Photocatalytic oxidation of acetonitrile in aqueous suspension of titanium dioxide irradiated by sun

二氧化钛纳米管对亚甲基蓝的吸附3高　卓,徐　瑛,王　燕,何　娇,丁亚平,韩　苗(武汉理工大学理学院化学系,湖北　武汉　430070)摘　要:采用水热法制备了Ti O 2纳米管,借助X 射线衍射(XRD )、透射电镜(TE M )对产物进行了表征。

以亚甲基蓝溶液为体系,考察了Ti O 2纳米管的吸附性能。

结果表明:Ti O 2纳米管为锐钛矿相,管径小、管形均匀。

黑暗条件下Ti O 2纳米管对亚甲基蓝具有优异的吸附活性,30m in 可达到吸附平衡,吸附量达38.3mg/g,最佳吸附质量比为w (MB ):w (Ti O 2)≈0.075。

关键词:二氧化钛;水热法;吸附;亚甲基蓝Stud i es on the Adsorpti on of M ethylene Blue on T it an i a Nanotubes3G AO Z huo,XU Ying,WAN G Yan,HE J iao,D I N G Ya -ping,HAN M iao(College of Science,W uhan University of Technol ogy,HubeiW uhan 430070,China )Abstract:Ti O 2nanotubes were p repared by hydr other mal synthesis,and the p r oducts were characterized by X -ray diffracti on (XRD )and trans m issi on electr on m icr oscope (TE M ).The ads or p ti on of Ti O 2nanotubes obtained was investiga 2ted in a methylene blue (MB )aqua syste m.The results showed that Ti O 2nanotubeswas anatase phase with s maller dia me 2ter and evenly shape .The Ti O 2nanotubes had high ads or p ti on activity f or methylene blue in the dark,whose ads or p ti on e 2quilibriu m was reached within 30m in .The ads orbility capacities of MB could reach 3813mg/g and the best ads or p ti on mass rati o of MB /Ti O 2was about 01075.Key words:Ti O 2;hydr other mal method;ads or p ti on;methylene blue3基金项目:湖北省自然科学基金(2008CDB260);湖北省攻关(20051g0052);武汉理工大学大学生创新研究训练计划。

药学专业文献翻译Enzymatic Synthesis and Antioxidant Properties of Poly (rutin) 聚(芦丁)的酶促合成与抗氧化性质†‡†‡††Motoichi Kurisawa, Joo Eun Chung, Hiroshi Uyama,* and Shiro Kobayashi*Abstract 摘要Rutin, quercetin-3-rutinoside, is one of the most famous glycosides of flavonoid and widely present in many plants. In this study, we performed an oxidative polymerization of rutin using Myceliophthora laccase as catalyst in a mixture of methanol and buffer to produce a flavonoid polymer and evaluated antioxidant properties of the resultant polymer. Under selected conditions , the polymer with molecular weight of several thousands was obtained in good yields. The resulting polymer was readily soluble in water, DMF, and DMSO, although rutin monomer showed very low water solubility. UV measurement showed that the polymer had broad transition peaks around 255 and 350 nm in water, which were red-shifted in an alkaline solution. Electron spin resonance (ESR) measurement showed the presence of a radical in the polymer. The polymer showed greatly improved superoxide scavenging activity and inhibition effects on human low-density lipoprotein (LDL) oxidation initiated by 2,2‘-azobis(2-amidino-propane) dihydrochloride (AAPH), compared with the rutin monomer. The polymer also protected endothelial cells from oxidative injuryinduced by AAPH as a radical generator with a much greater effect than the rutin monomer.芦丁，槲皮素芸香糖苷，是最著名的黄酮类糖苷之一，广泛存在于很多植物中。

'£朽知库环境工程学报第15卷第3期2021年3月Vol. 15, No.3 Mar. 2021Eco-Environmental Knowledge Web C hinese Journal of Environmental Engineering@(010) 62941074文章栏目：水污染防治DOI 10.12030/j.cjee.202008112 中图分类号X701.3 文献标识码A丁丽丹，周家斌，刘文博，等.Cu0/Bi203光催化耦合过一硫酸盐氧化降解盐酸四环素[J].环境工程学报，2021. 15(3): 898- 910.DING Lidan, ZHOU Jiabin, LIU Wenbo, et al. Oxidative degradation of tetracycline hydrochloride by Cu0/Bi203 photocatalysis coupling with peroxymonosulfate[J]. Chinese Journal of Environmental Engineering, 2021, 15(3): 898-910.C u0/B i203光催化耦合过一硫酸盐氧化降解盐酸 四环素丁丽丹、周家斌刘文博\陈新2,冯芹芹2,杨玉玲\张天磊11. 西南石油大学化学化工学院，成都6105002. 武汉理工大学资源与环境工程学院，武汉430070第一作者：丁丽丹（1995—)，女，硕士研究生。

研究方向：水处理高级氧化技术。

E-mail: ***************** *通信作者：周家斌（1972—），男，博士，教授。

研究方向：环境功能材料与污染控制：E-mail: ****************摘要利用共沉淀-浸渍法合成了基于可见光响应的Cu0/Bi203复合催化剂，并对其光催化活化过一硫酸盐 (PM S)去抗生素盐酸四环素（TC-HC1)的性能进行了探究。

一．好的论文题目是成功的一半好的论文，每一个部分都需要精雕细琢。

我们先来看看Science, Nature 子刊上用的都是些什么题目，到底这些题目暗含哪些玄机？以下是从2016年发表的论文中随机挑选的一些题目，我将其做了一下简单的分类：1. Water splitting–biosynthetic system with CO2reductionefficiencies exceeding?photosynthesis. (Science, 2016, 352, 1210)类似: Scalable water splitting on particulate photocatalyst sheets with asolar-to-hydrogen energy conversion efficiency?exceeding1%(Nature Materials 2016,15,611-615)这种题目适合哪类文章？适合于那种性能极其显着的文章（可以创纪录的文章），比如说Nocera et al. 的Science, 2016, 352, 1210，直接与光合作用进行对比，给人的震撼是非常强的。

这种对比效果能够一下子抓住人们的眼球，吸引着读者进行阅读。

要点：使用这样的题目首先你的实验结果得够牛，你对于实验结果要足够自信，对于背景知识的了解得要足够深。

因为取这样的题目意味着你要真正达到了某一个高度。

如果明明有很多大海在那里，你个小池塘和小水坑进行比较，那么会闹笑话的。

2.1 Quantifying?the promotion of Cu catalysts by ZnO for methanol synthesis ( Science,2016, 352, 969-974.)2.2Exploring the origin of high optical absorption in conjugated polymers. (Nature Materials 2016,DOI:10.1038/nmat4645)2.3 Promoting?solution phase discharge in Li–O2 batteries containing weakly solvatingelectrolytesolutions (Nature Materials 2016, DOI: 10.1038/nmat4629)2.4 Reconstructing?solute-induced phase transformations within individual nanocrystals (NatureMaterials 2016,doi:10.1038/nmat4620)2.5 Tailoring the nature and strength of electron–phonon interactions in the SrTiO3(001) 2D electronliquid (Nature Material, 2016, doi:10.1038/nmat4623)我简单地检索了下Nature Materials上面的文章题目，发现这种类型的题目真的非常多。

二硼化钛陶瓷在不同温度下的氧化行为黄飞，傅正义，王为民，王皓，王玉成，张金咏，张清杰(武汉理工大学，复合材料新技术国家重点实验室，武汉 430070)摘要：采用静态氧化法对不同温度下TiB2陶瓷的氧化行为进行研究，利用X射线衍射仪、扫描电镜、X射线光电子能谱仪对氧化前后的样品进行表征。

结果表明：低温下TiB2陶瓷氧化动力学满足抛物线规律，并在表面形成液相B2O3，阻止氧化反应的进一步进行，冷却后B2O3以玻璃态覆盖在表面。

高温下TiB2氧化反应在4h前满足抛物线规律，表面形成一层TiO2多孔结构；氧化4h后，随着氧扩散距离的延长，扩散阻力加大，从而使氧化速率降低，氧化反应不再满足抛物线规律。

关键词：二硼化钛；氧化动力学；微观结构中图分类号：TF123；TB332 文献标识码：A 文章编号：0454–5648(2008)05–0584–04OXIDATION BEHA VIOR OF TITANIUM DIBORIDE CERAMIC AT DIFFERENT TEMPERATURES HUANG Fei，FU Zhengyi，W ANG W eimin，W ANG Hao，W ANG Yucheng，ZHANG Jinyong，ZHANG Qinjie(State key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University ofTechnology, Wuhan 430070, China)Abstract: The oxidation behavior of TiB2 ceramics at different temperatures was investigated using the static oxidation kinetic method. The samples before and after oxidation have been characterized by X-ray diffractometer, scanning electron microscope and X-ray photoelectron spectrometer. The results show that the oxidation kinetics appear the parabolic law at low temperature. A liquid B2O3 coating on the surface of TiB2 ceramic could prevent from further oxidation. After the ceramic samples were cooled, their sur-faces were covered with glassy B2O3. At high temperature, the oxidation reaction of TiB2 ceramics showed the parabolic law only before 4h. Porous rutile TiO2 formed on the surface. But the oxidation behavior with the parabolic law for the TiB2 ceramics was not observed after oxidation for 4h because of the long path of diffusion, strong diffusion resistance and low reaction rate.Key words: titanium diboride; oxidation kinetics; microstructureTitanium diboride with P6/mmm structure is a uniquely stable compound of the boron element and tita-nium element.[1] TiB2 based materials have received wide attention because of their high hardness and elastic modulus, good abrasion resistance and superior thermal and electrical conductivity.[2–3] Potential applications in-clude high temperature structural materials, cutting tools, armor, electrodes in metal smelting and wear parts. De-spite its useful properties, the application of monolithic TiB2 is limited by poor sinterability, exaggerated grain growth at high temperature and poor oxidation resistance above 800.℃[4–5]The starting temperature to oxidize TiB2 ceramics is about 400℃ and oxidation kinetics is controlled by outward diffusion of interstitial titanium ions and inner diffusion of oxygen ions.[5–6] But there are conflicting viewpoints about the detailed oxidation process, for ex-ample, about the oxidation products and oxidation mechanism. Koh et al.[7] investigated the oxidation be-havior of dense TiB2 specimens with 2.5% in mass (the same below) Si3N4 and found that TiB2 exhibited two distinct oxidation behaviors depending on the tempera-ture. At temperatures below 1000℃, the oxidation layer comprised two layers: an inner layer of crystalline TiO2 and an outer layer mainly composed of B2O3. When the oxidation temperatures were higher than 1000℃, the收稿日期：2007–09–23。

DOI: 10.1126/science.1061051, 269 (2001);293 Science , et al.R. Asahi Visible-Light Photocatalysis in Nitrogen-Doped Titanium OxidesThis copy is for your personal, non-commercial use only.clicking here.colleagues, clients, or customers by , you can order high-quality copies for your If you wish to distribute this article to othershere.following the guidelines can be obtained by Permission to republish or repurpose articles or portions of articles): November 23, 2010 (this infomation is current as of The following resources related to this article are available online at/content/293/5528/269.full.html version of this article at:including high-resolution figures, can be found in the online Updated information and services, /content/293/5528/269.full.html#related found at:can be related to this article A list of selected additional articles on the Science Web sites 2325 article(s) on the ISI Web of Science cited by This article has been /content/293/5528/269.full.html#related-urls 3 articles hosted by HighWire Press; see:cited by This article has been/cgi/collection/chemistry Chemistrysubject collections:This article appears in the following registered trademark of AAAS.is a Science 2001 by the American Association for the Advancement of Science; all rights reserved. The title Copyright American Association for the Advancement of Science, 1200 New York Avenue NW, Washington, DC 20005. (print ISSN 0036-8075; online ISSN 1095-9203) is published weekly, except the last week in December, by the Science o n N o v e m b e r 23, 2010w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o m␣S,were obtained from nsbury [J.C.Rochet et al.,Biochemistry 39,10619(2000)].21.The silver-stained band at 22kD in an HP2A immu-noprecipitate of normal human brain and a co-mi-grating silver-negative slice from an adjacent lane of a parkin-preabsorbed HP2A precipitate were excised,trypsin digested and subjected to blind analysis by mass spectrometry at MDS Proteomics,Inc.(Toronto,ON)[A.Shevchenko et al.,Anal.Chem .68,850(1996)].The HP2A-specific 22-kD protein yielded tryptic peptides corresponding to aa 13–21,44–58,46–58,59–80,61–80,81–96,and 81–97of human ␣S (GenBank accession #L08850),each ending with a lysine,as expected.No ␣S sequence was detected in the co-migrating slice from the preabsorbed lane.22.Y.Mizuno,N.Hattori,H.Mori,Biomed.Pharmaco-ther.53,109(1999).23.H.Shimura et al.,Ann.Neurol.45,668(1999).24.N.Hattori et al.,Ann.Neurol.44,935(1998).25.A.L.Talis,J.M.Huibregtse,P.M.Howley,J.Biol.Chem.273,6439(1998).26.M.Scheffner,J.M.Huibregtse,R.D.Vierstra,P.M.Howley,Cell 75,495(1993).27.Y.Jiang,E.Lev-Lehman,J.Bressler,T.F.Tsai,A.L.Beaudet,Am.J.Hum.Genet.65,1(1999).28.Human UbcH7and UbcH8were expressed in M15E.coli harboring the Lac -repressor expressing plasmid pREP4,using the QIA express system (QIAGEN,Va-lencia,CA)with an NH 2-terminal 6xHis tag.Proteinswere purified on nickel NTA-agarose (QIAGEN).En-zymatic activity was tested in Ub shift assays.29.Parkin was immunoprecipitated (yielding IP-parkin)from frontal cortex homogenates or HEK293cells transiently transfected with myc-parkin cDNA (10␮g)(13).IP parkin was incubated at 37°C in 50␮l of reaction buffer containing ATP (4mM ATP in 50mM Tris-HCl,pH 7.5,2mM MgCl 2),100ng of recombi-nant human E1,2␮g of UbcH7(E2),and 2␮g His-Ub (all from Affinity Research Products,Exeter,UK).The reaction was terminated by adding 20␮l of 4X sample buffer,and 25␮l aliquots of the reaction mixtures were electrophoresed and immunoblotted.30.We prepared WT and ARPD-mutant parkin cDNAs [N.Hattori et al.,mun.249,754(1998);L.Terreni et al.,Neurology 56,463(2001)]in a pcDNA3.1(ϩ)vector using the QuikChange site-directed mutagenesis kit (Strat-agene,La Jolla,CA)and transiently transfected them into HEK293cells using Lipofectamine 2000(Gibco,Rockville,MD),as per manufacturers’instructions.31.For enzymatic digestion of HP2A precipitates,N -glycosidase,sialidase A,endo-O-glycosidase [with bovine fetuin as a control protein (ProZyme,San Leandro,CA)],and protein phosphatase-1(Sigma)were used as per manufacturers’instructions.32.C.A.Joazeiro,A.M.Weissman,Cell 102,549(2000).33.P.J.Kahle et al.,J.Neurosci.20,6365(2000).34.M.Ivan et al.,Science 292,464(2001).35.P.Jaakkola et al.,Science 292,468(2001).36.J.Q.Trojanowski,M.Goedert,T.Iwatsubo,V.M.Lee,Cell Death Differ.5,823(1999).37.M.S.Goldberg,nsbury,Nature Cell Biol.2,E115(2000).38.N.F.Bence,R.M.Sampat,R.R.Kopito,Science 292,1552(2001).39.C.J.Cummings et al.,Neuron 24,879(1999).40.L.Wells,K.Vosseller,G.W.Hart,Science 291,2376(2001).41.We thank H.Mori,Y.Mizutani,and K.Yamane for ARPDbrain specimens;J.Chan for providing normal human brain;and the patients’families for the donation of tissue.We also thank K.Wynn and P.Howley for anti-E6-AP (JH-16),T.Suzuki and K.Tanaka for a parkin cDNA-containing vector,nsbury for reagents and critical review of our manuscript,and M.Medina for experimental advice.H.S.is supported by a Pergolide Fellowship (Eli Lilly,Japan K.K.).M.G.S.is supported by the Grass Foundation (Robert S.Morison Fellowship),the Lefler Foundation,and the NIH (NS 02127).M.P.F.is supported by a Beeson Scholar Award.R.S.received grants from the National Bank of Austria.Supported by the Morris R.Udall Center of Excellence in PD (NS 38375)at Brigham and Women’s Hospital (M.P.F.,K.S.K.,and D.J.S.).12March 2001;accepted 6June 2001Published online 28June 2001;10.1126/science.1060627Include this information when citing this paper.Visible-Light Photocatalysis in Nitrogen-Doped TitaniumOxidesR.Asahi,*T.Morikawa,T.Ohwaki,K.Aoki,Y.TagaTo use solar irradiation or interior lighting efficiently,we sought a photocatalyst with high reactivity under visible light.Films and powders of TiO 2-x N x have revealed an improvement over titanium dioxide (TiO 2)under visible light (wavelength Ͻ500nanometers)in optical absorption and photocatalytic ac-tivity such as photodegradations of methylene blue and gaseous acetaldehyde and hydrophilicity of the film surface.Nitrogen doped into substitutional sites of TiO 2has proven to be indispensable for band-gap narrowing and photocat-alytic activity,as assessed by first-principles calculations and x-ray photo-emission spectroscopy.Since photoinduced decomposition of water on TiO 2electrodes was discovered (1),semicon-ductor-based photocatalysis has attracted exten-sive interest.One particular focus has been on applications in which organic molecules are photodegraded,such as water and air purifica-tions (2–4).Most of the investigations have focused on TiO 2(5–7),which shows relatively high reactivity and chemical stability under ul-traviolet (UV)light [wavelength (␭)Ͻ387nm],whose energy exceeds the band gap of 3.2eV in the anatase crystalline phase.The development of photocatalysts that can yield high reactivity under visible light (␭Ͼ380nm)should allow the main part of the solar spectrum,and even poor illumination of interior lighting,to be used.One approach has been to dope transition metals into TiO 2(8–10),and another has been to form reduced TiO x photo-catalysts (11,12).However,doped materials suffer from a thermal instability (9),an increase of carrier-recombination centers,or the require-ment of an expensive ion-implantation facility (10).Reducing TiO 2introduces localized oxy-gen vacancy states located at 0.75to 1.18eV below the conduction band minimum (CBM)of TiO 2(12),so that the energy levels of the optically excited electrons will be lower than the redox potential of the hydrogen evolution (H 2/H 2O)located just below the CBM of TiO 2(13)and that the electron mobility in the bulk region will be small because of the localization.We have considered whether visible-lightactivity could be introduced in TiO 2by doping,and we set the following requirements:(i)dop-ing should produce states in the band gap of TiO 2that absorb visible light;(ii)the CBM,including subsequent impurity states,should be as high as that of TiO 2or higher than the H 2/H 2O level to ensure its photoreduction ac-tivity;and (iii)the states in the gap should overlap sufficiently with the band states of TiO 2to transfer photoexcited carriers to reactive sites at the catalyst surface within their lifetime.Conditions ii and iii require that we use anionic species for the doping rather than cationic met-als,which often give quite localized d states deep in the band gap of TiO 2and result in recombination centers of carriers.We have cal-culated densities of states (DOSs)of the substi-tutional doping of C,N,F,P,or S for O in the anatase TiO 2crystal,by the full-potential lin-earized augmented plane wave (FLAPW)for-malism (14,15)in the framework of the local density approximation (LDA)(16)(Fig.1).The substitutional doping of N was the most effective because its p states contribute to the band-gap narrowing by mixing with O 2p states.Although doping with S shows a similar band-gap narrowing,it would be difficult to incorporate it into the TiO 2crystal because of its large ionic radius,as evidenced by a much larger formation energy required for the substi-tution of S than that required for the substitution of N (17).The states introduced by C and P are too deep in the gap to satisfy condition iii.The calculated imaginary parts of the dielectric functions of TiO 2-x N x indeed show a shift of the absorption edge to a lower energy by the N doping (Fig.2A)(18).Dominant transitions at the absorption edge have been identified withToyota Central R&D Laboratories,Nagakute,Aichi 480-1192,Japan.*To whom correspondence should be addressed.E-mail:rasahi@mosk.tytlabs.co.jpR E S E A R C H A R T I C L E S SCIENCE VOL 29313JULY 2001269o n N o v e m b e r 23, 2010w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o mthose from N 2p ␲to Ti d xy ,instead of from O 2p ␲as in TiO 2(19).Jansen and Letschert dem-onstrated tunable colorings in modified perov-skite oxinitrides,which suggested a similar band-gap control by N,although they did notaddress the detailed electronic states in these pigments (20).Photocatalysts for the present purpose,however,require more elaborate controls for doping besides the optical absorption;i.e.,conditions ii and iii.To this end,we have made a theoretical comparison among three systems:substitutional N doping,interstitial N doping,and both types of doping in the anatase TiO 2.In optimizing the positions of N in the eight TiO 2units per cell,we ob-served molecularly bonding states—NO and N 2—for the last two cases;the obtained bond lengths of N–O and N–N were 1.20and 1.16Å,respectively,which are compared with those of the NO molecule (1.15Å)and the N 2molecule (1.10Å).Such molecularly existing dopants give rise to the bonding states below the O 2p valence bands and antibonding states deep in the band gap (Fig.1B,N i and N i ϩs ).However,these states are well screened and hardly interact with the band states of TiO 2,and thus are unlikely to be effective for photocatalysis because of con-dition iii.The importance of substitutional site N doping is emphasized in the experi-mental results discussed below.We prepared TiO 2-x N x films by sputtering the TiO 2target in an N 2(40%)/Ar gas mixture.After being annealed at 550°C in N 2gas for 4hours,the films were crystalline,with features assignable to a mixed structure of the anatase and rutile crystalline phases,as determined by x-ray diffraction (XRD).The TiO 2-x N x films were yellowish and transparent.TiO 2films were prepared in a similar fashion by sputtering the TiO 2target in an O 2(20%)/Ar gas mixture and subsequently annealing it at 550°C in O 2gas for 4hours.XRD showed that the homo-geneous anatase crystalline phase was formed.Optical absorption spectra (Fig.2B)show that the TiO 2-x N x films noticeably absorb the light at less than 500nm,whereas the TiO 2films do not,which is in good agreement with the theo-retical results.Photocatalytic activity was evaluated by measuring decomposition rates of methylene blue as a function of the cutoff wavelength of the optical high-path filters under fluorescent light (Fig.3A).Substantial photocatalyticac-Fig.1.(A )Total DOSs of doped TiO 2and (B )the projected DOSs into the doped anion sites,calculated by FLAPW.The dopants F,N,C,S,and P were located at a substitutional site for an O atom in the anatase TiO 2crystal (the eight TiO 2units per cell).The results for N doping at an interstitial site (N i -doped)and that at both substitutional and interstitial sites (N i ϩs -doped)are also shown.The energy is measured from the top of the valence bands of TiO 2,and the DOSs for doped TiO 2are shifted so that the peaks of the O 2s states (at the farthest site from the dopant)are aligned with each other.Arb.unit,arbitraryunits.Fig.2.Optical proper-ties of TiO 2-x N x (thick lines)compared with TiO 2(thin lines).(A )Calculated imaginary parts of the dielectric functions (␧2),which are averaged over three (x ,y ,and z )po-larization vectors.(B )Experimental optical absorption spectra of TiO 2-x N x and TiO 2films.Fig.3.Photocatalytic proper-ties of TiO 2-x N x samples (solid circles)compared with TiO 2samples (open squares).(A )Decomposition rates [measur-ing the change in absorption of the reference light (⌬abs)]of methylene blue as a func-tion of the cutoff wavelength of the optical high-path filters under fluorescent light with the integrated photon flux of 2.45ϫ10Ϫ9einstein (E)s Ϫ1cm Ϫ2between 350and 520nm,compared with the re-sults under BL illuminationwith the integrated photon flux of 3.51ϫ10Ϫ9E s -1cm -2in the UV range.(B )CO 2evolution as a function of irradiation time (light on at zero)during the photodegradation of acetaldehyde gas [with an initial concentration of 485parts per million (ppm)]under UV irradiation (BL with a peak at 351nm and the light power of 5.4mW cm Ϫ2)and visible irradiation [fluorescent light cut by the optical high-path filter (SC42,Fuji Photo Film),with a peakintensity at 436nm and a light power of 0.9mW cm Ϫ2].(C )Contact angles of water as a function of time under interior lighting (with light powers of 28.5and 159.4␮W cm Ϫ2in the UV and visible ranges,respectively).All these light powers were measured by the UV radiometer (UVR-2,TOPCON,Tokyo,Japan)with detectors (UD-36for the UV range and UD-40for the visible range).13JULY 2001VOL 293SCIENCE 270 o n N o v e m b e r 23, 2010w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o mtivity under 500nm has been observed in TiO 2-x N x films,and the cutoff wavelength for photocatalytic activity corresponds well with the optical absorption spectra (21,22).Both TiO 2-x N x and TiO 2films reveal similar activity under UV light [represented by the results un-der black light (BL)illumination].We also evaluated the photodecomposition of gaseous acetaldehyde of TiO 2-x N x powder samples that were prepared by treating anatase TiO 2powder (ST01,Ishihara Sangyo Kaisha,Osaka,Japan)in the NH 3(67%)/Ar atmosphere at 600°C for 3hours.The Brunaer-Emmett-Teller surface areas of the TiO 2-x N x and TiO 2powders were measured as 67and 270m 2/g,respectively.Figure 3B shows CO 2concentra-tions,evolved as a result of the photodecompo-sition of acetaldehyde,as a function of irradia-tion time.The photocatalytic activity of the TiO 2-x N x sample is superior to that of the TiO 2sample in the visible range of irradiation,whereas both samples yield similar UV activity.We used the photodegradation process of acet-aldehyde proposed in (23)to estimate quantum yields for the CO 2evolution,based on the number of incident photons being 0.42%(TiO 2-x N x )and 0.14%(TiO 2)at 436nm,and 3.0%(TiO 2-x N x )and 2.6%(TiO 2)at 351nm.Our final evaluation of the photocatalytic activity was to measure contact angles of water on the sample films under interior lighting.The so-called photoinduced hydrophilic surface is known as an important application of TiO 2(24,25).In this experiment,we used the TiO 2-x N x and TiO 2films,on which SiO 2with a nominal thickness of 5nm was deposited to hold ad-sorbed water (25).The results show an excel-lent hydrophilic surface of the SiO 2/TiO 2-x N x film,which maintained a contact angle of 6°even after 30days,in contrast to the SiO 2/TiO 2film,whose contact angle constantly increased with time (Fig.3C).As with usual TiO 2spec-imens,our TiO 2-x N x samples resisted the attack of acid and alkaline solvents such as H 2SO 4,HCl,H 2O 2,and NaOH at the ambient temper-ature,and their photocatalytic performance wasstable during successive use under 100-W mer-cury lamp irradiation for more than 3months.To investigate N states in TiO 2-x N x ,we measured N 1s core levels with x-ray photo-emission spectroscopy (XPS).Three peak structures at the binding energies of 402,400,and 396eV were observed for the TiO 2-x N x films (Fig.4A).We observed similar XPS spectra for the TiO 2-x N x powder samples.The TiO 2films also included a small amount of N;however,the peak at 396eV was not observed.Saha et al .(26)investigated the N 1s XPS spectra during the oxidation process of TiN and assigned the peaks as atomic ␤-N (396eV)and molecularly chemisorbed ␥-N 2(400and 402eV).To elucidate relations to photocatalytic activity systematically,we prepared TiO 2-x N x samples by annealing the TiO 2powder in the NH 3(67%)/Ar atmo-sphere at 550°to 600°C.The powder samples were used here,because the reaction temper-ature and the N concentration in the samples can be easily controlled by changing temper-ature and time of the NH 3treatment rather than by changing the sputtering conditions.Figure 4B shows the decomposition rates of methylene blue under visible light (␭Ͼ400nm)as a function of the ratio of the decom-posed area in the XPS peak at 396eV to the total area of N 1s .Each powder sample includ-ed the total N concentration of about 1atomic %.An increase of photocatalytic activity with an increase of the component of N with the XPS peak at 396eV is clearly observed.The decrease in photocatalytic activity observed in the powder sample (e)may be attributed to a change in the crystal structure of the sample caused by the high doping of N in the crystal,although we did not find a noticeable change in XRD.An optimum concentration of N with the XPS peak at 396eV,which may depend on the preparation process,was found at ϳ0.25atomic %(read from Fig.4B and the total concentra-tions of N in the samples)or TiO 1.9925N 0.0075.All these results,combined with the theoretical analyses described before (along with Fig.1),consistently show that the active sites of N for photocatalysis under visible light are the substi-tutional ones that can be identified with the atomic ␤-N states peaking at 396eV in the XPS spectra.The active wavelength of TiO 2-x N x ,of less than 500nm,promises a wide range of applications,as it covers the main peak of the solar irradiation energy beyond Earth’s atmo-sphere (around 460nm)and an excellent light source peaking at 390to 420nm,provided by recently developed light-emitting indium gal-lium nitride diodes (27).References and Notes1.A.Fujishima,K.Honda,Nature 238,37(1972).2.M.A.Fox,M.T.Dulay,Chem.Rev.93,341(1993).3.M.R.Hoffmann et al.,Chem.Rev.95,69(1995).4.D.F.Ollis,H.Al-Ekabi,Eds.,Photocatalytic Purifica-tion and Treatment of Water and Air (Elsevier,Am-sterdam,1993).5.K.I.Hadjiivanov,D.K.Klissurski,Chem.Soc.Rev.25,61(1996).6.A.Heller,Acc.Chem.Res.28,503(1995).7.A.Linsebigler,G.Lu,J.T.Yates,Chem.Rev.95,735(1995).8.A.K.Ghosh,H.P.Maruska,J.Electrochem.Soc.124,1516(1977).9.W.Choi et al.,J.Phys.Chem.98,13669(1994),and references therein.10.M.Anpo,Catal.Surv.Jpn.1,169(1997).11.R.G.Breckenridge,W.R.Hosler,Phys.Rev.91,793(1953).12.D.C.Cronemeyer ,Phys.Rev.113,1222(1959).13.T.Sakata,T.Kawai,in Energy Resources Through Photochemistry and Catalysis ,M.Gra ¨tzel,Ed.(Aca-demic Press,New York,1983)pp.332–358.14.E.Wimmer et al .,Phys.Rev.B 24,864(1981).15.H.J.F.Jansen,A.J.Freeman,Phys.Rev.B 30,561(1984).16.L.Hedin,B.I.Lundqvist,J.Phys.C 4,2064(1971).17.The calculations have been done without any geom-etry optimization for the S doping,because the re-sulting atomic forces are too large to obtain reason-able positions in the present unit cell (the eight TiO 2units per cell),giving the positive formation energy of 4.1eV required for the substitution of S for O,compared with that of 1.6eV for the substitution of N.18.We used a rigid shift of the band gaps,1.14eV,for both TiO 2-x N x and TiO 2as in (19),assuming that the amount of the band-gap underestimation in LDA would not be affected by doping,because long-range screening properties in TiO 2-x N x are expected to be similar to those in TiO 2.19.R.Asahi et al.,Phys.Rev.B 61,7459(2000).20.M.Jansen,H.P.Letschert,Nature 404,980(2000).21.A possibility of the degradation of methylene blue through the so-called sensitization process in a visible range (␭Ͼ500nm)(22)can be negligible in the present measurement,because this influence,if any,would have appeared in the results equally at any cutoff wavelength of the high-path filter in the mea-surement range,which,however,we did not observe.22.K.Vinodgopal et al.,Environ.Sci.Technol.30,1660(1996).23.I.Sopyan et al.,J.Photochem.Photobiol.A Chem.98,79(1996).24.R.Wang et al .,Nature 388,431(1997).25.M.Machida et al.,J.Mater.Sci.34,2569(1999).26.N.C.Saha,H.G.Tompkins,J.Appl.Phys.72,3072(1992).27.N.M.Johnson et al.,Phys.Today 53,31(October 2000)and references therein.28.We thank A.J.Freeman and W.Mannstadt for their continuous support with the FLAPW code,and K.Tanaka and N.Isomura for their experimental sup-port.28December 2000;accepted 25May2001Fig.4.(A )N 1s XPS spectra of the (upper lines)TiO 2-x N x and (lower lines)TiO 2films.(B )Decomposi-tion rates (measuring the change in absorp-tion of the reference light after 10hours)of methylene blue in the aqueous solution un-der visible light (the same light source as the visible irradiation in Fig.3B)as a func-tion of the ratio of the decomposed area inthe XPS spectra with the peak at 396eV to the total area of N 1s .The total N concentrations for the powder samples were evaluated to be 1.0atomic %,a;1.1atomic %,b;1.4atomic %,c;1.1atomic %,d;and 1.0atomic %,e. SCIENCE VOL 29313JULY 2001271o n N o v e m b e r 23, 2010w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o m。

原位红外研究纳米管TiO2光催化降解乙醇陈 好，李新勇，祝巍(大连理工大学环境与生命学院，辽宁 大连 116024)E-mail: dlut725@纳米管，并采用TEM、XRD等分析手摘要：采用水热化学反应的方法制备了TiO2纳米管的形貌和晶相进行了表征。

利用原位红外光谱技术研究纳米管段对TiO2TiO光催化降解气相乙醇反应，并考察影响反应光催化性能的主要因素。

2关键词：原位红外；光催化；纳米管；二氧化钛；乙醇；气相1.引言近年来， VOC s的污染治理问题已成为人们研究的热点问题。

当前有多种VOC s 污染的治理方法，但由于技术和条件的限制，仍存在一些问题。

而以半导体氧化物作催化剂进行气相光催化降解反应，直接利用包括太阳光在内的各种途径的紫外光，在常温下使 VOC s最终氧化为 CO2和H2O 等无机小分子，从而有效消除其对环境的污染。

这是一种经济、有效、合理的 VOC s污染治理方法，因而研究光催化降解 VOC s具有很强的实际应用价值。

乙醇通常被认为是一种重要的溶剂，广泛应用于涂料、染料、药物、橡胶、洗涤剂以及食品和酿造等工业的生产中。

同时，乙醇也是一种相对简单的重要VOC污染物，其在工业区附近空气中的含量极高，故常被用作模型反应物来考察光催化氧化VOC s反应的机理性问题[1-3]。

从近年来的文献看，原位红外光谱技术在光催化氧化乙醇反应的研究中应用广泛，尤其是在原位条件下对催化剂表面吸附物种、反应中间活性物种以及催化剂表面结构的研究优势明显。

而利用原位红外光谱法开展纳米管TiO2光催化降解 VOC s的研究尚未见报道。

本文以纳米管TiO2为光触媒，利用原位红外光谱法，在常温常压下，研究了光催化降解气相乙醇的反应。

2.实验设备与方法2.1实验设备本实验利用日本岛津产IRPrestige-21型傅立叶变换红外光谱仪，将催化剂压成可红外透过的自支撑片，放入自制气体吸收池，并按实验要求摄谱。

紫外灯为4W的杀菌灯(主波长254nm)。

HEB大学毕业设计（论文）掺铁二氧化钛的制备与其对罗丹明B的降解学生姓名 pp指导教师 cp专业环境工程学院 SPGC2011年06月01日Graduation Project(Thesis)HarbinUniversity of CommerceThe preparation of iron-doped TiO2 andthe degradation of Rhodamine BStudentSupervisorSpecialty Environment EngineeringSchool2011-06-01毕业设计（论文）任务书毕业设计（论文）审阅评语毕业设计（论文）审阅评语毕业设计（论文）答辩评语摘要对改性TiO2的制备方法进行了研究。

以钛酸丁酯为前躯物，采用溶胶凝胶法制备纳米TiO2光催化材料。

对罗丹明B溶液进行光催化降解，寻求光催化降解罗丹明B 溶液条件。

实验结果表明：Fe-TiO2光催化材料的最优制备条件为前驱体配比（摩尔比）为n=Ti(OC4H9)4: C2H5OH: HNO3: H2O=1: 15:0.01:1，掺铁量W (Fe3+/TiO2)=0.6%，锻烧温度为450℃，锻烧时间为2h。

在此基础上，选择273nm波长的紫外灯对罗丹明B溶液催化进行催化降解实验，实验结果表明：紫外光下，pH=4最佳条件下Fe-TiO2处理罗丹明B溶液的脱色率达到90.2%。

研究表明，通过掺杂铁离子对二氧化钛进行的改性使反应的响应光谱向可见光拓展，并有效抑制电子—空穴对的复合，很大程度提高了光催化反应效率。

关键词：二氧化钛光催化掺铁制备AbstractIn this paper the preparation methods of modified TiO2was studied. Itis suggested that sol-gel method using Ti(OC4H9)4, is the best method forpreparation of TiO2photocatalytic materials. Rhodamine B solution to seek photocatalytic degradation,photocatalytic degradation Rhodamine B solution conditions．The optimal reaction condition was gotten after experiments and analysis：n=Ti(OC4H9)4:C2H5OH:HNO3:H2O=1:15:0.01:1(mol ratio)，W(Fe3+/TiO2)=0.6%(molratio)，calcinations at 450℃ for 2 hours．On this basis using ultraviolet germicidal lamp with wavelength of 273nm as Liaht-source, the contaminants removal effect in Rhodamine B．Experimental results show that: Under UV irradiation, pH=4 best conditions Fe-TiO2processing Rhodamine B determined.the decolored rate reached the solution as high as 90.2 %．The experiment results showed that photocatalytic activity was improved by sol-gel method by doping of Fe3+ and the photocatalytic efficiency were also raised obviously. The addition of appropriate amount of Fe3+is effective forimproving the photo-catalytic activities of TiO2by inhibiting the formation of recombination centers of photo-generated electron-hole pairs on thesurface of TiO2particles．Keywords：TiO2photocatalytic iron-doped preparing目录摘要IAbstractII1 绪论01.1 引言01.2 纳米TiO2光催化机理01.3 纳米TiO2的改性方法11.4 纳米TiO2的发展概况21.5 纳米TiO2光催化氧化技术的研究现状与应用前景31.6 本课题研究的目的和意义42 纯TiO2和掺铁TiO2的制备52.1 实验原理52.2 主要实验设备和药品52.3 二氧化钛和掺铁二氧化钛的制备过程62.4 正交实验确定制备TiO2各药品配比62.5 正交实验确定制备Fe-TiO2最佳条件82.6 Fe- TiO2光催化剂制备条件的影响102.6.1 锻烧温度的影响102.6.2 锻烧时间的影响112.6.3 掺铁量W(Fe3+/ TiO2)的影响122.7 小结133 光催化实验与其影响因素143.1 光催化机理143.2 光催化降解实验153.2.1 实验方法153.2.2 分析方法163.3 处理溶液pH的影响173.4 光催化时间影响183.5 小结19结论19参考文献21致221 绪论1.1引言二氧化钛，化学式为TiO2，俗称钛白粉，英文：Titanium (IV) oxide。

第42卷第2期2022年2月Vol.42No.2Feb.，2022工业水处理Industrial Water TreatmentDOI：10.19965/ki.iwt.2022-0020钛酸盐/活性炭吸附协同光催化去除水中4-氯酚刘月1，钱天伟1，刘晓娜1，冀豪栋2，3，李璠2，3，刘文2，3（1.太原理工大学环境科学与工程学院，山西太原030024；2.北京大学环境科学与工程学院，水沙教育部重点实验室，北京100871；3.北京大学国家环境保护河流全物质通量重点实验室，北京100871）[摘要]通过一步水热法制备了一种钛酸盐/活性炭复合材料（TAC），可高效吸附水中污染物实现预富集，进而在紫外光下光催化降解污染物。

研究显示，TAC可在5min内吸附86.9%的4-氯酚（4-CP），具有比活性炭更快的吸附速率和更大的吸附量，得益于微碳改性钛酸盐后对4-CP的毛细管凝聚作用。

TAC可在4h内光催化降解95.6%预富集的4-CP，实现85.8%的脱氯率。

TAC光催化性能显著提升的机理在于其中的活性炭和微碳组分可高效传导光激发生成的光生电子，由此抑制光生载流子复合。

猝灭实验与自由基鉴定证实羟基自由基（·OH）是主要活性物种，并通过福井指数理论计算结合中间产物鉴定，确定了4-CP的降解路径主要为·OH取代所导致的C—Cl键断裂及·OH加成。

［关键词］钛酸盐；活性炭；预富集；光催化降解［中图分类号］X52［文献标识码］A［文章编号］1005-829X（2022）02-0067-08Synergy of adsorption and photocatalysis for4−chlorophenolremoval using titanate/activated carbonLIU Yue1，QIAN Tianwei1，LIU Xiaona1，JI Haodong2，3，LI Fan2，3，LIU Wen2，3（1.School of Environmental Science and Engineering，Taiyuan University of Technology，Taiyuan030024，China；2.The Key Laboratory of Water and Sediment Sciences，Ministry of Education，College of Environmental Sciencesand Engineering，Peking University，Beijing100871，China；3.State Environmental Protection KeyLaboratory of All Material Fluxes in River Ecosystems，Peking University，Beijing100871，China）Abstract：Titanate/activated carbon composite（TAC）was synthesized through a one‑step hydrothermal treatment method，which could efficiently pre‑concentrate the target organic pollutant through adsorption in water，and then de‑graded through photocatalysis under UV light.Results showed that TAC achieved86.9%of4-chlorophenol（4−CP）adsorption within5min，demonstrating that TAC had faster adsorption kinetic rate and larger adsorption capacity compared with original activated carbon.Moreover，TAC could degrade95.6%of pre‑concentrated4-CP within4h through photocatalysis and achieved85.8%of dechlorination rate.The mechanism enhanced photocatalytic activity of TAC was attributed to the activated carbon and micro‑carbon components，which could efficiently transfer the photo‑excited electron，thus inhibiting the recombination of photo‑generated charge carrier.Hydroxyl radicals （·OH）were proved to be the main reactive species in this reaction system via radical quenching test and radical identification.Meanwhile，the degradation pathway of4-CP was also confirmed through theoretical calculation on Fukui index and intermediates analysis，which proceeded as C—Cl cleavage after·OH substitution and·OH addi‑tion.Key words：titanate；activated carbon；pre‑concentration；photocatalytic degradation［基金项目］国家重点研发计划青年科学家项目（2021YFA1202500）；国家自然科学基金（21906001）；北京市科技新星计划（Z191100001119054）；中国博士后科学基金资助项目（2021M700213）试验研究工业水处理2022-02，42（2）氯酚类物质（CPs）是工业废水中最常见的持久性有机污染物之一，主要来源包括工业制革与防腐剂、杀虫剂、防污剂的合成等。