Mg掺杂锐钛矿相TiO_2的第一性原理计算

利用基于密度泛函理论的第一性原理对不同浓度Mg掺杂锐钛矿相TiO2的电子结构和光学特性进行理论计算。结果表明,随着Mg掺杂浓度的增大,锐钛矿相TiO2的晶格膨胀程度越大,带隙宽度增大并且吸收边蓝移;不同掺杂浓度下Mg的3s和2p轨道对锐钛矿相TiO2的价带和导带组成贡献较小;在波长约为200⁵95、595595、595⁸00 nm的光区内,Mg掺杂锐钛矿相TiO2的光吸收能力分别减弱和增强。     

Visible light induced electron transfer process over nitrogen doped TiO(2) nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).     

(N, F)-codoped TiO2 Nanocrystals as Visible Light-activated Photocatalyst

(N, F)-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The (N, F)-codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.     

Absorption characteristic and nonvolatile holographic recording in LiNbO3:Cr:Cu crystals

The absorption characteristic of lithium niobate crystals doped with chromium and copper (Cr and Cu) is investigated. We find that there are two apparent absorption bands for LiNbO3:Cr:Cu crystal doped with 0.14 wt.% Cr2O3 and 0.011 wt.% CuO; one is around 480 nm, and the other is around 660 nm. With a decrease in the doping composition of Cr and an increase in the doping composition of Cu, no apparent absorption band in the shorter wavelength range exists. The higher the doping level of Cr, the larger the absorbance around 660 nm. Although a 633 nm red light is located in the absorption band around 660 nm, the absorption at 633 nm does not help the photorefractive process; i.e., unlike other doubly doped crystals, for example, LiNbO3:Fe:Mn crystal, a nonvolatile holographic recording can be realized by a 633 nm red light as the recording light and a 390 nm UV light as the sensitizing light. For LiNbO3:Cr:Cu crystals, by changing the recording light from a 633 nm red light to a 514 nm green light, sensitizing with a 390 nm UV light and a 488 nm blue light, respectively, a nonvolatile holographic recording can be realized. Doping the appropriate Cr (for example, NCr = 2.795 x 10(25) m(-3) and NCr/NCu = 1) benefits the improvement of holographic recording properties.     

Synthesis, characterization and photocatalytic evaluation of visible light activated C-doped TiO2 nanoparticles

We have demonstrated heterogeneous photocatalytic degradation of microcystin-LR (MC-LR) by visible light activated carbon doped TiO(2) (C-TiO(2)) nanoparticles, synthesized by a modified sol-gel route based on the self-assembly technique exploiting oleic acid as a pore directing agent and carbon source. The C-TiO(2) nanoparticles crystallize in anatase phase despite the low calcination temperature of 350 °C and exhibit a highly porous structure that can be optimized by tuning the concentration of the oleic acid surfactant. The carbon modified nanomaterials exhibited enhanced absorption in the broad visible light region together with an apparent red shift in the optical absorption edge by 0.5 eV (2.69 eV), compared to the 3.18 eV of reference anatase TiO(2). Carbon species were identified by x-ray photoelectron spectroscopy analysis through the formation of both Ti-C and C-O bonds, indicative of substitution of carbon for oxygen atoms and the formation of carbonates, respectively. Electron paramagnetic resonance spectroscopy revealed the formation of two carbon related paramagnetic centers in C-TiO(2), whose intensity was markedly enhanced under visible light illumination, pointing to the formation of localized states within the anatase band gap, following carbon doping. The photocatalytic activity of C-TiO(2) nanomaterials was evaluated for the degradation of MC-LR at pH 3.0 under visible light (λ > 420 nm) irradiation. The doped materials showed a higher MC-LR degradation rate than reference TiO(2), behavior that is attributed to the incorporation of carbon into the titania lattice.     

掺杂纳米TiO_2粉体的制备及其光电性能研究

利用Zn2+离子掺杂纳米二氧化钛,以提高其光电转化性能,通过溶胶-凝胶法制备了Zn2+离子掺杂的纳米二氧化钛粉体,采用X射线衍射、扫描电镜、紫外可见光谱和光诱导产生光电流法对掺杂二氧化钛的物相、形貌、光吸收性能和光电性能进行了表征。研究发现,Zn2+掺杂有利于锐钛矿的结晶,掺杂二氧化钛较纯二氧化钛的紫外吸收边红移了约10nm,当Zn2+掺杂量为Ti物质的量的1%时光电转化性能最佳。     

CNT-CdS-TiO_2光催化剂的制备及其光催化性能

采用溶胶凝胶法,以硝酸镉为镉源、钛酸四丁酯为钛源、硫脲为硫源,碳纳米管(CNT)为载体,分别制备了TiO_2、CdS-TiO_2、CNT-CdS-TiO_2催化剂。对TiO_2,CdS-TiO_2,CNT-CdS-TiO_2的晶型和微观形貌进行了表征。结果表明:TiO_2为锐钛矿,CdS为六方相;TiO_2与CdS均匀包覆在CNT的表面。对TiO_2、CdS-TiO_2、CNT-CdS-TiO_2分别进行了紫外-可见吸收光谱的测试和可见光条件下降解亚甲基蓝的光催化性能测试。结果表明CdS-TiO_2、CNT-CdS-TiO_2吸收峰发生红移;TiO_2、CdS-TiO_2、CNT-CdS-TiO_2在可见光下对亚甲基蓝的降解率依次提高,CNT-CdS-TiO_2的降解率可达到55%。     

Ce-TiO2光催化剂的制备与性能研究

采用溶胶-凝胶法制备了稀土Ce离子掺杂的纳米TiO2光催化剂(Ce-TiO2),通过XRD、FT-IR、UV-Vis、PL、Nano-sizer纳米粒度分析仪等对Ce-TiO2样品进行了表征和分析,并以亚甲基蓝(MB)作为目标降解物,考察了不同掺杂浓度及经不同温度热处理后的Ce-TiO2样品对MB的光催化降解效果,结果表明所制备样品的晶型均为锐钛矿相和金红石相的混晶相,Ce离子的掺杂拓展了TiO2在可见光区的光谱响应范围,提高了TiO2光催化活性。当pH值为1.5,Ce的掺杂量为n(Ce)∶n(TiO2)=1∶300,热处理温度为600℃条件下制备的样品其催化活性显著高于Degussa P25。     

Photocatalytic activity of La, Y Co-doped TiO2 nanoparticles synthesized by ultrasonic assisted sol-gel method

Bare TiO2 (T), La-doped TiO2 (LT), Y-doped TiO2 (YT), La, Y co-doped TiO2 (LYT) were successfully prepared by facile ultrasonic assisted sol-gel synthesis using Ti(OC4H9)4 as the precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-visible diffuse reflectance spectra (DRS), and X-ray photoelectron spectroscopy (XPS), respectively. The photocatalytic activities of anatase samples, with the average particle diameters ranging from 14 nm to 21 nm, were evaluated for photodegradation of methyl orange (MO). The XPS results indicated that Y atoms were incorporated into titania lattice, while La atoms existed on the crystal surface. Due to doping, the optical absorption edges of LT, YT, and LYT shifted to the visible light region by 21 nm, 29 nm and 35 nm, respectively. The photocatalytic performances of the doped samples, such as LT, YT and LYT, were much higher than that of bare TiO2 under UV-visible light irradiation. And the photoreactivity efficiency of the LYT was the highest. It indicated that a strong La-Y synergistic interaction appeared to play a decisive role in driving the excellent photocatalytic performance of titania.     

Thin films of TiO2:N for photo-electrochemical applications

Dc-pulsed magnetron sputtering from Ti target in reactive Ar+O2+N2 atmosphere was used to grow stoichiometric TiO2:N and non-stoichiometric TiO2-x:N thin films. X-ray diffraction at glancing incidence, atomic force microscopy AFM, scanning electron microscopy SEM, X-ray photoelectron spectroscopy XPS, and optical spectrophotometry were applied for sample characterization. Measurements of photocurrent versus voltage and wavelength over the ultraviolet uv and visible vis ranges of the light spectrum were performed in order to assess the performance of nitrogen-doped titanium dioxide thin films as photoanodes for hydrogen generation in photoelectrochemical cells, PEC. Undoped TiO2 and TiO2-x films were found to be composed of anatase and rutile mixture with larger anatase crystallites (25-35 nm) while the growth of smaller rutile crystallites (6-10 nm) predominated at higher nitrogen flow rates etaN2 as measured in standard cubic centimeters, sccm. Nitrogen-to-titanium ratio increased from N/Ti = 0.05 at etaN2 = 0.8 sccm for stoichiometric TiO2:N to N/Ti = 0.11 at etaN2 = 0.8 sccm for nonstoichiometric TiO2-x:N thin films. A red-shift in the optical absorbance was observed with an increase in etaN2. Doping with nitrogen improved photoelectrochemical properties over the visible range of the light spectrum in the case of nonstoichiometric samples.     

具有高可见光催化性能W掺杂纳米TiO_2的制备与表征

利用水热合成法成功地制备具有高活性可见光响应的W掺杂TiO2纳米粉体,采用X射线衍射、场发射扫描电镜、场发射透射电镜、可见光吸收光谱、光致发光光谱等对W掺杂TiO2纳米粉体进行表征;W掺杂TiO2纳米粉体的光催化性能通过测试其在可见光和紫外光照射下降解罗明丹B染料的催化效率来检验。结果表明,W掺杂TiO2纳米粉体在可见光照射下的光催化效率要远远大于商品P25和纯TiO2,W的最佳掺杂摩尔分数为40%。     

A new nano-TiO2 immobilized biodegradable polymer with self-cleaning properties

This study concentrated on the direct immobilization of anatase nano titanium dioxide particles (TiO(2), 10nm particle size) into or onto a biodegradable polymer, polycaprolactone, by solvent-cast processes. The self-cleaning, namely photocatalytic properties of the produced materials were tested by photocatalytic removal of methylene blue as model compound and antimicrobial properties were investigated using Candida albicans as model microorganism. Produced TiO(2) immobilized polymer successfully removed methylene blue (MB, 1 × 10(-5)M) from aqueous solution without additional pH arrangement employing a UV-A light (365 nm) source. Almost 83.2% of dye was removed or decomposed by 5 wt% TiO(2) immobilized into PCL (0.08 g) and removal percentage reached to 94.2% with 5 wt% TiO(2) immobilized onto PCL after a 150 min exposure period. Although removal percentage decrease with increased ionic strength and usage of a visible light source, produced materials were still effective. TiO(2) immobilized onto PCL (5 wt%) was quite effective killing almost 54% of C. albicans (2 × 10(6)CFU/mL) after only 60 min exposure with a near visible light source. Control experiments employing PCL alone in the presence and absence of light were ineffective under the same condition.     

Phase-junction Ag/TiO2 nanocomposite as photocathode for H2 generation

Developing anatase/rutile phase-junction in TiO2 to construct Z-scheme system is quite effective to improve its photoelectrochemical activity.In this work,the anatase/rutile phase-junction Ag/TiO2 nanocomposites are developed as photocathodes for hydrogen production.The optimized Ag/TiO2 nanocomposite achieves a high current density of 1.28 mA cm-2,an incident photon-to-current con-version efficiency(IPCE)of 10.8％,an applied bias photon-to-current efficiency(ABPE)of 0.32 at 390 nm and a charge carriers'lifetime up to 2000s.Such enhancement on photoelectrochemical activity can be attributed to:(i)the generated Z-scheme system in the anatase/rutile phase-junction Ag/TiO2 photocath-ode enhances the separation,diffusion and transformation of electron/hole pairs inside the structure,(ii)Ag nanodots modification in the anatase/rutile phases leading to the tuned band gap with enhanced light absorption and(iii)the formed Schottky barrier after Ag nanodots surface modification provides enough electron traps to avoid the recombination of photogenerated electrons and holes.Our results here sug-gest that developing phase-junction nanocomposite as photocathode will provide a new vision for their enhanced photoelectrochemical generation of hydrogen.     

Effect of V doping concentration on the electronic structure,optical and photocatalytic properties of nano-sized V-doped anatase TiO2

V-doped TiO₂ with V/Ti ratio of 1–5% has been synthesized by hydrothermal method and then characterized by XRD, TEM, BET specific surface area, XPS and UV–vis. absorption spectra. The photocatalytic activity of the as-synthesized samples was investigated by the degradation of methylene blue in aqueous solution under visible light irradiation. Density functional theory (DFT) based calculations were performed to investigate the mechanism of band gap narrowing, the shift of light absorption edge, the location of V in the TiO₂ lattice and the variation in electronic and optical properties of TiO₂ with the increase of V doping concentration. Irrespective of the V doping concentration, TEM images indicate that all the doped samples were composed of equiaxed spherical anatase TiO₂ particles with good crystallinity and uniform particle size distribution. Both the experimental results from XPS survey and the theoretical calculation argue that the doped V replaces the lattice Ti and form substitutional impurity. The visible light absorption can be optimized by adjusting the V doping concentration. Among the doped samples with different V doping concentrations, the sample with V/Ti ratio of 2% depicts better visible light photocatalytic activity due to the enhanced visible light absorption and improved separation of electron–hole pairs.     

掺杂基团对氮改性TiO2紫外光催化活性影响的机理研究

以TiCl₄为钛前驱体,采用沉淀法制备了氮掺杂和纯TiO₂. X射线衍射（XRD）和N₂吸附－脱附等温线表征结果表明：所制催化剂以锐钛矿相为主,具有介孔结构. X射线光电子能谱（XPS）证实掺杂的氮以系列NO_x存在. 由紫外－可见漫反射吸收光谱（UV-Vis）可知：氮掺杂TiO₂ ( N-TiO₂ )在400～550nm的可见光区出现新的吸收带. 4-氯苯酚(4-CP)降解实验表明,N-TiO₂的紫外和可见光催化活性均高于纯TiO₂. N-TiO₂具有较高紫外光活性的原因可归于催化剂中含有的NO_x. NO_x在不改变TiO₂禁带宽度的情况下,拓展了它的感光范围,激发更多的光生电子和空穴参与反应,并可降低电子和空穴的复合几率,从而提高了催化剂的紫外光活性.     

TiO2 nanoparticles co-doped with silver and nitrogen for antibacterial application

We have prepared a series of TiO2 nanoparticles for antibacterial applications. These TiO2 nanoparticles were prepared by the hydrolysis precipitation method with Ti(OBu)4, silver nitrate and ammonia. Crystal structure, particle size, interfacial structure and UV-visible light response of the prepared nanoparticles were characterized by X-ray diffraction measurements (XRD), Transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRs). The XRD spectra showed that all samples were anatase structure calcined at 450 degrees C for 3 hours. The Ag doping made the peak of diffraction wider. The results of TEM showed that the nanoparticles of TiO2, N-TiO2 and 1% Ag-N-TiO2 were all spherical in shape and well distributed with a mean size of 19.8 nm, 39.2 nm and 20.7 nm, respectively. N doping caused the nanoparticle size to increase, while, when the doped amount of Ag+ increased, the TiO2 particle size decreased. The FTIR revealed that Ag and N doping of TiO2 appeared to have strong absorption by -OH group and showed the characteristic absorption band of NH4+ and Ag. The UV-Vis-DRs indicated that the absorption band of Ag-N co-doped TiO2 had red shift and that the optical absorption response (between 400 nm and 700 nm) had obvious enhancement. The antibacterial properties of nanoparticles were investigated by agar diffusion method toward Escherichia coli and Bacillus subtilis. The results indicated that both Ag- and N-doped TiO2 could increase the antibacterial properties of TiO2 nanoparticles under fluorescent light irradiation. A 1% Ag-N-TiO2 had the highest antibacterial activity with a clear antibacterial circle of 33.0 mm toward Escherichia coli and 22.8 mm toward Bacillus subtilis after cultivation for 24 hours.     

Synthesis and photo-degradation application of WO3/TiO2 hollow spheres

A WO(3)/TiO(2) composite, hollow-sphere photocatalyst with average diameter of 320 nm and shell thickness of 50 nm was successfully prepared using a template method. UV-vis diffuse reflectance spectra illustrated that the main absorption edges of the WO(3)/TiO(2) hollow spheres were red-shifted compared to the TiO(2) hollow spheres, indicating an extension of light absorption into the visible region of the composite photocatalyst. The WO(3) and TiO(2) phases were confirmed by X-ray diffraction analysis. BET isotherms revealed that the specific surface area and average pore diameter of the hollow spheres were 40.95 m(2)/g and 19 nm, respectively. Photocatalytic experiments indicate that 78% MB was degraded by WO(3)/TiO(2) hollow spheres under visible light within 80 min. Under the same conditions, only 24% MB can be photodegraded by TiO(2). The photocatalytic mineralization of MB, catalyzed by TiO(2) and WO(3)/TiO(2), proceeded at a significantly higher rate under UV irradiation than that under visible light, and more significant was the increase in the apparent rate constant with the WO(3)/TiO(2) composite semiconductor material which was 3.2- and 3.5-fold higher than with the TiO(2) material under both UV and visible light irradiation. The increased photocatalytic activity of the coupled nanocomposites was attributed to photoelectron/hole separation efficiency and the extension of the wavelength range of photoexcitation.     

Investigation of Eu-doped mesoporous titania phosphor with enhanced luminescence

A novel mesoporous TiO2 phosphor doped with Eu was synthesized through a facile hydrothermal synthesis method using cetyltrimethylammonium bromide as structure template reagent. The samples were characterized by X-ray diffraction, N2 adsorption-desorption, scanning electron microscope, high-resolution transmission electron microscopy, ultraviolet visible diffuse reflectance, X-ray photoelectron spectroscopy, and three dimensional Photoluminescence. The X-ray diffraction results demonstrated that the products were anatase type with polycrystalline. N2 adsorption-desorption analysis showed that the samples were of high ordered double mesoporous structures. Eu-doped mesoporous TiO2 indicated the typical fluorescent spectra of Eu3+ ion occurred: the excited-states at 5L6 (394 nm), 5D2 (465 nm) and 5D1 (535 nm); the main emission peaks at 592 and 617 nm, corresponding with the transitions 5D0 --> 7F1 and 5D0 --> 7F2, respectively. Meanwhile, the phenomena of Eu(3+)-doped mesoporous TiO2 phosphor with efficient nonradiative energy transfer from the mesoporous TiO2 host to the activator Eu3+ ions was observed and possible emission mechanism was proposed. High dispersion of Eu in mesoporous TiO2 matrix was responsible for enhanced luminescence.     

Preparation of Fe3+-doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation

Fe3+-doped TiO2 (Fe-TiO2) porous microspheres were prepared by controlled hydrolysis of Ti(OC4H9)4 with water generated "in situ" via an esterification reaction between acetic acid and ethanol, followed by hydrothermal treatment. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), electron paramagnetic resonance (EPR) spectrum, X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption-desorption methods. All of the undoped TiO2 and Fe-TiO2 samples exclusively consist of primary anatase crystallites, which further form porous microspheres with diameters ranging from 150 to 500 nm. The photocatalytic activity of Fe-TiO2 catalysts was evaluated from the photodegradation of methyl orange (MO) aqueous solution both under UV and visible light irradiation. Fe3+ doping effectively improves the photocatalytic activity under both UV light irradiation and visible light irradiation with an optimal doping concentration of 0.1 and 0.2%, respectively. The photocatalytic mechanisms of Fe-TiO2 catalysts were tentatively discussed.     

N掺杂对TiO2结构及可见光光催化性能影响的研究

采用溶胶-凝胶法,在钛酸丁酯水解过程中加入一定量的尿素,制备了不同N掺杂量的光催化剂TiO2-xNx.以亚甲基蓝溶液为降解对象,研究催化剂在可见光区的催化性能;利用XRD、XPS、SEM、UV-Vis对催化剂的结构、形貌和光催化性能进行了表征.实验结果表明,掺杂的N以O-Ti-N的形式存在于TiO2结构中,N元素抑制了锐钛矿相向金红石相的转变和晶粒的长大;样品中形成了新的能级结构,提高了TiO2在可见光下的光量子效率和光催化能力.掺杂量为3.84%(质量分数)的TiO2-xNx在可见光区的响应能力最高,吸收波长延伸至520nm,其光催化活性最大,1.5h降解率达到55.54%.