超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

磁性纳米TiO2/SiO2/Fe3O4光催化剂的制备及表征

以纳米Fe3O4磁粉为核心，采用溶胶一凝胶法制备了TiO2／SiO2／Fe3O4复合光催化剂．用XRD、TEM及元素分析对其结构和表面形貌进行了表征．以具有偶氮染料结构的甲基橙水溶液为目标反应物，评价其光催化活性．结果表明，所制TiO2／SiO2／FeaO4样品为双层包覆型结构，SiO2为中间层，最外层是锐钛矿型的TiO2,该复合光催化剂对甲基橙溶液有较高的光催化活性，并具有可利用其磁性回收重用的特点，应用前景广泛。     

Preparation and photocatalytic properties of nanometer-sized magnetic TiO2/SiO2/CoFe2O4 composites

Magnetic TiO2/SiO2/CoFe2O4 nanoparticles (TiO2/SCFs) were prepared by a sol-gel process in a reverse microemulsion combined with solvent-thermal technique. TiO2/SCFs were characterized by Fourier transform infrared spectrometry, thermogravimetric analysis-differential scanning calorimetry, X-ray diffraction, Raman spectrometry, TEM, BET specific surface area measurement, and magnetic analysis. Structure analyses indicated that TiO2/SCFs presented a core-shell structure with TiO2 uniformly coating on SiO2/CoFe2O4 nanomagnets (SCFs) and typical ferromagnetic hysteresis. TiO2/SCFs showed larger specific surface area and better photocatalytic activities than TiO2 and TiO2/CoFe2O4 photocatalysts prepared by the same method. The doping interaction between TiO2 and CoFe2O4 reduced thanks to the inert SiO2 mesosphere.     

煅烧温度、煅烧时间和Fe3+掺杂量对TiO2光催化性能的影响

以钛酸四正了酯为先驱物,采用溶胶-凝胶法制备了纯TiO2和Fe3+掺杂的纳米TiO2(Fe3+/TiO2)光催化剂,并用XRD、UV-Vis等进行了表征,系统研究了煅烧温度、煅烧时间和Fe3+掺杂量对催化剂在自然光条件下光催化降解甲基橙性能的影响.结果表明,相同煅烧温度下,Fe3+/TiO2的粒径比纯TiO2的粒径小.制备纯TiO2和Fe3+/TiO2的最佳煅烧时间分别为4h和3h,最佳煅烧温度均为773K.适量掺入Fe3+可以显著提高纳米TiO2在自然光条件下的光催化降解活性,Fe3+/TiO2中Fe3+的最佳掺杂量为10.00%,相应的脱色效率为28.37%.     

Mn、N共掺杂TiO_2负载竹质活性炭纤维的制备及可见光光催化性能

为研究Mn、N共掺杂TiO_2负载竹质活性炭纤维(Mn-N/TiO_2-BACF)的可见光光催化性能,首先,以MnSO_4·H_2O为锰源,尿素为氮源,采用溶胶-凝胶法制备了光催化复合材料Mn-N/TiO_2-BACF;然后,利用SEM、XRD及XPS等考察了煅烧温度对Mn-N/TiO_2-BACF结构和可见光光催化性能的影响。结果表明:Mn、N共掺杂使光催化复合材料的光响应范围由紫外光区域拓宽至可见光区域;随煅烧温度的提高,光催化复合材料表面的晶格氧含量逐渐降低,吸附氧含量先降低后增加,而羟基氧含量有所增加;光照400min后,350℃锻烧制备的Mn-N/TiO_2-BACF在可见光下对亚甲基蓝的光降解率达99.7%。同时,还发现Mn-N/TiO_2-BACF在可见光下的光降解率与煅烧温度没有相关性。     

磁性La3+掺杂TiO2的制备及性能

利用溶胶-凝胶法,在室温条件下,以钛酸四丁酯、硝酸镧为主要原料,无水乙醇为溶剂,冰醋酸为抑制剂,浓硝酸为催化剂制得稳定的掺La3+TiO2溶胶,陈化后的凝胶经不同温度煅烧3h后制得不同掺La3+量的TiO2。通过XRD对不同煅烧温度及不同掺La3+量的TiO2进行了表征;以紫外光为光源,研究了掺La3+-TiO2对甲基橙溶液的光降解效果。用化学共沉淀法制备了具有强磁性的Fe3O4水基磁流体,再与La3+掺杂TiO2进行复合,制备了Fe3O4负载量不同的磁性La3+掺杂TiO2,研究了Fe3O4负载量不同的La3+掺杂TiO2对甲基橙的光催化降解效果、磁分离回收率的影响。结果表明,掺La3+量及煅烧温度对TiO2的晶型、各晶型TiO2的相对含量及对甲基橙的光降解效果均有影响。La3+掺杂TiO2比纯TiO2显示出更强的光催化性能,掺La3+量2%,热处理温度450℃的La3+掺杂TiO2光催化活性最高。Fe3O4负载量为10%的Fe3O4/La3+-TiO2对甲基橙的降解率8h时为99.4%;磁分离回收率达97.39%。     

H(2)O(2)-sensitized TiO(2)/SiO(2) composites with high photocatalytic activity under visible irradiation

TiO(2)/SiO(2) composite photocatalysts were prepared by depositing of TiO(2) onto nano-SiO(2) particles. X-ray diffraction (XRD), transmission electron micrograph (TEM), Raman spectrometer, UV-Vis diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy (FT-IR) were employed to characterize the properties of the synthesized TiO(2)/SiO(2) composites. These results indicated that the products without calcination were amorphous, and calcination could enhance the crystallinity of TiO(2). Increases in the amount of TiO(2) would decrease the dispersion in the composites. H(2)O(2)-sensitized TiO(2)/SiO(2) composite photocatalysts could absorb visible light at wavelength below 550 nm. The photocatalytic activity of as-prepared catalysts was characterized by methyl-orange degradation. The results showed the uncalcined composite photocatalysts with amorphous TiO(2) exhibited higher photocatalytic activity under visible light, and the activity of catalysts with TiO(2) content over 30% decreased with increasing of TiO(2) content. Increases in the calcination temperature and TiO(2) content promote the formation of bulk TiO(2) and result in a decrease in activity.     

片状磁性纳米TiO2/SiO2/NiFe2O4制备及光催化性能

以锐钛矿磁性纳米TiO2/SiO2/NiFe2O4(TSN)为原料,采用水热法制备了片状磁性纳米TSN.利用XRD、TEM等技术对样品进行了表征.水热法处理后核壳结构的TSN部分转变为片状,催化剂磁性增强.以亚甲基兰溶液为模拟水样测试了样品的光催化性能,考察了催化剂加入量、反应时间、pH值等因素的影响.实验表明:片状磁性纳米TSN光催化性能明显优于粒状TSN.片状TSN具有良好的吸附性能,提高了光催化反应的初始速率.用于处理亚甲基兰废水时受pH值的影响较小,1小时的脱色率在90%以上.     

热处理温度对TiO2/SiO2复合气凝胶光催化性能的影响

采用溶胶–凝胶法在常压下经不同温度热处理制备了TiO2/SiO2复合气凝胶光催化剂,利用XRD、TGA和BET等手段对其微观结构进行表征,以甲基橙溶液光催化降解实验评价其光催化性能,研究了热处理温度对TiO2/SiO2复合气凝胶的微观结构及光催化性能影响规律.结果表明:随着热处理温度升高,TiO2/SiO2复合气凝胶中锐钛矿结晶度升高,晶粒尺寸增大,比表面积减小,使TiO2/SiO2复合气凝胶对甲基橙溶液的光催化降解活性呈现先升后降的变化趋势.当热处理温度为700℃左右,紫外光照20 min TiO2/SiO2复合气凝胶对甲基橙溶液的降解率达到95.4%.     

均匀沉淀法制备ZnO、Fe/ZnO光催化剂

以六水合硝酸锌、九水合硝酸铁和CO(NH2)2为原料,采用均匀沉淀法并且改变实验条件制备了纯纳米ZnO和纳米Fe/ZnO光催化剂。通过X射线衍射(XRD)和扫描电子显微镜(SEM)对所有样品进行表征,并对部分样品进行了X射线能谱分析仪(EDS)测试。结果显示所有样品均为六方纤锌矿结构。此外,所有样品均由小颗粒聚集在一起而形成了形状、大小各不相同的团聚物或颗粒膜。而且随煅烧温度和Fe掺杂浓度的改变,Fe/ZnO样品的晶粒尺寸和表面形貌也随之变化。以甲基橙溶液作为污染物,在高压汞灯的照射下进行了光降解实验,实验结果表明:Fe掺杂Fe/ZnO样品的光催化性能相较纯纳米ZnO样品得到了改善。当Fe掺杂量为1.5%时Fe/ZnO样品的光催化性能最好;另外,适当煅烧温度也使Fe/ZnO样品的光催化活性得到了提升,其中最适煅烧温度为500℃。无论是Fe的掺杂浓度还是煅烧温度,适当的Fe的掺杂浓度和煅烧温度都有利于改善Fe/ZnO样品光催化剂的性能。     

Direct formation of reusable TiO2/CoFe2O4 heterogeneous photocatalytic fibers via two-spinneret electrospinning

A reusable photocatalytic TiO2/CoFe2O4 composite nanofiber was directly formed by using a vertical two-spinneret electrospinning process and sol-gel method, followed by heat treatment at 550 degrees C for 2 h. The high photocatalytic activity of the composite nanofibers depends on the good morphology of the fibers and the appropriate calcination temperature. The crystal structure and magnetic properties of the fibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). The photocatalytic activity of the TiO2/CoFe2O4 fibers was investigated through ultraviolet-visible absorbance following the photo-oxidative decomposition of phenol. Meanwhile, the presence of CoFe2O4 not only broadens the response region of visible light, but also enhances the absorbance of UV light. Furthermore, these fibers displayed photocatalytic activity associated with magnetic activity of CoFe2O4 ferrites, allowing easy separated of the photocatalysts after the photo-oxidative process and effectively avoided the secondary pollution of the treated water.     

复合半导体光催化材料ZnFe2O4-TiO2/SiO2结构与光响应性能研究

采用溶胶．凝胶法制备了负载型复合半导体光催化材料ZnFe2O4-TiO2／SiO2，并通过DTA-TG、XRD、XPS、Raman、TPR及UV-Vis DRS等实验技术对复合材料的晶体结构、表面组成及光响应性能进行了表征和评价．结果表明：ZnFe2O4晶相以高分散状态存在于光催化材料的表面；ZnFe2O4与TiO2复合可使部分Fe^3＋进入体相TiO2的晶格中，促进其由锐钛矿向金红石的相转变，同时表面剩余的少量Zn计聚集形成ZnO物相；TiO2的相变由体相开始，随着ZnFe2O4含量的增加逐渐向表面扩展；SiO2的加入使活性组分更加分散，TiO2平均粒径〈10nm；ZnFe2O4的加入明显拓宽了TiO2的吸光域，并增强了对可见光的吸收．     

Photocatalytic degradation of Direct Red 23 dye using UV/TiO2: Effect of operational parameters

In this study, the photocatalytic degradation of Direct Red 23 (Scarlet F-4BS) was investigated in UV/TiO2 system. The effect of catalyst loading and pH on the reaction rate was ascertained and optimum conditions for maximum degradation were determined. The results obtained showed that acidic pH is proper for the photocatalytic removal of Direct Red 23. In addition, the effects of several cations (Cu2+, Al3+, Cr3+, and Sn4+) and anions (BiO3(-), SO4(2-), and CN(-)) and C2H5OH were examined in this photocatalytic process. On the order hand, three types of catalysts (Fe2O3, SnO2, and ZnO) were compared with TiO2. After 90 min reaction, the relative decomposition order established was UV/TiO2>UV/SnO2>UV/Fe2O3>UV/ZnO.     

H2O2 sensor based on the room-temperature phosphorescence of Nano TiO2/SiO2 composite

A TiO2/SiO2 composite prepared by the sol-gel route can produce highly emissive broadband room-temperature phosphorescence at an excitation wavelength of 403 nm. The white phosphorescence of TiO2/SiO2 could be quenched by H2O2. The phosphorescence quenching effect demonstrated excellent sensitivity and high selectivity to H2O2. Furthermore, the phosphorescence of TiO2/SiO2 can be recovered when it is dipped in a hydroxylamine hydrochloride solution. Therefore, the TiO2/SiO2 was used to develop a reproducible phosphorescence sensor for H2O2. It has been successfully applied to the determination of H2O2 in the enzymatic catalytic reaction and real samples.     

TiO2 and SnO2 magnetic nanocomposites: influence of semiconductors and synthetic methods on photoactivity

A number of reports have been published on use of TiO2 in thin films, magnetic nanocomposites, or heterostructures such as TiO2/Ag and TiO2/SnO2, as catalysts for water decontamination. Hence, semiconductor materials such as SnO2, associated with TiO2 in such nanocomposites, should be assessed in depth for such applications, especially those involving complex structures, such as magnetic photocatalytic nanocomposites. The present study describes the synthesis, characterization and testing of the photocatalytic potential of TiO2 or SnO2 magnetic nanocomposites obtained by the polymeric precursor and the hydrolytic sol-gel methods. The nanocomposites TiO2/CoFe2O4 and SnO2/CoFe2O4 were synthesized from polymeric precursors while TiO2/Fe3O4 and SnO2/Fe3O4 were synthesized by the hydrolytic sol-gel method. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (FEG/SEM) and transmission electron microscopy (TEM). The photocatalytic potentials were evaluated by rhodamine B dye photodegradation under UV-C radiation. Compared to SnO2, the nanocomposites with a coating of TiO2 were found to show better photocatalytic activity, but the SnO2 magnetic nanocomposites showed some photocatalytic activity, even though SnO2 is reported to be inactive for these purposes. As for the synthesis method, the nanocomposites obtained from polymeric precursors had smaller surface areas, but higher photocatalytic activity, than those obtained by the hydrolytic sol-gel method. This observation was attributed to the higher crystallinity and a more active surface resulting from calcination of the polymeric precursor material.     

溶胶-凝胶法制备TiO2粉体及其光催化性能研究

以钛酸丁酯为前驱物,无水乙醇为溶剂,采用溶胶-凝胶法制备了TiO2粉体,并采用紫外分光光度计、XRD等表征手段对TiO2的粒度、晶型结构进行了表征,分析了煅烧温度、TiO2晶型比例、溶液初始pH值等因素对TiO2结构性能及光催化活性的影响.结果表明:TiO2的锐钛矿晶型与金红石晶型的转相温度为700 ℃左右;采用溶胶-凝胶法制备TiO2时,控制溶液的pH值为4,煅烧温度为600 ℃,所得产物晶型全部为锐钛矿;当无水乙醇与钛酸丁酯的体积比为10:1时,产物的粒径为617 nm;且当配制溶液pH值为4,煅烧温度为600℃条件下,煅烧时间为40~60 min时,所制备TiO2的光催化效果较好,降解率较高;当光催化体系的pH值为9、以质量浓度为10 mg/L的亚甲基兰溶液浸泡2 h,TiO2的用量为0.25 g/L时,产物的降解率高达95.3%.     

铁铕共掺杂的TiO_2空心微球的制备及光催化活性

通过溶胶-凝胶法制备铁铕共掺杂的TiO_2(Fe~(3+)-Eu~(3+)/TiO_2)空心微球,采用XRD、TEM、BET和XPS等对样品进行表征,以亚甲基蓝(MB)的光催化降解为目标反应,评价其光催化活性。结果表明:SiO_2微球表面均匀地包覆了1层TiO_2,超声有利于提高SiO_2@TiO_2复合微球间的分散性,同时也发现煅烧前对SiO_2@TiO_2复合微球进行研磨处理后所得的Fe~(3+)-Eu~(3+)/TiO_2空心微球部分塌陷,而未研磨和煅烧后研磨所得Fe~(3+)-Eu~(3+)/TiO_2空心微球完整性较好。XRD和BET分析表明,Fe~(3+)-Eu~(3+)/TiO_2空心微球为锐钛矿且具有良好的介孔结构,铁铕共掺杂在TiO_2空心微球中产生协同作用,使Fe3+-Eu3+/TiO2空心微球的粒径进一步减小,比表面积增大。当Fe~(3+)的掺杂量为1.0%、Eu~(3+)的掺杂量为0.5%时,Fe~(3+)-Eu~(3+)/TiO_2空心微球的光催化活性最高。     

静电纺丝法制备Fe3+/TiO2纳米纤维及表征

以聚乙烯吡咯烷酮(PVP)为纤维模板,钛酸四丁酯(Ti[O(CH2)3CH3]4)和Fe3+为前驱体,乙醇为溶剂,醋酸为催化剂,采用静电纺丝法制备不同含铁量的复合纳米纤维Fe3+/TiO2,经500℃煅烧得到以锐钛矿为主的Fe3+/TiO2纳米纤维。采用扫描电子显微镜(SEM)和X射线衍射仪(XRD)分别表征了Fe3+/TiO2纳米纤维的形貌与晶态,计算了样品的晶粒尺寸和锐钛矿所占的比例,并比较了5%Fe3+/TiO2纳米纤维、5%Fe3+/TiO2粉体以及纯TiO2纳米纤维三者光催化降解亚甲基蓝(MB)的效果。研究表明:由静电纺丝法制备的5%Fe3+/TiO2纳米纤维的光催化降解效果比相同含铁量的粉体的降解效果好,TiO2纳米纤维比5%Fe3+/TiO2纳米纤维的光催化活性高。     

Fe~(3+)/Ti~(4+)赋存状态对钛酸铝/莫来石复合材料结构的影响

借助XRD、SEM和能谱分析仪等手段,研究了1 600℃煅烧中低品位矾土制备的钛酸铝/莫来石(Al_2TiO_5ss/3Al_2O_3·2SiO_2ss)复合材料经1 200℃保温12h后结构的稳定性。结果表明:高温煅烧中低品位矾土后,其合成材料的结晶物相组成为3Al_2O_3·2SiO_2ss、Al_2TiO_5ss和少量残存的方石英;Fe~(3+)或Ti~(4+)离子以不同形态赋存于结晶相(3Al_2O_3·2SiO_2ss和Al_2TiO_5ss)和非晶相。含Fe~(3+)/Ti~(4+)离子的3Al_2O_3·2SiO_2ss将Al_2TiO_5ss结晶相分割,使其蜷缩其间,并抑制Al_2TiO_5ss的分解;高温下,二者因组成元素相近而致使晶界融合,进而共同构建了体系牢固的致密骨架结构。由3Al_2O_3·2SiO_2ss和Al_2TiO_5ss等高温物相构成的致密结构将非晶相挤压于空隙结构的3Al_2O_3·2SiO_2ss晶间,避免了低熔点相富集带来的不利影响,进而赋予该Al_2TiO_5ss/3Al_2O_3·2SiO_2ss复合材料良好的结构稳定性。     

铝合金表面制备二氧化钛薄膜及其光催化活性研究

分别以阳极氧化处理的6061铝合金和纯铝为载体,用液相沉积的方法在载体上制备了二氧化钛薄膜.结果表明,在6061铝合金上的TiO2纳米薄膜呈现带有孔洞的竹节状结构,而纯铝基片上的TiO2纳米薄膜具有良好的一维贯通结构.这主要是在AAO模板制备过程中,由于铝合金中的合金元素Mg被氧化,其产生的氧化物体积比Al2O3的体积小所致.在铝合金表面的TiO2薄膜光催化性能优于纯铝表面的TiO2薄膜.铝合金表面制备的TiO2薄膜因其特殊的带孔洞的竹节状结构,使其比表面积比纯铝上的TiO2薄膜大,因此其光降解甲基蓝效果更好.TiO2对甲基蓝的光催化降解符合一级反应动力学公式,在0.1 mol/L的氟钛酸铵溶液中沉积得到的TiO2薄膜光催化性能最好,表观反应速率为k=0.00444/min.