Study on the optical property and surface morphology of N doped TiO2 film deposited with different N2 flow rates by DCPMS

N doped TiO₂ films were deposited by direct current pulse magnetron sputtering system at room temperature. By using UV-Vis spectrophotometer and atomic force microscope, we studied the influence of N₂ flow rate on the optical property and surface morphology of films. The results indicate that the optical property and surface morphology of N doped TiO₂ film was dominated by the N₂ flow rate. The mean absorbency in visible range of pure TiO₂ films is near to 0%, which means that the pure TiO₂ could hardly display the photocatalytic property in visible range. When N₂ flow rate is 2 sccm, the mean absorbency in visible range of N doped TiO₂ film could reach at 24%. In this case, the film could be used as photocatalyst induced by visible light. While with increasing N₂ flow rate, the mean absorbency in visible range of N doped TiO₂ film decreased abruptly. Especially when N₂ flow rate exceeded 8 sccm, the mean absorbency in visible range of N doped TiO₂ film decreased to about 0%, which is like pure TiO₂ fimls.     

Composition and crystal structure of N doped TiO2 film deposited at different O2 flow rate by direct current sputtering

N doped Ti0₂ films were deposited by direct current pulse magnetron sputtering system at room temperature. The influence of 0₂ flow rate on the crystal structure of deposited films was studied by Stylus profilometer, X-ray photoelectron spectroscopy, and X-ray diffractometer. The results indicate that the 0₂ flow rate strongly controls the growth behavior and crystal structure of N doped Ti0₂ film. It is found that N element mainly exists as substitutional doped state and the chemical stiochiometry is near to TiO_1.68±0.06N_0.11±0.01 for all film samples. N doped Ti0₂ film deposited with 2 sccm (standard-state cubic centimeter per minute) 0₂ flow rate is amorphous structure with high growth rate, which contains both anatase phase and rutile phase crystal nucleuses. In this case, the film displays the mix-phase of anatase and rutile after annealing treatment. While N doped Ti0₂ film deposited with 12 cm³/min 0₂ flow rate displays anatase phase before and after annealing treatment. And it should be noticed that no TiN phase appears for all samples before and after annealing treatment.     

Synthesis and enhanced visible-light responsive of C,N,S-tridoped TiO2 hollow spheres

C,N,S-tridoped TiO2 hollow spheres （labeled as C,N,S-THs） were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by X- ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-Vis diffuse reflectance spectrum （DRS）, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy （XPS） and Photoluminescence emission spectroscopy （PL）. The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet （UV） to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B （Reactive Brilliant Red dye, C.I. Reactive Red 2） aqueous solution under visible-light （λ 〉 420 nm） irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.     

SiO2纳米粉掺杂对薄膜光催化剂结构和活性的影响

针对固定膜光催化剂吸附能力差的缺陷,在催化剂的涂覆溶胶中掺杂具有较大比表面积的SiO₂纳米粉制备了一种新的TiO₂薄膜.通过X射线衍射(XRD)、扫描电镜(TEM)和红外光谱(FTIR)等手段对催化剂进行表征发现,催化剂的晶相以锐钛矿为主,并含有少量的金红石,平均晶粒尺寸为27nm左右.其中掺杂的SiO₂以十几到几十纳米的无定型团簇形式分散于薄膜中,除了能增大薄膜的表面积外,对TiO₂的晶体结构和表面基团等性质几乎没有影响.光催化降解试验表明,SiO₂掺杂后薄膜的活性大大改善,并受掺杂SiO₂的原始粒径和掺杂量影响很大.此外,该催化剂还具有很好的稳定性,在连续30多天的使用中,对活性艳红X-3B的去除率一直维持在80%左右,活性未见降低.     

上转换发光剂掺杂纳米TiO2的制备及可见光降解乙基紫的研究

合成了一种新型含有稀土金属Er的上转换发光剂40CdF₂·60BaF₂·1.6Er₂O₃,此上转换发光剂在488 nm可见光的激发下,产生了5个波长均小于387 nm的上转换紫外光发射峰.采用超声波分散的方法制备出了上转换发光剂掺杂的纳米TiO₂可见光光催化剂.利用X-射线衍射(XRD)及透射电镜(TEM)对催化剂进行了表征.以乙基紫染料为研究对象,研究了在(三基色灯下发出的)可见光的照射下该可见光光催化剂的催化降解性能,并与未掺杂的纳米TiO₂粉末的催化性能进行了对比.结果表明,作为掺杂成分的上转换发光剂可有效地将可见光转化为紫外光并被纳米TiO₂粉末吸收利用,在可见光照射12.0 h后乙基紫降解率达到了99.68%,大大高于未掺杂纳米TiO2时的降解率.     

Visible light responsive N-F-codoped TiO2 photocatalysts for the degradation of 4-chlorophenol

Visible light responsive N-F-codoped TiO₂ photocatalysts exhibit a higher catalytic activity than N-doped TiO₂ for the degradation of 4-chlorophenol due to the synergistic effect of nonmetal elements.     

Photo-catalytic decolourisation of toxic dye with N-doped titania: A case study with Acid Blue 25

Dyes are one of the hazardous water pollutants.Toxic Acid Blue 25,an anthraquinonic dye,has been decolourised by photo-catalysing it with nitrogen doped titania in aqueous medium.The photo catalyst was prepared from 15% TiCl 3 and 25% aqueous NH 3 solution as precursor.XRD and TEM revealed the formation of well crystalline anatase phase having particle size in the nano-range.BET surface area of the sample was higher than that of pure anatase TiO 2.DRS showed higher absorption of radiation in visible range compared to pure anatase TiO 2.XPS revealed the presence of nitrogen in N-Ti-O environment.The experimental parameters,namely,photocatalyst dose,initial dye concentration as well as solution pH influence the decolourisation process.At pH 3.0,the N-TiO 2 could decolourise almost 100% Acid Blue 25 within one hour.The influence of N-TiO 2 dose,initial concentration of Acid Blue 25 and solution pH on adsorption-desorption equilibrium is also studied.The adsorption process follows Lagergren first order kinetics while the modified Langmuir-Hinselwood model is suitably fitted for photocatalytic decolourisation of Acid Blue 25.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

Cr3+掺杂对TiO2薄膜光催化活性的影响

采用溶胶-凝胶法制备了TiO2粉末和以釉面瓷砖为载体的TiO2薄膜,讨论了不同Cr3+掺杂浓度对TiO2光催化活性的影响,并采用UVVIS对其光学性能进行了检测.结果表明,Cr3+掺杂和釉面瓷砖的交互作用能够显著提高TiO2薄膜的光催化活性,最佳掺杂浓度为6.04×1017个·cm-3,且随着TiO2光催化活性的提高,薄膜的吸收带边发生了明显的红移,提高了可见光的利用率.     

可见光响应手性TiO2复合光催化剂及其降解有机污染物

通过空穴和自由基捕获剂的加入,首先研究了可见光激发下手性TiO₂复合光催化剂降解罗丹明B和四环素的机理. 结果表明,可见光激发TiO₂光催化剂降解罗丹明B和四环素的机理是相同的,其形成的光生空穴是降解有机物的关键影响因素.利用D型手性表面活性剂在低温时可以构建右旋非对称手性堆积结构的D-TiO₂. 这种非对称结构在介孔TiO₂内部引入氧空穴和Ti-N键,使D-TiO₂也具有显著的可见光响应和可见光降解活性. La³⁺ 或者Fe³⁺的掺杂几乎不影响催化剂的形貌及其TiO₂的结晶过程, 但可以在催化剂中形成光生空穴和电子的捕获中心,显著提升可见光激发下TiO₂催化剂中光生空穴和电子的分离率,从而增强催化剂对四环素的光降解活性.     

TiO2诱导下左旋氧氟沙星的可见光降解及其机制

左旋氧氟沙星是一种新型污染物.单一的左旋氧氟沙星(LFV)和Ti O2无可见光响应,但二者共存下左旋氧氟沙星能发生显著的可见光降解.为此研究Ti O2用量、溶液p H以及左旋氧氟沙星浓度对Ti O2/Vis(可见光)降解左旋氧氟沙星的影响及机制.结果表明,左旋氧氟沙星能吸附在Ti O2表面,吸附服从准二级吸附动力学和Langmuir吸附等温线.吸附左旋氧氟沙星的Ti O2漫反射UV-Vis光谱进一步表明二者形成表面复合物.左旋氧氟沙星的Ti O2/Vis降解动力学符合LangmuirHinshelwood方程.合适的Ti O2浓度和中性p H有利于光解过程的进行.自由抑制实验、N2保护下左旋氧氟沙星的Ti O2/Vis降解实验揭示·O-2是该过程中的主要活性物种.同时,无氧左旋氧氟沙星-Ti O2悬浮液光照不同时间的UV-Vis光谱证明体系中存在电子向Ti O2导带的注入.依据实验结果提出吸附在Ti O2表面的左旋氧氟沙星与Ti O2形成表面复合物,在可见光照下发生电子迁移,从而引发左旋氧氟沙星降解.本研究表明利用污染与Ti O2形成表面复合物诱导其可见光降解可用来去除水中某些有机污染物.     

Promotional effect of Si-doped V2O5/TiO2 for selective catalytic reduction of NOx by NH3

TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia (V2O5) loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites (especially the Br nsted-acid) and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.     

聚苯胺/TiO2-SiO2复合催化剂去除空气中甲醛的研究

为提高空气净化效果,研究了聚苯胺(PANi)/TiO2-SiO2复合催化剂对甲醛的吸附和协同光催化作用.考察了TiO2-SiO2涂敷层数、PANi浓度和不同酸(有机酸、盐酸)掺杂对紫外光催化氧化甲醛的影响,以及PANi/TiO2-SiO2在可见光下去除甲醛的效果.结果表明,复合聚苯胺的存在使吸光范围拓展到可见光区,提高了对甲醛的吸附.涂敷3层TiO2-SiO2、吸附浓度0.26g/L的PANi溶液所得复合催化剂紫外光催化效果最好,与没有PANi的催化剂相比,使甲醛去除率提高2倍.有机酸掺杂比无机酸掺杂的PANi复合催化剂紫外光催化甲醛的初期反应快,但最终甲醛的去除率相同.PANi/TiO2-SiO2具有显著的可见光催化氧化去除甲醛的活性,对低浓度甲醛氧化去除速率更快.     

Photocatalytic degradation of paraquat using nano-sized Cu-TiO2/SBA-15 under UV and visible light

Photocatalytic degradation of paraquat using mesoporous-assembled Cu-TiO₂/SBA15 under UV and visible light was investigated. The catalyst was synthesized by impregnation of Cu-TiO₂ colloids onto SBA-15. The colloids of Cu-TiO₂ were prepared via sol-gel method while the mesoporous support was prepared using hydrothermal technique. The catalyst was characterized using X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, UV diffuse reflectance spectroscopy, Zeta potential and X-ray adsorption spectroscopy. Results from characterizations showed that Cu doped TiO₂ had a small crystalline size and was well-dispersed on SBA-15. The inclusion of SBA-15 significantly enhanced the photocatalytic activity of the catalyst. Among the three types of undoped catalyst in this study (P25, TiO₂, TiO₂/SBA-15), TiO₂/SBA-15 yielded the highest degradation of paraquat for all pH under UV illumination. Meanwhile 2 wt.% Cu-TiO₂/SBA-15 yielded the highest activity under visible light.     

TiO2催化剂薄膜背光催化的研究

利用TiO₂催化剂薄膜进行光催化反应时,根据光照方式的不同可分为正光催化和背光催化.两者相比,背光催化可以避免光在溶液中的衰减而造成的光能损失.本文研究了背光催化时薄膜的厚度,光源波长的选择,及其非均掺杂V对催化效率的影响,同时与正光催化的情况作了比较.结果表明:与正光催化明显不同,背光催化时催化剂薄膜厚度对应于光源波长有一个最佳值,光源波长也只能选择大约在30 0～388nm之间;非均匀掺杂情况与正光催化相同,能提高薄膜的催化效率.     

煅烧结合光辐照提高纳米AgI/TiO2的可见光响应

为提高AgI/TiO₂的可见光响应能力,采用煅烧结合光辐照的工艺对其进行改性.紫外-可见光吸收分析表明,改性AgI/TiO₂的敏感光谱范围覆盖了整个可见区,吸收边带从465 nm红移至800 nm,在500 nm处的吸光度提高了近3倍.X-射线衍射分析结果指出,煅烧提高了金红石型TiO₂的相对含量,导致禁带宽度从2.89 eV降到2.81 eV,氙灯辐照进一步增加了锐钛型TiO₂、金红石型TiO₂和AgI的相对含量,并生成了新的晶体AgCl,使其禁带宽度又降至1.55 eV左右.AgCl的产生、AgI和金红石型TiO₂相对含量的增加是降低改性材料禁带宽度和增强可见光响应能力的主要原因.研究还表明,只有煅烧后的AgI/TiO₂才能通过光辐照来拓宽可见光敏感范围,而且,光辐照中起作用的主要是紫外光,可见光的作用甚小.研究最后提出将2种或2种以上的卤化银负载在纳米TiO₂上,更能有效地增强TiO₂的可见光响应能力.     

可见光驱动下氧掺杂氮化碳活化过硫酸盐降解罗丹明B

采用双氧水溶剂热处理法处理石墨相氮化碳（g-C₃N₄）合成氧掺杂石墨相氮化碳（O-g-C₃N₄）,并通过SEM、XRD、XPS、UV-visDRS等技术手段对O-g-C₃N₄进行表征.结果表明,O-g-C₃N₄表面光滑度降低,纳米片层呈现阶梯状形貌,可见光吸收性能和催化性能有了明显提高.同时,该改性方法能够有效地通过取代sp²杂化N原子的方式将O原子掺杂到g-C₃N₄中.以波长为430 nm的LED灯作为可见光光源,将O-g-C₃N₄用于活化过硫酸盐降解罗丹明B（RhB）.结果表明,该实验体系能够大幅度提高RhB的去除率.当所加LED灯的电源功率为18.00 W,O-g-C₃N₄投加量为0.08 g·L^-1,PS投加量为1.428 g·L^-1,溶液初始pH为5.6时,反应30 min后,浓度为10 mg·L^-1的RhB的降解率可以达到97.8%,矿化率可达9.738%.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

TiO2复合催化剂弱光催化降解模拟海水中苯酚及其催化活性的影响

为了获得适用于海水中有机污染物光降解催化剂,分别选用纳米SiO_2粒子和氧化石墨烯GO为载体,利用吸附相反应技术并结合热处理过程制备了基于TiO_2的复合催化剂,研究了弱光(光强小于1mW·cm~(-3))激发下复合催化剂光催化降解模拟海水中苯酚.结果表明,吸附相反应技术结合焙烧得到的La~(3+)掺杂TiO_2-SiO_2,表面亲水性较强和对苯酚吸附能力较弱,难以克服盐离子的干扰并有效降解模拟海水中高浓度苯酚.而吸附相反应技术结合醇溶剂热还原处理后,La~(3+)掺杂TiO_2-SiO_2催化剂表面亲水性显著减弱,但该催化剂在模拟海水中不能形成稳定的悬浮体系.吸附相反应技术得到的TiO_2-GO和La~(3+)掺杂TiO_2-GO中,TiO_2粒子粒径小于10nm且均匀负载于GO的表面.醇溶剂热还原处理可使TiO_2形成晶型结构,从而提高其催化活性,同时还能将GO表面的含氧基团还原,降低催化剂表面亲水性.从而提升催化剂对苯酚的吸附能力和对盐离子的抗干扰能力.另外,还原GO与小粒径TiO_2粒子紧密结合,使光生电子能很快转移至还原GO表面,增大光生电荷分离率,进一步提升催化剂的光降解性能.     

N,N’-二(2-羟丙基)哌嗪-H2SO4水溶液吸收SO2动力学

在鼓泡式反应器中,以N,N’-二(2-羟丙基)哌嗪(HPP)-硫酸水溶液为吸收剂,利用初始速率法探讨了SO2吸收反应动力学.结果表明:HPP-H2SO4水溶液吸收SO2为快速反应;吸收速率NA随着SO2进口体积浓度yA和吸收剂浓度CN的增大而增大,随着吸收温度T的升高而降低;吸收速率对CN是0.5级反应,对yA为0.85级反应.同时,建立了HPP-H2 SO4水溶液吸收SO2的吸收速率NA与CN、yA及T之间的经验关系式,发现该经验关系式的预测值与实验值符合较好,可用于工程设计计算.