Pt/Fe_2O_3/TiO_2的制备、表征及其光催化活性研究

报道了担载不同贵金属或过渡金属氧化物的TiO2 催化剂对空气中微量甲醛的光催化氧化的研究结果。实验发现 ,TiO2 上担载Fe2 O3 或Pt时对甲醛均有较高的光催化氧化活性。同时担载双组分的光催化剂Pt Fe2 O3 TiO2 ,由于 2种组分的协同作用 ,具有更高的光催化活性。研究了催化剂制备因素、催化剂的结构及表面特性对催化活性的影响     

炭包覆TiO2复合物对低浓度苯的光催化降解

通过将TiO2粉末和聚乙二醇混合,随后在氮气气氛下热处理合成了炭包覆TiO2.利用粉末X射线衍射、紫外-可见漫反射光谱、透射电子显微镜和氮吸附对炭包覆TiO2复合物样品进行了表征,并研究了其对浓度为～1.2×10-5苯的光催化活性.结果表明:炭包覆量受热处理温度和聚乙二醇用量的影响,随着温度的升高和聚乙二醇量的减少而减少;TiO2的结晶度随着温度的升高而提高,但是炭包覆对TiO2晶体的生长有抑制作用.炭包覆锐钛矿样品比纯TiO2表现出对苯更高的光催化活性,这是由于炭吸附作用导致锐钛矿颗粒周围的苯浓度增加以及包覆炭可导致电荷的有效分离;另一个原因是锐钛矿相结晶度的提高.因此,要获得对苯具有高光催化活性的炭包覆TiO2需要综合考虑碳含量和锐钛矿晶体结构.

Abstract：

Carbon-coated TiO2 was synthesized by mixing TiO2 powders and polyethylene glycol,followed by heat treatment in nitrogen atmosphere. All samples were characterized by powder X-ray diffraction,UV diffuse reflectance spectroscopy,high-resolution transmission electron microscopy,and nitrogen adsorption. The photocatalytic activity of carbon-coated TiO2 for benzene degradation was investigated with a benzene concentration of ～ 1.2 × 10-5. Results showed that the residual carbon content was influenced greatly by heat treatment temperature (HTT)and the amount of PEG,which decreased and increased with increasing the temperature and the amount of PEG,respectively. The crystallinity of TiO2 was improved when the HTT increased. However,the carbon residue had an inhibition effect on the crystal growth of TiO2. The carbon-coated anatase samples were shown to exhibit higher photocatalytic activities than the pristine TiO2 because of the adsorption enrichment of benzene by carbon around the anatase particles and of the effective charge separation due to the electronic conduction of carbon. Another important factor affecting photocatalytic activity was the crystallinity of the anatase phase. High photocatalytic activity for benzene requires a balance between the carbon content and the anatase crystalline structure.     

TiO2薄膜的结构和光催化活性研究

薄膜型的TiO2光催化剂克服了悬浮型的许多缺点,具有广阔的应用前景.阐述TiO2的结构及其影响因素;评述了晶型、晶粒尺寸、结晶度和晶格缺陷、表面积和表面预处理、表面羟基、温度、薄膜厚度、基体、光源及光强等因素对TiO2薄膜光催化活性的影响;探讨了提高TiO2薄膜光催化活性的措施,包括掺杂、贵金属沉积、半导体复合、表面光敏化等.指出需进一步研究的问题:加强影响因素的综合研究,探索最佳的工艺条件和反应条件;进一步提高TiO2薄膜的光催化效率;将光源种类从紫外光扩展到可见光;将TiO2薄膜的光催化性能同其它性能结合起来研究.     

Photocatalytic decomposition of 2-chlorophenol in aqueous solution by UV/TiO2 process with applied external bias voltage

The decomposition of 2-chlorophenol by UV/TiO2 process with the application of external bias voltage was examined in this study. Experiments were conducted in a batch reactor using TiO2-coated titanium sheet as anode and platinum sheet as cathode. The anode photocatalysis of 2-chlorophenol was totally inhibited for experiments conducted with the application of external anodic bias voltage lower than the flat band potential of TiO2. The decomposition rate of 2-chlorophenol was then increased with increasing external anodic bias voltage applied up to 0.0 V (versus SCE). The application of external bias voltage higher than 1.0 V did not markedly promote the photocatalysis of 2-chlorophenol possibly because the photocurrent induced was constant. Experimental results indicated that the decomposition of 2-chlorophenol was more effective for experiments conducted in acidic solutions due to the lower flat band potential of TiO2 and the higher photocurrent induced. The presence of electron scavengers in aqueous solution, such as oxygen molecules, may increase the decomposition rate of 2-chlorophenol. However, the effect of dissolved oxygen was diminished for experiments conducted with applied external bias voltage. The photocatalytic decomposition rate of 2-chlorophenol was enhanced linearly with the increasing UV light intensity when the external bias voltage was applied.     

银修饰氮掺杂TiO_2薄膜的制备及光催化性能研究

TiO2具有光催化活性,因而被广泛应用于废水处理、空气净化、尾气处理等领域。研究表明,经掺杂的TiO2薄膜具有更优异的光催化活性。在众多的可掺杂元素中,N和Ag具有独特的性能特征,因此其可使TiO2薄膜的光催化活性得到较大提升。本文使用直流磁控溅射法和拼靶工艺制备了不同Ag含量的银修饰掺氮TiO2薄膜,并分析了薄膜的形貌结构、表面元素化学态、光学性能和可见光催化活性。研究表明:薄膜沉积过程中Ag含量对薄膜性能影响较大。在TiO2的表面,颗粒细小而均匀。随着Ag含量的增加,薄膜表面出现凸起颗粒,为Ag2O颗粒,且其尺寸逐渐增大;薄膜对350~800 nm波段光的吸收增强。当Ag含量为6.76%(原子比)时,薄膜具有最高的可见光催化活性。     

Photocatalytic Property of TiO2 Films Deposited by Pulsed DC Magnetron Sputtering

TiO2 thin films were prepared by DC magnetron sputtering with the oxygen flow rate higher than the threshold. The film deposited for 5 h was of anatase phase with a preferred orientation along the <220> direction, but the films deposited for 2 and 3 h were amorphous. The transmittance and photocatalytic activity of the TiO2 films increased constantly with increasing film thickness. When the annealing temperature was lower than 700℃, only anatase grew in the TiO2 film. TiO2 phase changed from anatase to rutile when the annealing temperature was above 800℃. The photocatalytic activity decreased with increasing annealing temperature.     

Photocatalytic activity of manganese, chromium and cobalt-doped anatase titanium dioxide nanoporous electrodes produced by re-anodization method

Transition metal-doped TiO₂ electrodes were prepared by re-anodization and characterized. The structure of these electrodes was investigated by X-ray diffraction and electron diffraction, which mainly showed typical characteristic anatase reflections without any dopant-related peaks. The amount of transition metal dopant in TiO₂ was kept at approximately 1.0 at.%, as measured by energy dispersive X-ray spectroscopy. The effects of different types of dopants on the photocatalytic activity were revealed by measuring the degradation of an organic aqueous solution containing a dye (acid red G) using a combination of ultraviolet (UV) light energy in the presence of these electrodes. The photocatalytic efficiency was remarkably enhanced by the incorporation of Mn ²⁺ and Cr³⁺. Mn²⁺ showed the most significant enhancement. However, Co²⁺ accelerated the rate of acid red G degradation only slightly. Langmuir-Hinshelwood rate expression was employed for the degradation of acid red G by UV/TiO₂ electrodes system. The adsorption equilibrium constant, the rate constant, and the initial degradation rate were determined for different electrodes. The effect of the concentration of Mn²⁺ on the degradation of acid red G was also investigated and the results showed that there is an optimal value (about 1.0 at.%) of the concentration of Mn²⁺ for inducing faster degradation of the dye. The enhanced photocatalytic degradation rate of acid red G in the presence of transition metals is attributed to the increase of the charge separation in these systems.     

Photocatalytic activity studies of TiO2 thin films prepared by r.f. magnetron reactive sputtering

A series of transparent titanium dioxide thin films have been obtained on microscope glass slides by means of r.f. magnetron reactive sputtering using Ar and O₂ mixed gases. The photocatalytic activity of the TiO₂ thin films was evaluated by the degradation of rhodamine B dye wastewater. The influences of substrate temperatures and total sputtering pressures on the photocatalytic activity of the TiO₂ films were investigated. It was observed that substrate temperature had little influences on the photocatalytic activity, but the photocatalytic activity of the TiO₂ thin films was improved by decreasing the total sputtering pressure.     

(Bi, C and N) codoped TiO2 nanoparticles

Bi, C and N codoped TiO2 photocatalysts were prepared by doping TiO2 with BiCl3 and KSCN in a sol-gel process (denoted as (Bi,SCN)-TiO2). The catalyst samples were then characterized by XRD, TEM, diffuse reflectance spectra (DRS), XPS, FT-IR and N2 sorption. Bi, C and N elements were detected both by XPS and elemental analysis, while S element was not found, suggesting that SCN- group may have decomposed during the sol-gel process. The effects of the doping on the properties and photocatalytic activity of the TiO2 were investigated. It was found that the cation and the anion affected the properties of TiO2 differently. The optical absorption onset of TiO2 red shifted in the presence of Bi3+, while long tail occurred in the presence of SCN-. The order of photoreactivity for TiO2 samples was as follow: (Bi,SCN)-TiO2>Bi-TiO2>undoped TiO2>p25 TiO2, whatever under UV or visible light illumination. The high photoreactivity of the doped TiO2 was also discussed.     

Low-temperature Preparation of Photocatalytic TiO2 Thin Films on Polymer Substrates by Direct Deposition from Anatase Sol

Anatase TiO2 sol was synthesized under mild conditions （75℃ and ambient pressure） by hydrolysis of titaniumn-butoxide in abundant acidic aqueous solution and subsequent reflux to enhance crystallization. At room temperature and in ambient atmosphere, crystalline TiO2 thin films were deposited on polymethylmethacrylate （PMMA）, SiO2-coated PMMA and SiO2-coated silicone rubber substrates from the as-prepared TiO2 sol by a dip-coating process. SiO2 layers prior to TiO2 thin films on polymer substrates could not only protect the substrates from the photocatalytic decomposition of the TiO2 thin films but also enhance the adhesion of the TiO2 thin films to the substrates. Field-emission type scanning electron microscope （FE-SEM） investigations revealed that the average particle sizes of the nanoparticles composing the TiO2 thin films were about 35-47 nm. The TiO2 thin films exhibited high photocatalytic activities in the degradation of reactive brilliant red dye X-3B in aqueous solution under aerated conditions. The preparation process of photocatalytic TiO2 thin films on the polymer substrates was quite simple and a low temperature route.     

氨气热处理对TiO2自组装薄膜光催化性能的影响

利用静电自组装工艺制备了结构有序的TiO2/PSS纳米多层膜,并在不同工艺条件下对薄膜进行热处理.利用UV-Vis吸收光谱、XRD、α台阶膜厚测试仪等手段对薄膜的性能进行了表征,研究了工艺条件对薄膜光催化性能的影响.结果表明:TiO2/PSS纳米多层膜在450℃氨气气氛中热处理后具有很好的光催化性能,薄膜的响应深度约为120nm,热处理过程中氨气流量小所得薄膜光催化性能佳.     

Prevenient dye-degradation mechanisms using UV/TiO2/carbon nanotubes process

Photocatalysis research heavily emphasizes increasing photo-efficiency. This study presents the application of carbon nanotubes (CNTs) to increase the photocatalytic activity of TiO(2). It elucidates the effect of CNTs dose on the decolorization efficiency of aqueous azo dye, C.I. Reactive Red 2 (RR2), determines the effects of SO(4)(2-) formation and removal of total organic carbon (TOC), and measures the effects of various ultraviolet wavelengths. Scanning electron microscopy was used to elucidate the mixing phenomenon and the size of TiO(2) and CNTs; X-ray diffraction was used to determine crystallinity; a BET meter was used to measure surface area and a spectrophotometry was used to determine the decolorization of RR2. Experimental results indicated significant effects of photodegradation on the combination of TiO(2) with CNTs and electron transfer is higher for 410 nm irradiation than for 365 nm, revealing that solar light can be used. The electron transfer in the TiO(2)/CNTs composites reduced the electron/hole recombination and increased the photon efficiency and the prevenient dye-degradation mechanisms using UV/TiO(2)/CNTs were established.     

负载型纳米二氧化钛光催化剂制备及其光催化性能研究

以粉煤灰分离出来的微珠为载体,采用不同方法制备TiO2负载膜光催化剂,通过XRD、SEM技术对粉煤灰微珠负载TiO2光催化剂的晶型结构和形貌进行了表征,以偶氮染料甲基橙为降解对象,考察不同负载方法、负载层数以及负载量对TiO2光催化活性的影响.结果表明:改良溶胶-凝胶法负载的TiO2薄膜催化剂的催化活性最高,同时负载的薄膜催化剂的催化活性明显高于TiO2 粉末催化剂.     

二氧化钛纳米晶的制备及光催化活性研究

本文用溶胶—凝胶法制备了不同晶相的TiO2纳米晶，将其负载于镍网上，以苯酚的降解为模型反应，研究对比了不同晶相TiO2纳米晶的光催化活性。结果表明，纯锐钛矿相的TiO2纳米晶的降解能力要强于锐钛矿与金红石混合相的TiO2纳米晶。     

TiO2薄膜溅射工艺参数对其光催化性能的影响

利用中频交流反应磁控溅射方法制备TiO2薄膜光催化剂,研究了溅射工艺参数对薄膜光催化能力的影响.采用动态反应系统,紫外光源为TUV,降解对象为0.02 mmol/L亚甲基蓝溶液.结果发现:Ar/O2混合反应溅射在O2分压大于9%之后亦可制备出光催化能力与纯O2溅射相近的TiO2薄膜.TiO2薄膜厚度是影响其光催化降解能力的最敏感因素,800 nm以下TiO2薄膜降解能力基本与厚度成正比.TiO2薄膜在黑暗环境下长期放置,光催化性能会出现一定下降,但紫外光预照射可以使其有效恢复.     

二氧化钛/硅胶的液相沉积法制备与性能研究

采用硫酸钛水解沉积法在硅胶载体上包覆纳米二氧化钛,研究载体表面负载二氧化钛的结构、表面形态及其光催化性能。实验发现,包覆在硅胶表面的二氧化钛大小约为400nm,且分布均匀,二氧化钛粒子为锐钛矿相,并且在样品的紫外-可见漫反射谱图中没有观测到蓝移现象,以偶氮染料甲基橙作为降解对象研究所制备样品的光催化性能。     

中频反应磁控溅射TiO2薄膜对敌敌畏的光催化降解性能

作者利用中频反应磁控溅射技术制备了厚度低于 4 0 0nm的TiO2 薄膜 ,并对其在紫外线作用下对敌敌畏 (DDVP)的光催化降解性能进行了系统的研究。实验结果显示 :敌敌畏的降解速率与光照时间和紫外辐照强度成正比 ,在TiO2 薄膜催化下 ,12 5W紫外灯辐照 4h后降解率可达 97%。 30 0℃下退火处理有利于提高薄膜的催化能力。薄膜厚度的增加亦可提高其催化能力     

二氧化钛纳米粒子对胺类化合物的光催化降解

研究了晶粒粒径相近的金红石相、锐钛矿相和混晶纳米二氧化钛对苯胺、甲萘胺和邻氯苯胺3种物质的光催化降解。结果表明,晶粒粒径相近的金红石相和锐钛矿相二氧化钛纳米粒子对胺类化合物的光催化效果相近,特别是在反应的开始阶段,两者的差异很小;随着反应时间的增加,金红石相纳米二氧化钛的催化能力稍优于锐钛矿相纳米二氧化钛。成分不同的混晶的催化能力相差较大,随着混晶中的金红石相含量增加,催化剂的催化效果有了显著的提高。实验中还发现,不同的催化剂对苯胺、甲萘胺和邻氯苯胺3种物质同时催化过程中,3种有机物降解程度的顺序均为甲萘胺>邻氯苯胺>苯胺。     

Study of Nd-doping effect and mechanical cracking on photoreactivity of TiO2 thin films

Pure and Nd-doped TiO₂ thin films were fabricated by reactive d.c. magnetron sputtering at low-temperature from a pure Ti target. The structure of films was analyzed by X-ray diffraction (XRD). In order to study the Nd-doping effect on TiO₂ photocatalytic activity, some films were deposited on microscope glass substrates under a constant total sputtering pressure and using different Nd-doping concentrations. The effect of different Nd-dopant concentrations and its influence on the photocatalytic efficiency has been explored by measuring the photodegradation of rhodamine-B (RhB) aqueous solution under radiation of UV light. It is principally that for comparison between heat treatment and doping process on TiO₂ photocatalytic efficiency (important under the point of view of energy costs related with industrial sputtering techniques), crystalline TiO₂ films were also produced by thermal annealing. It was found that comparing with annealed pure TiO₂ films, Nd-doping do not improve the photocatalytic activity. At the same time, it was observed that there seems to exist a dopant concentration band for optimal photoreactivity. In order to study the effect of the film mechanical strength on photocatalytic activity, fragmentation tensile tests were also done on TiO₂/PET (polyethylene terephthalate) substrates at increasing applied strains. It was found that increasing the magnitude of the applied tensile strain, pure TiO₂ becomes more photocatalytic efficient.     

Photocatalytic Activities of TiO2 Coated on Different Semiconductive SiC Foam Supports

Different semiconductive SiC foam supports were prepared by varying the sintering temperature and atmosphere, and with or without alkaline solution treatment and high temperature oxidation following a macromolecule pyrogenation combined with reaction bonding method. Nano-TiO2 particles were immobilized onto these SiC foam supports by a composite sol-gel method. The phase, surface morphology, the type of conduction and the photocatalytic activity of the TiO2-SiC composite photocatalysts were studied. The TiO2 coated on p-type Si-free SiC support showed the highest photocatalytic efficiency in degradation of 4- aminobenzenesulfonic acid （4-ABS） in aqueous solution as compared to that coated on n-type SiC support and p-type SiC supports with residual Si or Si02 on the surface. The result showed that the TiO2 coatings immobilized on p-type semiconductive SiC foam supports exhibited obviously higher photocatalytic activity in comparison to that coated on n-type SiC foam support. The p-n heterojunctions formed between the p-type SiC supports and n-type TiO2 coatings might be able to account for the better charge separation and transfer as well as the photocatalytic activity of the TiO2-SiC composite photocatalyst.