可见光活性纳米TiO2光催化涂料的抗菌性能研究

基于过渡金属离子掺杂技术,制备了在室内光辐照条件下具有良好光催化抗菌性能的可见光响应型铁掺杂TiO2光催化涂料。研究结果表明,在可见光活性光催化涂料中添加1%的纳米TiO2时,抗菌效果最好,光照24 h后对大肠杆菌、白色念珠球菌、黑曲霉的杀菌率分别达到99.9%、97.2%、82%。采用致孔剂聚乙二醇6 000对光催化剂改性后,能加快该涂料的抗菌性能,光照6 h后杀菌率就能达到99.9%。表明该涂料在室内可见光照射下具有较好的广谱抗菌效果,能抑制和杀灭多种微生物。     

无机抗菌剂在建筑涂料中的应用研究

研究了5种无机抗菌剂：锌型沸石抗菌剂、银型沸石抗菌剂、氧化锌晶须复合抗菌剂、纳米TiO2光催化抗菌剂和Ca10-x-yTixZny（PO4）6（OH）2复合抗菌剂在涂料中的应用.以对大肠杆菌（E.coli）的灭菌效果评价抗菌性能.结果表明：锌型抗菌涂料的抗菌效果较差,后4种类型抗菌涂料具有很好抗菌效果.但是,银型抗菌剂和氧化锌晶须复合抗菌剂在涂料中存在易引起涂料变色和难分散问题;纳米TiO2光催化型抗菌剂在涂料中易加快涂料老化;而Ca10-x-yTixZny（PO4）6（OH）2复合抗菌剂既具有良好的抗菌性能,又对涂料的基本性能没有影响,它能够应用到抗菌涂料中.     

模拟室内环境下掺杂TiO2纳米晶体的光催化性能

采用环境测试舱模拟可见光下的室内环境,以甲醛气体的光催化降解为探针反应,评价了通过溶胶-凝胶法分别制备的8种(银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S和氯C1)掺杂TiO2纳米晶体的光催化活性及对甲醛气体的去除效果.用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂钠米TiO2的微晶尺寸、晶体结构与光学性能.结果表明,Cu掺杂可以提高TiO2对氧的吸附能力,减少纳米粒子表面光生电子与光生空穴的复合,使TiO2的光吸收带边发生红移且有利于对可见光的吸收,从而使Cu掺杂TiO2在模拟室内环境下光催化甲醛气体的能力得到明显提高.     

无机抗菌剂在建筑涂料中的应用研究

研究了5种无机抗菌剂:锌型沸石抗菌剂、银型沸石抗菌剂、氧化锌晶须复合抗菌剂、纳米TiO2光催化抗菌剂和Ca10-x-yTixZny(PO4)6(OH)2复合抗菌剂在涂料中的应用。以对大肠杆菌(E.coli)的灭菌效果评价抗菌性能。结果表明:锌型抗菌涂料的抗菌效果较差,后4种类型抗菌涂料具有很好抗菌效果。但是,银型抗菌剂和氧化锌晶须复合抗菌剂在涂料中存在易引起涂料变色和难分散问题;纳米TiO2光催化型抗菌剂在涂料中易加快涂料老化;而Ca10-x-yTixZny(PO4)6(OH)2复合抗菌剂既具有良好的抗菌性能,又对涂料的基本性能没有影响,它能够应用到抗菌涂料中。     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程.采用X射线衍射(XRD)、紫外可见分光光度法(UV-Vis)等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系.结果表明,掺杂的TiO2在520℃、650℃焙烧2 h呈锐钛矿结构,在520℃焙烧2 h的TiO2的晶粒尺寸大约为20 nm,而掺杂Ce后其晶粒尺寸均减小,大约为12nm.UV-Vis吸光度分析表明,掺Ce后吸收带边明显发生红移,但随着Ce掺杂浓度的增大,其对可见光的吸收影响不大.光催化降解反应表明,未掺杂Ce的TiO2反应2 h后对甲醛的没有降解作用,而Ce掺杂TiO2反应2 h后甲醛降解率达15%.     

模拟可见光下掺杂TiO_2对甲醛溶液光催化降解

模拟自然条件下的可见光,以甲醛的光催化降解为探针反应,评价了通过溶胶-凝胶法分别制备的8种（银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S、氯Cl）掺杂TiO2纳米晶体的光催化活性及对甲醛水溶液的去除效果。用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂纳米TiO2的微晶尺寸、晶体结构与光学性能。结果表明：Ce离子尽管有较大的半径但是主要还是掺杂到晶格中,Ce掺杂可以促进TiO2由非正分锐钛矿相向锐钛矿相和金红石相的转变,抑制载流子复合,使TiO2的光吸收带边发生红移且有利于对可见光的吸收,从而使Ce掺杂TiO2在模拟可见光下光催化甲醛水溶液的能力得到明显提高。     

模拟室内环境下掺杂TiO_2纳米晶体的光催化性能

采用环境测试舱模拟可见光下的室内环境,以甲醛气体的光催化降解为探针反应,评价了通过溶胶-凝胶法分别制备的8种（银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S和氯C l）掺杂TiO2纳米晶体的光催化活性及对甲醛气体的去除效果。用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂钠米TiO2的微晶尺寸、晶体结构与光学性能。结果表明,Cu掺杂可以提高TiO2对氧的吸附能力,减少纳米粒子表面光生电子与光生空穴的复合,使TiO2的光吸收带边发生红移且有利于对可见光的吸收,从而使Cu掺杂TiO2在模拟室内环境下光催化甲醛气体的能力得到明显提高。     

Ag+-TiO2/AC复合材料的可见光吸附-光催化协同作用

采用水热法制备活性炭负载银掺杂纳米TiO2复合材料(Ag+-TiO2/AC),对样品进行了TEM、XRD、FT-IR和UV-Vis表征,分析了Ag+-TiO2/AC的微结构、吸收谱特性和掺杂银离子后的半导体带隙变化,并研究了其在可见光下对甲基橙溶液(MO)的降解性能。结果表明,水热法不需要高温处理即可得到高活性的锐钛矿相纳米TiO2,Ag+掺杂和AC负载均明显提高TiO2光催化剂的光催化活性,在可见光下光照180 min,0.2 g/L的Ag+-TiO2/AC对10 mg/L的甲基橙溶液的降解率为73.7%,主要由于存在持续的活性炭局域强吸附-TiO2光催化降解协同作用,明显提高了甲基橙的降解效率。     

碘掺杂TiO2可见光光催化性能研究

在低于100℃温度条件下,采用溶胶-凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂(I-TiO2),运用X-射线衍射(XRD)、透射电镜(TEM)及X-射线光电子能谱(XPS)等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下(λ>420 nm)以罗丹明B(Rhodamine B,RhB)的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为nI:nTi=0.05∶1,焙烧温度为400℃,降解介质条件pH=7时,I-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱(IR),总有机碳(TOC)跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚(4-CP)的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生.OH高活性氧化物种从而氧化降解目标化合物。     

掺Ni2+的TiO2颗粒光催化性能的研究

通过溶胶-凝胶法制备掺杂Ni2 的纳米TiO2,并用XRD和TEM进行了表征,发现Ni2 的掺杂减小了TiO2颗粒的粒径,Ni2 /TiO2晶型为锐钛型.通过对目标物罗丹明B的光催化降解实验,发现Ni2 的掺杂提高了TiO2的光催化活性,其降解罗丹明B的反应遵从一级反应动力学方程,Ni2 惨杂量为1.2%时的光催化活性最高.     

Investigation of the antibacterial effects of silver-modified TiO2 and ZnO plasmonic photocatalysts embedded in polymer thin films

Nanosilver-modified TiO₂ and ZnO photocatalysts were studied against methicillin-resistant Staphylococcus aureus on the surface and against naturally occurring airborne microorganisms. The photocatalysts/polymer nanohybrid films were prepared by spray coating technique on the surface of glass plates and on the inner surface of the reactive light source. The photoreactive surfaces were activated with visible light emitting LED light at λ?=?405 nm. The optical properties of the prepared photocatalyst/polymer nanohybrid films were characterized by diffuse reflectance measurements. The photocatalytic properties were verified with the degradation of ethanol by gas chromatography measurements. The destruction of the bacterial cell wall component was examined with transmission electron microscope. The antibacterial effect of the photocatalyst/polymer nanohybrid films was tested with different methods and with the associated standard ISO 27447:2009. With the photoreactive coatings, an extensive disinfectant film was developed and successfully prepared. The cell wall component of S. aureus was degraded after 1 h of illumination. The antibacterial effect of the nanohybrid films has been proven by measuring the decrease of the number of methicillin-resistant S. aureus on the surface and in the air as the function of illumination time. The photocatalyst/polymer nanohybrid films could inactivate 99.9 % of the investigated bacteria on different thin films after 2 h of illumination with visible light source. The reactive light source with the inner-coated photocatalyst could kill 96 % of naturally occurring airborne microorganisms after 48 h of visible light illumination in indoor air sample. The TEM results and the microbiological measurements were completed with toxicity tests carried out with Vibrio fischeri bioluminescence bacterium.     

Enhanced photocatalytic activity using GO/TiO<Subscript>2</Subscript> catalyst for the removal of DCA solutions

This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO₂) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO₂ photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO₂ ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO₂ was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO₂. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO₂ weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO₂, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.     

纳米TiO2/活性炭复合光催化剂的制备及其对甲醛气体降解

研究了纳米TiO2/活性炭复合光催化剂对空气中典型污染气体甲醛的光催化降解特性。采用扫描电镜(SEM)表征复合催化剂的表面特征。结果显示,经改性后的纳米TiO2在复合催化剂表面分布均匀,呈球状。对甲醛气体的降解实验显示TiO2负载量为1%时对甲醛的去除效果最好,6 h去除率为61.7%。结果显示复合催化剂把甲醛气体分解成CO2,可以直接排空,无二次污染。     

Decomposition of indoor ammonia with TiO2-loaded cotton woven fabrics prepared by different textile finishing methods

Addition of urea-based antifreeze admixtures during cement mixing in construction of buildings has led to increasing indoor air pollution due to continuous transformation and emission of urea to gaseous ammonia in indoor concrete wall. In order to control ammonia pollution from indoor concrete wall, the aqueous dispersion was firstly prepared with nano-scale TiO₂ photocatalysts and dispersing agent, and then mixed with some textile additives to establish a treating bath or coating paste. Cotton woven fabrics were used as the support materials owing to their large surface area and large number of hydrophilic groups on their cellulose molecules and finished using padding and coating methods, respectively. Two TiO₂-loaded fabrics were obtained and characterized by X-ray diffractometer (XRD) and scanning electron microscopy (SEM). Moreover, a specifically designed ammonia photocatalytic system consisting of a small environmental chamber and a reactor was used for assessing the performance of these TiO₂-loaded fabrics as the wall cloth or curtains used in house rooms in the future and some factors affecting ammonia decomposition are discussed. Furthermore, a design equation of surface catalytic kinetics was developed for describing the decomposition of ammonia in air stream. The results indicated that increasing dosage of the TiO₂ aqueous dispersion in treating bath or coating paste improved the ammonia decomposition. And ammonia was effectively removed at low ammonia concentration or gas flow rate. When relative humidity level was 45%, ammonia decomposition was remarkably enhanced. It is the fact that ammonia could be significantly decomposed in the presence of the TiO₂-padded cotton fabric. Whereas, the TiO₂-coated cotton fabric had the reduced photocatalytic decomposition of ammonia and high adsorption to ammonia owing to their acrylic binder layer. Finally, the reaction rate constant k and the adsorption equilibrium constant K values were determined through a curve-fitting method and the TiO₂-padded cotton fabric had the higher k value and lower K value than the TiO₂-coated cotton fabric.     

Photocatalytic pre-treatment with food-grade TiO2 increases the bioavailability and bioremediation potential of weathered oil from the Deepwater Horizon oil spill in the Gulf of Mexico

Using the 2010 Deepwater Horizon oil spill in the Gulf of Mexico as an impetus, we explored the potential for TiO₂-mediated photocatalytic reactive oxygen species (ROS) generation to increase the bioavailability (solubility) and biodegradability of weathered oil after a spill. Food grade TiO₂, which is FDA approved for use as food additive in the United States, was tested as a photocatalyst for this novel application. Photocatalytic pre-treatment (0.05 wt.% TiO₂, UV irradiation 18 W m^?2, 350–400 nm) for 24 h in a bench top photoreactor increased the soluble organic carbon content of weathered oil by 60%, and enhanced its subsequent biodegradation (measured as O₂ consumption in a respirometer) by 37%. Photocatalytic pre-treatment was also tested outdoors under sunlight illumination, but no significant increase in solubility or biodegradation was observed after 11 d of exposure. Although sunlight irradiation of food-grade TiO₂ generated ROS (assessed by the degradation of 4-chlorophenol as a probe compound), the efficacy of weathered oil pre-treatment was apparently hindered by sinking of the photocatalysts under quiescent conditions and illumination occlusion by the oil. Overall, results indicate that photocatalytic pre-treatment to stimulate bioremediation of weathered oil deserves further consideration, but controlling the buoyancy and surface hydrophobicity of the photocatalysts will be important for future efforts to enable ROS generation in proximity to the target compounds.     

Carbofuran degraded by iron-doped anatase: Weakening the cholinesterase inhibitory activity in the photoproducts mixture

Carbofuran is a toxic carbamate pesticide, and its use has increased in recent years. While marketing information indicates stability in different chemical media, carbofuran exhibits relative photolability. The aim of this research was to decompose carbofuran and to identify the photoproducts achieved when two different doped titania photocatalysts were employed under UV irradiation. The iron-doped TiO₂ materials were obtained (a) via a hydrothermal method and (b) by an ultrasound-assisted sol–gel method. The precursors were TiOSO₄?xH₂O and Fe₃(NO₃)·9H₂O. X-ray studies confirmed that the anatase phase of the iron-doped TiO₂ resulted from the two preparation methods. The photocatalytic performance of the prepared materials was monitored by LC/ESI-QTOF-MS, enabling the identification of photoproducts: oxo-carbamates, hydroxylated benzofuranes, a carboxamide, and one amine. By using the iron-doped TiO₂ materials, 2,2-dimethyl-2,3-dihydrobenzofuran-3,7-diol was the most abundant photoproduct, and N,2,2-trimethyl-2,3-dihydrobenzofuran-7-amine was the only compound that had not been previously reported in the photolysis and photocatalysis of carbofuran. The product 3-hydroxy carbofuran, a cholinesterase inhibitor, was quantified and was found to be transformed into compounds that lack this inhibitive property.     

Solar light–driven photocatalytic degradation and mineralization of beta blockers propranolol and atenolol by carbon dot/TiO2 composite

Herein improved solar light–driven photocatalytic degradation and mineralization of two emerging pollutants as well as recalcitrant beta blockers propranolol (PR) and atenolol (AT) have been demonstrated by metal-free carbon dot/TiO₂ (CDT) composite. Hydrothermally synthesized TiO₂ has been decorated with electrochemically synthesized carbon dots (CDs) and was well characterized by various analytical techniques viz. XRD, FTIR, Raman, XPS, UV–visible DRS, FESEM, and TEM. The optimized CDT composite, 2CDT (2 mL carbon dot/TiO₂), showed?~?3.45- and?~?1.75-fold enhancement in the photodegradation rate as compared to pristine TiO₂ for PR and AT respectively in 1 hour of irradiation along with complete degradation of PR and AT after 3 hours of irradiation. 2CDT exhibited 76% and 80% mineralization of PR and AT in contrast with 62% and 47% observed by pristine TiO₂. Further, the major reaction intermediates formed after degradation have been identified by HPLC/MS analysis, confirming more than 99% reduction of the parent compound for both PR and AT. Reusability of the optimized catalyst also showed successful degradation up to 3 cycles, showing reduction abilities of 97%, 95%, and 94% for 1st, 2nd, and 3rd cycle respectively. The enhanced degradation and mineralization efficiency of the 2CDT composite could be attributed to the excellent photosensitizer and electron reservoir properties of the CD along with upconverted photoluminescence behavior. The present study unlocks the possibility of using metal-free, facile CDT composite for effective degradation and mineralization of widely used beta blockers and other pharmaceuticals.

     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

Performance comparison of commercial TiO2: separation and reuse for bacterial photo-inactivation and emerging pollutants photo-degradation

This research aims to compare the disinfection and degradation effectiveness in water of a commercial suspension of nano-TiO₂ (TiO₂Levenger) with the standard TiO₂Degussa P25. Photo-inactivation and photo-degradation experiments were conducted with UVA-vis light. Concerning the disinfection, the effects of TiO₂ dose (0–2 g/l), water matrix, bacterium type (Gram-positive or Gram-negative), and bacterial regrowth after the photo-treatments were studied for each catalyst. The experimental results show that Enterococcus sp. (Gram-positive) was more resistant to the photo-treatments than Escherichia coli (Gram-negative) for both catalyst; however, postirradiation trends showed similar behavior for both bacteria, favoring regrowth for short-treated cells and decay for longer-treated ones. Caffeine was selected as a model substance of pharmaceuticals and personal care products. In terms of caffeine removal, the effects of TiO₂ dose (0–2 g/l) and water matrix were analyzed. Besides, the comparison between mechanical coagulation-flocculation-decantation and simple decantation of TiO₂ was carried out. The results show that simple decantation allowed the recovery of 97.5% of TiO₂ Degussa P25 and TiO₂ Levenger within 1 day of simple decantation, while applying the proposed mechanical coagulation-flocculation decantation 99.7% of recovery of both catalysts was achieved in 2 hours. Finally, the subsequent reuse of both catalysts was proved with little loss of efficiency in terms of photo-disinfection during the four cycles. Nevertheless, the standard TiO₂ Degussa P25 photo-degradation efficiency of caffeine decreases considerably as compared to commercial suspension of TiO₂ Levenger concerning the reutilization.