N-TiO2/g-C3N4复合光催化剂的制备及其光催化性能

采用水热法制备N掺杂TiO2,将其与二氰二胺混合进行高温焙烧合成N-TiO2/g-C3N4复合光催化剂。采用XRD、UV-Vis、N2吸附-脱附和SEM等对催化剂进行微观结构表征,以200W氙灯模拟光源并过滤掉420nm以下的紫外光,对比研究TiO2、g-C3N4、N-TiO2和复合光催化剂对罗丹明B的可见光降解性能。结果表明,N掺杂后TiO2的禁带宽度降低,催化活性提高;而复合光催化剂可见光吸收边距相对N-TiO2进一步红移,禁带宽度为2.75eV,降解罗丹明B的一级动力学常数k可达0.12158min-1,是g-C3N4、N-TiO2的2倍;复合催化剂重复使用4次后,对罗丹明B的降解率仍达92%以上,表明催化剂具有较好的光催化活性和稳定性。     

活性炭纤维负载Pr3+:Y2SiO5/TiO2复合材料的制备与性能

为了提高纳米TiO₂对太阳光的利用率和实现光催化剂的回收再利用,采用溶胶-凝胶法将上转换荧光材料与纳米TiO₂复合,通过负载于活性炭纤维（ACF）表面制备了Pr³⁺：Y₂SiO₅/TiO₂/ACF复合材料。运用XRD、FT-IR、SEM、FS、UV-vis DRS等对材料的结构及性能进行了综合表征,并以亚甲基蓝为模拟污染物评价复合材料的可见光催化活性,考察了材料制备过程中煅烧温度、负载次数等制备条件对复合材料可见光下催化性能的影响。结果表明,在浸渍2次、800℃煅烧的制备条件下,复合材料中TiO₂为锐钛矿相（占34.1%）与金红石相（占65.9%）的混合相,亚甲基蓝（15 mg·L^-1）12 h内去除率高达93.8%,反应符合拟一级动力学,反应速率常数为0.2471 h^-1,回收再生利用4次后去除率仍保持在75%以上。     

Synthesis, characterization and photocatalytic activity of N-doped TiO2 modified by platinum chloride

Structures and photocatalytic performance of N-doped TiO₂ modified by platinum chloride (PtCl_x/N-TiO₂) was investigated. It was found that the PtCl_x/N-TiO₂ forms anatase structure of TiO₂ involving nitrogen, chloride species and platinum ions (+IV) as major species, and it exhibits higher photocatalytic activity than either N-TiO₂ or PtCl_x/TiO₂ for the decomposition of acetic acid or acetaldehyde in aqueous solutions under visible light irradiation (λ > 420 nm). An enhancement of the photocatalytic activity on PtCl_x/N-TiO₂ has been proposed as a Z-scheme mechanism for charge separation between platinum chloride and N-TiO₂.     

硼氮共掺杂TiO2粉末制备及光催化活性研究

采用溶胶-凝胶法制备硼氮共掺杂TiO₂光催化剂,利用X射线衍射、X射线光电子能谱及紫外-可见光漫反射光谱手段对制备的催化剂进行表征。结果表明,硼和氮均以间隙方式进入TiO₂晶格中,形成Ti-O-B、Ti-O-N和Ti-O-B-N结构,提高了催化剂活性;B-N-TiO₂吸收带边明显红移,表明催化剂对可见光吸收增强。可见光降解甲基橙结果表明,B-N-TiO₂的活性明显高于B-TiO₂和N-TiO₂,说明硼氮共掺杂改性对提高TiO₂可见光活性具有协同作用。     

破乳法合成N掺杂TiO2/粉煤灰及其可见光催化性能研究

粉煤灰表面负载TiO2制备光催化材料是粉煤灰高附加值资源化应用的一种新途径,通过破乳的方法在粉煤灰表面负载TiO2是一种新的尝试.以十二烷基苯磺酸钠改性的粉煤灰为载体,纳米TiO2胶体为钛源,NaOH为破乳剂,尿素为氮源,在反应釜中通过破乳的方法成功合成了N掺杂的TiO2/粉煤灰复合材料.通过扫描电子显微镜(SEM)、...     

N2等离子体改性介孔TiO2的可见光催化性能及机理

在石英平板介质阻挡放电（DBD）反应器中,采用氮气（N₂）低温等离子体改性制备介孔TiO₂光催化剂（M-TiO₂）。借助XRD、TEM、BET、UV-vis DRS和XPS等手段对M-TiO₂进行表征分析。结果表明,N₂等离子体与煅烧相结合的处理方式下制得的M-TiO₂较单纯煅烧处理方式具有更优的可见光催化性能。当CTAB/Ti摩尔比为1/3时,三种M-TiO₂中M-TiO₂(CTP+C)的比表面积最高（238.2m²/g）,禁带宽度最窄（2.51eV）,O_V/O最大（35.7%）;可见光持续照射240min时,M-TiO₂(CTP+C)对甲基橙（MO）的光降解率最高,达90%以上,且循环稳定性良好。N₂低温等离子体改性过程可有效改善M-TiO₂晶粒的分散性,促进Ti⁴⁺向Ti³⁺的转化,其可见光催化活性的提高主要归因于氧空位、间隙碳和间隙氮三者的共同作用。活性物种捕获实验和莫特-肖特基曲线测试结果表明,可见光下降解甲基橙的过程中起主要作用的是O₂^▪-和h⁺。在此基础上,给出了M-TiO₂(CTP+C)可见光催化的机理模型。     

Photocatalytic degradation of organic compounds diluted in water using visible light-responsive metal ion-implanted TiO2 catalysts: Fe ion-implanted TiO2

The application of metal ion-implantation method has been made to improve the electronic properties of the TiO₂ photocatalyst to realize the utilization of visible light. The photocatalytic properties of these unique TiO₂ photocatalysts for the purification of water have been investigated. By the metal ion-implantation method, metal ions (Fe⁺, Mn⁺, V⁺, etc.) are accelerated enough to have the high kinetic energy (150 keV) and can be implanted into the bulk of TiO₂. TiO₂ photocatalysts which can absorb visible light and work as a photocatalyst efficiently under visible light irradiation were successfully prepared using this advanced technique. The UV-Vis absorption spectra of these metal ion-implanted TiO₂ photocatalysts were found to shift toward visible light regions depending on the amount and the kind of metal ions implanted. They were found to exhibit an effective photocatalytic reactivity for the liquid-phase degradation of 2-propanol diluted in water at 295 K under visible light (λ>450 nm) irradiation. The investigation using XAFS analysis suggested that the substitution of Ti ions in TiO₂ lattice with implanted metal ions is important to modify TiO₂ to be able to adsorb visible light.     

Plasmonic Au nanoparticles supported on both sides of TiO2 hollow spheres for maximising photocatalytic activity under visible light

A strategy of intensifying the visible light harvesting ability of anatase TiO₂ hollow spheres (HSs) was developed, in which both sides of TiO₂ HSs were utilised for stabilising Au nanoparticles (NPs) through the sacrificial templating method and convex surface-induced confinement. The composite structure of single Au NP yolk-TiO₂ shell-Au NPs, denoted as Au@Au(TiO₂, was rendered and confirmed by the transmission electron microscopy analysis. Au@Au(TiO₂ showed enhanced photocatalytic activity in the degradation of methylene blue and phenol in aqueous phase under visible light surpassing that of other reference materials such as Au(TiO₂ by 77% and Au@P25 by 52%, respectively, in phenol degradation.     

Influence of activated carbon upon titania on aqueous photocatalytic consecutive runs of phenol photodegradation

The photocatalytic degradation of phenol was performed at room temperature in aqueous suspended mixtures of TiO₂ and activated carbon (AC). The main objective of the present work was to verify the potential of TiO₂/AC system in the photocatalytic degradation of phenol and the principal intermediate products after performing three consecutive runs. The phenol disappearance follows a first-order kinetics. Therefore, the apparent first-order rate constant of phenol and total organic carbon photodegradations were selected to evaluate the photoefficiency of the system. From the present results it can be concluded that there is a synergistic effect between both solids which is determined by the numbers of photocatalytic runs. From a practical point of view, TiO₂/AC is able to photomineralize phenol and total organic carbon for three and two, respectively, consecutive runs more efficiently than TiO₂ alone.     

Photodegradation of aromatic pollutants in water over TiO2 supported on molecular sieves

TiO₂ was supported on porous materials, including NaY and Na-mordenite zeolites, as well as mesoporous MCM-41 molecular sieve by using impregnation method with organic solvents. The products were characterized with powder XRD, BET surface area measurement, TEM, IR, Raman and UV–VIS spectroscopies. The supported TiO₂ was crystallized in anatase structure and the intensity of its X-ray diffraction peaks increased with TiO₂ loading. In contrast, the total surface area of the supported catalyst decreased with TiO₂ loading. A blue shift of the absorption edge in the UV–VIS spectra was observed when TiO₂ particle size decreased, a phenomenon corresponding to the particle size quantization effect. For photodegradation of aromatic pollutants in water, the activity was found strongly influenced by the chemical nature of the pollutant and the surface property of the support. For volatile pollutants such as benzene and chlorobenzenes, molecular sieve supports facilitated the photodegradation reaction by providing high surface area for adsorption. Moreover, there is an optimal loading of TiO₂ to achieve the best photocatalytic activity on various supports. The supports in contrast did not show positive contribution in degradation of hydrophilic pollutants such as phenol.     

银掺杂二氧化钛/活性炭复合材料的制备及其光催化性能研究

为提高二氧化钛/活性炭（AC）复合材料对可见光的利用率,基于溶胶-凝胶法制备了银掺杂的二氧化钛/活性炭复合光催化剂。利用一系列测试方法对光催化剂进行了表征,通过亚甲基蓝（MB）和Cr（Ⅵ）废水的降解效果研究了其光催化活性。结果表明,掺杂银的材料,吸附性能和可见光下的光催化性能均得到提升。在材料投加量为400 mg/L情况下,银-二氧化钛/AC复合光催化剂在30 min内对10 mg/L MB溶液的降解率达到98.55%,在60 min内对20 mg/L MB溶液、10 mg/L Cr（Ⅵ）溶液的降解率分别达到76.92%和53.90%;与未掺杂的材料相比,降解率分别提升了14%、47%、137%。这是由于Ag纳米颗粒可以有效地俘获价带电子,减少电子空穴的复合,从而提高了光催化效果。     

Ni-TiO_2薄膜的制备及可见光催化活性的研究

通过溶胶-凝胶法结合浸渍提拉法在陶瓷基片表面制备Ni掺杂改性TiO_2薄膜。研究不同Ni与Ti物质的量比、焙烧温度和保温时间等对Ni-TiO_2薄膜可见光光催化活性的影响。利用XRD、光化学反应仪、色差仪等对其进行表征。采用单因素分析法和正交实验法得到制备可见光催化活性最优Ni-TiO_2薄膜的Ni与Ti物质的量比为0.3,焙烧温度600℃,保温时间2 h。Ni-TiO_2薄膜在白炽灯光照2 h后,对表面涂覆的罗丹明B溶液的降解率高达93.02%。     

Influence of operating parameters on photocatalytic degradation of phenol in UV/TiO2 process

The use of hydrogen peroxide (H₂O₂) for improved photocatalytic degradation of phenol in aqueous suspension of commercial TiO₂ powders (Degussa P-25) was investigated. Photodegradation was compared using direct photolysis (UV alone), H₂O₂/UV, TiO₂/UV, and H₂O₂/TiO₂/UV processes in a batch reactor with high-pressure mercury lamp irradiation. The effects of operating parameters such as catalyst dosage, light intensity, pH of the solution, the initial phenol, and H₂O₂ concentrations on photodegradation process were examined. It was shown that photodegradation using H₂O₂/TiO₂/UV process was much more effective than using either H₂O₂/UV or TiO₂/UV process. The effect of the initial phenol concentration on TOC removal was also studied, demonstrating that more than 8 h was required to completely mineralize phenol into water and carbon dioxide. For all the four oxidation processes studied, photodegradation followed the first-order kinetics. The apparent rate constants with 400-W UV ranged from 5.0 × 10⁻⁴ min⁻¹ by direct photolysis to 1.4 × 10⁻² min⁻¹ using H₂O₂/TiO₂/UV process. The role of H₂O₂ on such enhanced photodegradation of phenol in aqueous solution was finally discussed.     

Pr3+:Y2SiO5/TiO2上转换复合膜光催化性能

为解决悬浮相TiO₂粉体处理水中污染物后难以分离和回收利用的缺点并进一步提高纳米TiO₂对太阳光的利用率,采用溶胶-凝胶法制备了Pr³⁺:Y₂SiO₅粉体、TiO₂薄膜以及Pr³⁺:Y₂SiO₅/TiO₂复合膜。利用XRD、SEM等表征方法对样品进行表征。重点考察了Pr³⁺:Y₂SiO₅/TiO₂复合材料薄膜对亚甲基蓝的光催化降解效率与镀膜层数等因素的关系。结果发现涂覆5层Pr³⁺:Y₂SiO₅/TiO₂复合膜时,降解率可高达95.7%,其对应的第2次和第3次降解率分别为82.46%和74.94%;随着Pr³⁺:Y₂SiO₅/TiO₂复合膜薄膜面积的增加降解率先增加后降低,使用8张薄膜时降解率最高达96.43%;增加光照强度有利于提高降解率,但当光照强度增加到100 W时,降解率达到稳定值96.18%;随着初始浓度的增加,降解率逐渐降低。     

Characterization and photocatalytic activity of N-doped TiO2 prepared by thermal decomposition of Ti–melamine complex

Nitrogen doped spherical TiO₂ has been prepared by thermal decomposition of Ti–melamine complex in air atmosphere. A clear shift in the onset light absorption from UV region (<400) to visible region (>520 nm) has been observed for the N-doped samples. It has been deduced from the optical absorption spectra that the higher calcination temperature results in the decrease in the amount of N-doping. The XRD results revealed the phase transition of TiO₂ from anatase to rutile crystalline phase, starting at calcination temperature ≥600 °C. The electron microscopic images reveal the formation of spherical and flakes of TiO₂ nanocrystals (25 nm). The chemical nature of N in the N-TiO₂ has been evolved through X-ray photoelectron spectroscopy. The presence of different types of N species have been observed corresponding to different oxidation states and the presence of Ti–N and O–Ti–N have been confirmed from the observed binding energy values. Photocatalytic decomposition of methylene blue has been carried out both in the visible region and UV + visible region. In the visible region, N-TiO₂ showed higher activity compared to the undoped commercial TiO₂ (Degussa P25).     

Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO2

A visible-light-active TiO₂ photocatalyst was prepared through carbon doping by using glucose as carbon source. Different from the previous carbon-doped TiO₂ prepared at high temperature, our preparation was performed by a hydrothermal method at temperature as low as 160 °C. The resulting photocatalyst was characterized by XRD, XPS, TEM, nitrogen adsorption, and UV–vis diffuse reflectance spectroscopy. The characterizations found that the photocatalyst possessed a homogeneous pore diameter about 8 nm and a high surface area of 126 m²/g. Comparing to undoped TiO₂, the carbon-doped TiO₂ showed obvious absorption in the 400–450 nm range with a red shift in the band gap transition. It was found that the resulting carbon-doped TiO₂ exhibits significantly higher photocatalytic activity than the undoped counterpart and Degussa P25 on the degradation of rhodamine B (RhB) in water under visible light irradiation (λ > 420 nm). This method can be easily scaled up for industrial production of visible-light driven photocatalyst for pollutants removal because of its convenience and energy-saving.     

Preparation of hollow B-SiO2@TiO2 composites and their photocatalytic performances for degradation of ammonia-nitrogen and green algae in aqueous solution

Hollow B-SiO₂@TiO₂ composites were prepared by the wet chemical deposition method starting from TiCl₄ and hollow B-SiO₂ microspheres. TiO₂ layers composed of anatase TiO₂ nanoparticles were coated on the surfaces of the hollow B-SiO₂ microspheres probably through the formation of Ti-O-Si and Ti-O-B bonds. A great number of-OH groups were also present at the TiO₂ coating layers. The presence of Ti-O-Si bonds and Ti-O-B bonds resulted in the formation of defects in the TiO₂ coating layers, which decreased the band gap of the TiO₂ coating layers to ca. 3.0 eV and endowed the TiO₂ coating layers with visible light absorption performance. The buoyancy hollow B-SiO₂@TiO₂ composites exhibited high photocatalytic activities for the degradation of ammonia-nitrogen and green algae. The conversion of ammonia-nitrogen reached 65% when the degradation of ammonia-nitrogen (43 mg·L^-1 at pH value of 8) was catalyzed by the B-SiO₂@TiO₂(100:10) composite under the simulated solar light irradiation at 35℃ for 660 min. The green algae (5 mg·L^-1) were almost completely degraded over the B-SiO@TiO₂(100:20) photocatalyst under the visible light irradiation at 35℃ for 510 min.     

用于环境净化的TiO2/AC复合材料的制备及其改性研究进展

二氧化钛（TiO₂）在光照下可以产生具有强氧化性能的活性基团,活性炭（AC）具有良好的吸附性能。将TiO₂负载在AC上制备的TiO₂/AC复合材料可以有效去除大部分难降解的有机污染物,因此在环境净化领域具有良好的应用前景。本文综述了TiO₂/AC复合材料的研究现状,介绍了目前TiO₂/AC复合材料的三种主要制备工艺：溶胶-凝胶法、溶剂热法和微波合成法。其中溶胶-凝胶法所制备的材料稳定性好、溶剂热法制备条件温和、微波合成法制备周期短。针对TiO₂/AC复合材料可见光吸收率低和量子利用率低等问题,介绍了离子掺杂、半导体复合、贵金属沉积等现有的TiO₂/AC复合材料改性方法。之后,概述了所制备的TiO₂/AC复合材料在去除难降解有机污染物（染料废水、药物类、酚类、挥发性有机物）中的应用。最后展望了TiO₂/AC复合材料在改性研究与实际应用过程中存在的挑战性问题及可行的解决方法,为TiO₂/AC复合材料深入研究和大规模工业生产应用提供参考。     

Ag-Zn_3(VO_4)_2催化剂的水热合成及其可见光催化活性

以Zn(NO_3)_2·6 H_2O、Ag NO_3和Na VO_3为原料,采用水热法合成Ag-Zn_3(VO_4)_2催化剂,并通过SEM、TEM和UV-Vis DRS等对催化剂进行表征分析。以甲基橙染料废水为探针污染物,考察Ag~+与Zn~(2+)物质的量比、水热温度和水热时间对Ag-Zn_3(VO_4)_2光催化剂催化活性和表面形貌的影响。结果表明,在Ag~+与Zn~(2+)物质的量比为0.15、水热温度160℃和水热时间16 h条件下,合成的Ag-Zn_3(VO_4)_2光催化剂光催化活性最好,光照5 h后,对甲基橙染料的脱色率达99.18%,较Zn_3(VO_4)_2催化剂(合成条件为p H=10和160℃水热反应16 h)提高43.99%。采用水热合成法制备的催化剂Ag-Zn_3(VO_4)_2具有较好的可见光活性。     

The kinetics of phenol decomposition under UV irradiation with and without H2O2 on TiO2, Fe–TiO2 and Fe–C–TiO2 photocatalysts

H₂O₂ used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe²⁺ to Fe³⁺ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H₂O₂ predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H₂O₂ under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H₂O₂ is used for phenol decomposition in the presence of TiO₂ and Fe–TiO₂, decrease of OH radicals formed on the surface of TiO₂ and Fe–TiO₂ has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO₂ photocatalyst in the presence of H₂O₂, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe²⁺ is likely oxidized to Fe³⁺, which is then efficiently recycled to Fe²⁺ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.