TiO_2光催化降解亚硝酸钠的研究

采用溶胶-凝胶法制备了TiO2光催化剂,以紫外光照射下的光催化降解亚硝酸钠为模型反应,以盐酸萘乙二胺显色法测定样品的吸光度,进而得出亚硝酸钠的转化率,并采用BET、XRD和IR对催化剂进行了表征。结果表明,500℃焙烧的TiO2催化剂比表面积为42.5 m2/g,平均孔径为5.8 nm,热稳定性好。400℃焙烧2 h的TiO2尚存在一定量的无定形相TiO2,500℃焙烧的TiO2完全转变为锐钛矿型TiO2,700℃时完全转化为金红石相。本实验最佳的反应条件为：TiO2（500℃,2 h）催化剂0.2 g,100 mL 0.125μg/mL亚硝酸钠溶液中,紫外光降解150 min,亚硝酸钠的降解率为100%;添加适量浓度的H2O2溶液,可促进亚硝酸钠溶液的转化。     

纳米TiO2光催化降解乐果影响因素的研究

以悬浮态TiO2为光催化剂,在紫外光的照射下催化降解乐果,研究了乐果初始浓度、纳米TiO2添加量、反应体系温度、初始pH及通入空气等因素对乐果降解率的影响。结果表明,与反应体系温度和体系初始pH相比,纳米TiO2添加量和乐果初始浓度对乐果降解效果影响较大;不同流速空气通入均能使乐果降解率在0～20 min反应阶段有较大幅度的提高;当纳米TiO2添加量为0.1 g/L,乐果初始浓度为20 mg/L,反应体系温度为30℃,初始pH为6.5的条件下,再辅以空气(2.5 L/min)通入,反应60 min后,乐果降解率可达97.15%。     

TiO2纳米管阵列膜光催化降解苯胺

利用TiO2纳米管阵列光催化降解含苯胺水样,考察了影响苯胺降解率的各种因素。结果表明,在照射光源波长254 nm,反应时间120 min和苯胺水溶液pH=9时,TiO2纳米管阵列光催化氧化苯胺的效果最好,苯胺降解率达到87%;另外在苯胺水样中加入含Fe3+、Cu2+的金属盐和少量的H2O2氧化剂后,对TiO2纳米管阵列的催化活性具有促进作用,其苯胺降解率分别提高了42%、31%和19%。探讨了TiO2纳米管阵列光催化降解苯胺的反应机理。     

TiO2光催化薄膜的制备及其性能

在稀硫酸溶液中的阳极氧化钛箔,采用混合增长模型技术控制氧化膜的生长,制备了TiO2光催化薄膜.TiO2薄膜通过苯酚的光催化降解实验检验,具有较高的催化活性及很好的催化稳定性.实验结果表明阳极氧化法固定TiO2薄膜切实可行,不仅解决了TiO2微粒光催化过程催化剂微粒与水难分离的问题,而且阳极氧化制膜所需时间短(几秒到几分)、工艺简单,十分有利于工业化制备.     

不同形貌TiO2对氯霉素的光催化降解研究

将浓碱水热法制备的钛酸盐纳米管(TNT),采用二次水热和高温煅烧法制备了不同形貌的锐钛矿相TiO2纳米管(NT)和TiO2纳米棒(NB)光催化剂,通过XRD、TEM、UV-vis漫反射吸收光谱(DRS)对产物进行表征,研究光催化剂对氯霉素的光催化降解性能。结果表明,不同形貌TiO2光催化剂对氯霉素具有不同的催化活性,TiO2纳米管(NT)比TiO2纳米棒(NB)有更好的吸附性能;在高压汞灯辐射下,TiO2纳米棒(NB)对氯霉素的光催化降解效率高于TiO2纳米管(NT)。在高压汞灯下TiO2纳米管(NT)和TiO2纳米棒(NB)对氯霉素的光催化降解过程均遵从Langmuir-Hinshelwood动力学模型。     

液相污染物降解中TiO2光催化性能的影响因素

TiO2光催化剂的改性、光催化反应器的设计以及操作参数等影响着TiO2在降解液相污染物时的光催化性能。综述了TiO2改性的各种机理,指出了反应器设计面临的难题,探讨了pH、温度、溶氧量、TiO2用量、污染物浓度、光强度等操作参数对催化性能的影响。最后,展望了TiO2光催化的发展趋势。     

TiO2/AC复合材料的制备及其对孔雀石绿的光催化降解

以活性炭为载体,用溶胶-凝胶法制备了不同TiO2负载量的TiO2/AC复合光催化剂,运用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和红外光谱仪(FT-IR)对该催化剂进行表征.探讨了TiO2的负载量、光催化剂质量浓度、溶液的初始质量浓度等因素对孔雀石绿降解效率的影响,并对催化剂进行了回收再生实验.结果表明,TiO2负载量为30％时的复合催化剂为锐钛矿相,对孔雀石绿的降解具有良好的光催化活性,且回收7次重复使用降解效果仍在95％以上.     

纳米TiO2-UV光催化降解乙酰甲胺磷影响因素的研究

考察了UV-纳米TiO2光催化降解乙酰甲胺磷的可行性,就高压汞灯照射时间及照射方式、催化剂种类及用量、pH值、反应温度、乙酰甲胺磷初始浓度等对光催化降解效率的影响进行了研究,并探索了催化剂的重复利用。结果表明,当添加0.1 g/L的纳米TiO2(德国P25),乙酰甲胺磷的起始浓度为20 mg/L,温度控制在25℃,反应体系的pH为11时,以高压汞灯持续照射80 min,即可实现对乙酰甲胺磷99.9%的光催化降解。     

TiO2纳米管对十二烷基苯磺酸钠的光催化降解

以多孔阳极氧化铝为模板制备TiO2纳米管.研究锐钛矿型TiO2纳米管对降解低浓度的十二烷基苯磺酸钠的光催化作用.实验表明,与TiO2膜相比,TiO2纳米管对十二烷基苯磺酸钠的降解具有更好的光催化效果.     

H3PW12O40/TiO2-SiO2光催化降解甲基红

采用溶胶-凝胶法制备TiO₂-SiO₂,用浸渍法将H₂PW₁₂O₄₀负载在TiO₂-SiO₂上,制得H₃PW₁₂O₄₀/TiO₂-SiO₂光催化剂。探究在模拟自然光条件下,光照时间、甲基红溶液初始浓度、催化剂用量和溶液pH对甲基红可见光催化降解的的影响。实验结果显示,在光照时间为15min.甲基红溶液初始浓度为15mg/L.催化剂用量为1.8g/L以及pH为2的优化条件下,甲基红的光降解率高达99.7%。光催化降解甲基红溶液为一级动力学反应。     

稀土元素Ce掺杂TiO_2光催化剂制备及微波强化光催化活性

在[Bmim]PF6离子液体介质中微波辅助制备稀土元素Ce掺杂改性的TiO_2光催化剂TiO_2-Ce,以甲基橙溶液和苯酚溶液为模拟污染物,在紫外光照和微波辐射-紫外光照降解条件下考察TiO_2-Ce催化剂的光催化活性。利用荧光技术以对苯二甲酸作为荧光探针检测TiO_2-Ce催化剂表面产生的羟基自由基,并对光催化降解反应进行动力学分析,以了解光催化降解反应机理。结果表明,通过优化反应条件制得的TiO_2-Ce催化剂具有较高光催化降解活性和热稳定性,在紫外光照和微波辐射-紫外光照条件下降解60 min后,甲基橙降解率分别为98.6%和99.3%,苯酚降解率分别为96.6%和97.2%。荧光光谱分析表明,TiO_2-Ce在微波辐射-紫外光照条件下产生的羟基自由基比紫外光照多,因而微波辐射-紫外光照具有强化TiO_2-Ce降解模拟污染物作用的效果。反应动力学数据表明,TiO_2-Ce光催化降解甲基橙溶液反应呈一级反应动力学规律,其表观速率常数k最大值为0.056 2 min-1。     

水基纳米TiO_2路径制备有序介孔TiO_2-SiO_2及其可见光催化性能

在多巴胺修饰的水基TiO_2纳米微粒(TiO_2NPs)悬浮液中,以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,分别采用碱性水热方法或酸性溶胶-凝胶方法,制备了有序介孔TiO_2-SiO_2(TiO_2NPs/MCM-41或TiO_2NPs/SBA-3)。采用XRD、TEM、ICP和N2吸附-脱附实验对样品进行表征。结果表明,制备的介孔TiO_2-SiO_2在TiO_2高负载质量分数(23.98%TiO_2NPs/MCM-41、17.27%TiO_2NPs/SBA-3)时,仍能保持长程有序的介孔氧化硅结构。TiO_2NPs随机地嵌入在有序介孔氧化硅孔道所组成的网络结构中。在可见光下催化甲基橙降解反应中,反应时间120 min时,在P25上甲基橙相对浓度降为57%,在TiO_2NPs/MCM-41上降为33%,而在TiO_2NPs/SBA-3上降为5.7%。     

硅藻土负载La~(3+)/TiO_2光催化剂的制备及其光催化性能

以钛酸四丁酯为前驱体,硅藻土为载体,采用溶胶-凝胶法制备TiO_2/硅藻土负载型光催化剂。以硝酸镧为镧源,采用等体积浸渍-焙烧法制备La~(3+)/TiO_2硅藻土光催化剂。通过XRD和SEM对制备的催化剂进行表征,以亚甲基蓝溶液模拟有机废水,考察n(Ti)∶n(Si)及La3+掺杂量对催化剂光催化性能的影响,结果表明,硅藻土可提高TiO_2分散性,降低TiO_2晶粒尺寸,并抑制其由锐钛矿相向金红石相的转变。在n(Ti)∶n(Si)=1∶1、焙烧温度550℃和La3+掺杂质量分数1%条件下,La~(3+)/TiO_2硅藻土光催化剂的光催化活性较好,紫外光连续照射180 min,亚甲基蓝降解率可达99.9%。     

Preparation, characterization and photocatalytic activity of Si-doped and rare earth-doped TiO2 from mesoporous precursors

Si-doped and rare earth-doped TiO₂ with large specific surface area were prepared by the hydrothermal method and sol–gel route, respectively, using C₁₈H₃₇NH₂ as template. The samples were characterized by XRD, FT-IR, low-temperature N₂ adsorption–desorption measurement, XPS and solid state UV–vis diffuse reflectance spectroscopy. The pore size for Si-doped TiO₂ exhibits both mesoporous and microporous distribution, and that for rare earth-doped TiO₂ exhibits a sharp and narrow distribution in microporous range. The photocatalytic activities were investigated with the degradation of phenol as probe reaction. Compared with pure TiO₂, the conversion of phenol and selectivity to CO₂ increases when adding rare earth elements, and the substitution of Si for Ti in an appropriate range also increases the conversion of phenol.     

溶胶-凝胶-微波法制备银掺杂TiO_2光催化剂及其光催化性能

用硝酸银和钛酸正丁酯为原料,采用溶胶-凝胶-微波辐射干燥法合成银掺杂TiO_2光催化剂TiO_2-Ag。为了提高催化剂的光催化活性和降解有机污染物的速率,用微波辅助Ti O2-Ag光催化剂降解有机污染物。通过扫描电子显微镜、红外光谱法、紫外可见光谱法和荧光光谱法对TiO_2-Ag催化剂进行测试和表征。以甲基橙为有机污染物,分别在太阳光照射和微波、紫外、紫外-微波条件下降解甲基橙以考察催化剂的光催化活性。结果表明,TiO_2-Ag光催化剂最佳制备条件为:银掺杂量n(Ag+)∶n(Ti~(4+))=0.003,离子液体用量3.0 m L,微波干燥功率210 W,微波干燥时间20 min,焙烧温度650℃,焙烧时间3 h,此条件下制备的TiO_2-Ag光催化剂在太阳光照射4 h下,紫外光照、微波辐射和紫外光照-微波辐射分别辐射55 min后,甲基橙降解率分别为98.70%、98.79%和99.05%。     

光催化剂TiO2的改性研究进展

光催化剂TiO₂在环境污染治理领域呈现出广阔的应用前景,但由于其自身存在不能响应可见光和量子效率低的缺陷而限制了它的应用,改性是提高TiO₂光催化性能的重要手段。在总结国内外科研成果的基础上,综述了现阶段TiO₂的主要改性方法（如光敏化、离子掺杂、复合半导体等）研究进展,并对TiO₂改性方法的发展趋势进行了展望。     

Characterization and photocatalytic activity of transition-metal-supported surface bond-conjugated TiO2/SiO2

TM/TiO₂/SiO₂ photocatalysts were prepared by the photodeposition method using transition metal salts (TM=Fe³⁺, Co²⁺, Ni²⁺ and Cu²⁺) as precursors and the surface bond-conjugated TiO₂/SiO₂ as supporter in N₂ atmosphere, and were characterized by XRD, XPS, UV-Vis diffuse reflection and zeta-potential. Their photocatalytic activities were evaluated using reactive brilliant red K-2G (K-2G) and cationic blue X-GRL (CBX) showing different adsorption behavior on the oxides. Fe, Cu supported TiO₂/SiO₂ can efficiently extend the light absorption to the visible region. XPS analysis verified that the introduction of transition metal lead to the changes of the electronic environmental of Ti cations and the zeta-potential of oxides. As a result, K-2G has higher adsorption on the modified TiO₂/SiO₂ than that on the baked one, while the adsorption of CBX has a little change on the both oxides. At the same time, for the photodegradation of K-2G, Fe³⁺, Co²⁺, Ni²⁺-modified catalysts show that their photoactivities are 3.3–2.2 times higher than the bare one. On the contrast, all transition-metal-supported catalysts have no significant activity improvement except that Fe/TiO₂/SiO₂ shows 1.68 times higher activity for the photodegradation of CBX. The results indicate that the photoactivity could be increased in photodegradation of dyes by changing the performances of adsorption to dyes and absorption to light of photocatalyst.     

Gd,B共掺杂改性TiO2纳米颗粒的可见光光催化活性

采用溶胶-凝胶法制备了Gd和B共掺杂的TiO2纳米颗粒,研究了TiO2纳米颗粒在可见光下的光催化活性。应用XRD、TEM和UV-Vis等手段对TiO2纳米颗粒的物相、粒径、形貌及光学性能进行了表征。结果表明,掺杂可以抑制TiO2晶粒增长,阻碍TiO2由锐钛矿相向金红石相的转变。紫外-可见吸收光谱显示,共掺杂纳米颗粒在可见光区吸收有较强提高,共掺杂离子以协同作用拓展TiO2光谱响应,使吸收带产生红移,提高光生载流子的分离效率。光催化降解实验表明,共掺杂TiO2纳米颗粒有很高的可见光光催化活性,以500℃热处理的共掺杂摩尔比为0.005 Gd和0.04 B的TiO2纳米颗粒光催化效果最好,在可见光下对甲基橙的降解率为98.9%。     

TiO2 deactivation during gas-phase photocatalytic oxidation of ethanol

The deactivation of TiO₂ Degussa P25 during the gas-phase photocatalytic oxidation of ethanol has been studied. Water vapor plays a clear competitive role for surface sites adsorption, thus hampering the ethanol photo-oxidation. Dark adsorption of ethanol on a fresh catalyst shows a Langmuirian behavior with the formation of a monolayer of adsorbate. Dark adsorption in a TiO₂ surface that has been used in consecutive photocatalytic experiments of ethanol degradation gives non-Langmuirian isotherms, indicating the existence of noticeable changes of the catalyst surface structure. After several irradiations the catalyst activity decreases. Such deactivation has been investigated, observing that the rate constant of ethanol and acetaldehyde (its main degradation product) oxidation decreases with irradiation time. Several surface treatments have been studied in order to find suitable procedures for catalytic activity recovery, but regular decay of activity is always observed after every treatment.