalyticactivation [4,11]. This is a technological limitation when aimingat implementation of large scale sustainable technologies withrenewable energy sources such as solar light, since UV radiationaccounts only for 5% of the total solar spectrum compared to thevisible region (45%) [12,13]. Several attempts have been directedtowards the development of modified TiO2 with visible lightresponse by dye sensitization, metal (Fe, Co, Ag) [14,15] andnonmental (N, F, C, S) [4,16–23] doping of the catalyst to reduceTiO2 band gab energy requirements for photocatalytic some metal doping approaches, the resulting visible lightphotocatalytic activity has some drawbacks including increase inthe carrier-recombination centers (electron–hole pair speciesgenerated after photo-excitation of the catalyst) and low thermalstability of the modified material [14]. Moreover, metal leachingand possible toxicity diminish the potential of employing metaldopedTiO2 for drinking and wastewater treatment applications. Amore successful approach involves nonmetal doping of doping of TiO2 for visible-light driven photocatalysisrevealed band gap narrowing from the mixing of nitrogen 2pstates with oxygen 2p states on the top of the valence band atsubstitutional lattice sites in the form of nitride (Ti–N) oroxynitride (Ti–O–N). A different arrangement is the formation ofoxyanion species at the interstitial lattice sites creating localizedintergap states [24]. Both configurations make it possible to shiftthe optical absorption towards visible light, thus, allowingphotocatalytic activity in the visible region [11,22,23]. Fluorinedoping is also effective to induce modifications of the electronicstructure of TiO2 by the creation of surface oxygen vacancies due tocharge compensation between F and Ti4+ but without producing asignificant change in the optical absorption of TiO2 [21]. Moreover,codoping of TiO2 with nitrogen and fluorine has demonstrated highphotocatalytic activity in the visible region with beneficial effectsinduced by both dopants [25–27]. Huang et al. confirmed strongvisible-light absorption and high photocatalytic activity of N-FTiO2for p-chlorophenol and Rhodamine B degradation undervisible light irradiation [26]. Xie et al. effectively decomposedmethyl orange with visible light-induced N-F-TiO2 photocatalyst[27]. Both attributed their findings to the synergistic effect ofnitrogen and fluorine addition to nonmetal doping, structural properties of TiO2 areof significant importance to enhance its physicochemical propertiesand photocatalytic response. For instance, the use of self-assemblysurfactant-based sol–gel methods has been reported as an effectiveapproach to tailor-design the structural properties of TiO2 nanoparticlesand films from molecular precursors [6,8–10]. Thehydrocarbon surfactant is used as pore directing agent and tocontrol the hydrolysis and condensation rates of the titaniumprecursor in the sol formulation. This method has the capacity toyieldtailor-designedTiO2withhighsurface area,highporosity, smallcrystal size with narrow pore size distribution and high photocatalyticactivity under UV [8–10] and visible light irradiation [4].One of the aims of this work is to develop highly efficient N-FcodopedTiO2 nanoparticles with enhanced structural propertiesand high photocatalytic activity under visible light irradiationusing a novel sol–gel route employing a nonionic fluorosurfactantas pore directing agent and fluorine dopant and ethylenediamineas nitrogen source. Fluorosurfactants or fluorinated surfactants,have been used mainly as antistatic, antifogging and wettingagents, and paint coating additives [28]. Only recent studies havefocused on the use of fluorinated surfactants as pore template formesoporous silica materials [29–32], signifying a great potentialfor novel ceramic second aim of this work is to focus on the application ofsuch nanoparticles in engineered water treatment processes forthe destruction of environmental contaminants of worldwideconcern. Drinking water treatment plants are facing moreprevalent occurrence of cyanobacterial harmful algae blooms(Cyano-HABs) and the release of their toxins in their water toxins are considered a serious health risk due to their highsolubility in water, toxicity (., hepatotoxicity, neurotoxicity, andcarcinogenicity) and chemical stability. Among them, microcystin-LR (MC-LR) is one of the most commonly found cyanotoxins inCyano-HABs and the most toxic derivative of the group ofmicrocystins [33]. Conventional TiO2 has been proven to beeffective in the treatment of MC-LR under UV radiation [34,35].Recent work demonstrated high degradation rates of MC-LR withnitrogen-doped TiO2 nanoparticles [4]. In this study, we presentresults on the destruction of MC-LR with N-F-TiO2 nanoparticlesunder visible light . . Synthesis of visible light-activated TiO2 nanoparticlesTo prepare the modified sol–gel solution, a nonionic fluorosurfactant(Zonyl FS-300 (FS), 50% solids in H2O, RfCH2CH2O(CH2CH2O)xH; Rf = F(CF2CF2)y where x = 14 and y = 3, Fluka), acting asboth pore directing agent and fluorine source, dissolved inisopropanol (i-PrOH), was used. Acetic acid (Fisher) was addedto maintain a low pH (). Before adding the titania precursor,anhydrous ethylenediamine (EDA, Fisher) was added in thesolution as nitrogen source. Then, titanium(IV) isopropoxide (TTIP,97%, Aldrich) was added dropwise under vigorous stirring andmore acetic acid was added for peptidization. The final sol obtainedwas transparent, homogeneous and stable after stirred overnightat room temperature. Afterwards, the sol was dried at roomtemperature for 24 h and then calcined in a multi-segmentprogrammable furnace (Paragon HT-22-D, Thermcraft) wherethe temperature was increased at a ramp rate of 60 8C/h to 100 8Cand maintained for 1 h. Then it was increased up to 400 8C underthe same ramp rate, maintained for 2 h and cooled down naturallyto finally obtain a yellowish powder. The FS:i-PrOH:aceticacid:EDA:TTIP molar ratio employed in the sol–gel for thepreparation of the denoted Particle 1 was , the i-PrOH/EDA molar ratio was and 14 forParticles 2, and 3, respectively. Nitrogen-doped TiO2 (Particle 4)and fluorine-doped TiO2 (Particle 5) where synthesized without FSand EDA, respectively, maintaining the same final volume by theaddition of more isopropanol. Reference TiO2 was synthesizedusing the same procedure but without the addition of nitrogen andfluorine sources. The synthesized nanoparticles were comparedwith Kronos vlp 7000, a commercially available visible lightactivatedTiO2 photocatalyst (Kronos International Inc., D-51373).. Characterization of synthesized TiO2An X-ray diffraction (XRD) analysis was performed with aKristalloflex D500 diffractometer (Siemens) using Cu Ka(l = ˚ ) radiation, to study the crystal structure andcrystallinity of the TiO2 nanoparticles. The Brunauer–Emmett–Teller (BET) surface area, pore volume, porosity, Barret–Joyner–Halenda (BJH) pore size and distribution (based on nitrogenadsorption and desorption isotherms) were determined by Tristar300 (Micromeritics) porosimeter analyzer. The samples werepurged with nitrogen gas for 2 h at 150 8C using Flow prep 060(Micromeritics). A high resolution-transmission electron microscope(HR-TEM) with field emission gun at 200 kV was employedto obtain crystal size and crystal structure at the nanoscale. Thesamples in ethanol were dispersed using an ultrasonicator (2510RDH,Bransonic) for 15 min and fixed on a carbon-coated copper grid(LC200-Cu, EMS). The particle morphology was characterized by anenvironmental scanning electron microscope (ESEM, Philips XL 30ESEM-FEG) at an accelerating voltage of 30 kV. The point of zerocharge (PZC) was measured using a Zetasizer (Malvern Instruments).The fine elemental composition and electronic structurewas determined with an X-ray photoelectron spectroscope (XPS,PerkinElmer Model 5300) with Mg Ka X-rays at a takeoff angle of458 and vacuum pressure of 108 to 109 Torr. The bindingenergies were calibrated with respect to C1s core level peak eV. To investigate the optical band gap of the synthesizedTiO2 nanoparticles, the UV–vis absorption spectra were obtainedwith a UV–vis spectrophotometer (Shimadzu 2501 PC) mountedwith an integrating sphere accessory (ISR1200) using BaSO4 asreference . Photocatalytic evaluation with microcystin-LR under visible lightThe photocatalytic activity of the synthesized TiO2 nanoparticleswas evaluated for the degradation of MC-LR. A borosilicatevessel (. cm) was employed as photocatalytic reactor. Anaqueous solution, previously adjusted at the desired pH withH2SO4 or NaOH without any buffer, was spiked with an aliquot ofMC-LR standard (Calbiochem Cat #. 475815) to achieve an initialconcentration of mg/L. A solution with TiO2 nanoparticleswas dispersed using an ultrasonicator (2510R-DH, Bransonic) for 24 hand transferred to the reactor containing MC-LR for a final volumesolution of 10 ml. The reactor was completely sealed and mixed tominimize mass transfer limitations. Two 15W fluorescent lamps(Cole-Parmer) mounted with UV block filter (UV420, Opticology) toeliminate spectral range below 420 nm were employed to irradiatethe reactors. The intensity of the radiation was below the detectionlimit when employing an IL 1700 radiometer (International Light)with a 365 nm sensor. The light intensity was determined using abroadband radiant power meter (Newport Corporation) for a totalvisible light intensity of 105Wcm2. During irradiation, a fanwas positioned near the reactor to cool it down. Sampling was done atspecific periods of time and the samples were quenched withmethanol to stop any further reaction, filtered (L815, Whatman) toremove the suspended nanoparticles, transferred to ml glassinserts and placed in sample vials. MC-LR samples were analyzed byliquid chromatography (LC, Agilent Series 1100) equipped with aphotodiode array detector set at 238 nm under isocratic conditions:60% (v/v) of trifluoroacetic acid (TFA) in MilliQ water and 40%(v/v) of TFA in acetonitrile with a flow rate of 1 ml/ column employed was a C18 Discovery (Supelco) column( mm 150 mm, 3 mm particle size) kept at 40 8C with aninjection volume of 50 ml [7]. The handling of the toxin must bedone with extreme care since it is highly toxic and irritant if , all the experiments were conducted in an AdvanceSterilchemgard III Class II biological safety cabinet (Baker Company,Sanford, ME) with full exhaust.