BiOCl/TiO_2复合材料的可见光活性及机理研究

采用水热法和溶胶凝胶法制备新型BiOCl/TiO2复合材料并明确了最优的掺杂比例(2%).随后利用X射线衍射(XRD)、紫外可见漫反射(DRS)、透射电镜(TEM)和X射线光电子能谱(XPS)对该材料进行表征.由于禁带宽度较大,纯BiOCl和TiO2的可见光催化性能极差,然而二者复合后,同条件下的苯降解率却大幅提升,可以达到40%以上.经证实,催化剂制备过程中,Bi的状态发生变化,在TiO2导、价带之间插入新的能级,使其禁带宽度变窄,电子可以实现可见光跃迁.     

硼掺杂CeO2/TiO2光催化剂的制备及其活性研究

在三氯化钛和钛酸丁酯水解过程中引入硼酸、硝酸铈,制备了具有可见光活性的硼(B)掺杂CeO₂/TiO₂复合氧化物光催化剂,采用XRD、DRS、XPS等手段进行表征,以偶氮染料酸性红B为模型污染物评估了催化活性.结果表明,硝酸铈加入量影响催化剂的吸收带边,随用量增加,吸收带边红移至481nm(Ce/Ti=1.0,摩尔比),继续增加用量,吸收带边轻微蓝移.催化剂晶相组成与焙烧温度有关,500℃时焙烧样品主要由立方晶型CeO₂和锐钛矿TiO₂组成,焙烧温度高于700℃时,TiO₂转化为金红石型,CeO₂则无显著变化.随焙烧温度升高,催化剂吸收带边明显蓝移,综合考虑催化剂稳定性和太阳能利用,认为500℃焙烧较为合适.B1s XPS显示仅有少量B原子进入复合氧化物晶格取代了氧原子,主要以B₂O₃形式存在.酸性红B降解试验显示B掺杂CeO₂/TiO₂可以提高TiO₂的催化活性,紫外光辐射10min最高可使96.0%的酸性红B分解,且反应彻底,表现出较强的氧化能力,但Ce/Ti>0.5(摩尔比)时催化活性显著下降.     

Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro

In this study,the cytotoxicity of two different crystal phases of TiO₂ nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO₂ nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO₂ nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC₅0=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC₅0of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO₂ nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O₂^-）.Data suggested that O₂^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O₂^- on rutile,but increased O₂^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.     

Photocatalytic degradation of phenanthrene on soil surfaces in the presence of nanometer anatase TiO2 under UV-light

The effect of nanometer anatase TiO₂ was investigated on the photocatalytic degradation of phenanthrene on soil surfaces under a variety of conditions. After being spiked with phenanthrene, soil samples loaded with different amounts of TiO₂ (0 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, and 4 wt.%) were exposed to UV-light irradiation for 25 hr. The results indicated that the photocatalytic degradation of phenanthrene followed the pseudo first-order kinetics. TiO₂ significantly accelerated the degradation of phenanthrene with the half-life reduced from 45.90 to 31.36 hr for TiO₂ loading of 0 wt.% and 4 wt.%, respectively. In addition, the effects of H₂O₂, light intensity and humic acid on the degradation of phenanthrene were investigated. The degradation of phenanthrene increased with the concentration of H₂O₂, light intensity and the concentration of humic acids. It has been demonstrated that the photocatalytic method in the presence of nanometer anatase TiO₂ was a very promising technology for the treatments of soil polluted with organic substances in the future.     

Fe2O3/TiO2负载膨胀珍珠岩光催化降解罗丹明B

为获得高效催化活性的光催化材料,研究不同煅烧氛围对材料在可见光下催化性能的影响,以膨胀珍珠岩（EP）为载体,采用溶胶-凝胶法,在不同煅烧氛围（O₂和/或NH₃）下制备Fe₂O₃/TiO₂负载EP的光催化复合材料〔Fe₂O₃-TEP（O₂）、Fe₂O₃-TEP（NH₃）、Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）〕,采用EDS（X-射线色散能谱）、BET（比表面积及孔径分析）、XRD（X射线衍射）、SEM（扫描电子显微镜）、XPS（X射线光电子能谱）等对复合材料进行表征,并研究了其在可见光下对罗丹明B的光催化降解效果.结果表明:①复合材料成功负载了Ti、Fe元素,负载的TiO₂以锐钛矿型存在,Fe₂O₃的掺杂增强了TiO₂对可见光的响应能力;②不同的煅烧氛围明显影响复合材料的晶粒尺寸、比表面积和光催化性能,其中,Fe₂O₃-TEP（O₂,NH₃）的光催化性能最好,4 h后罗丹明B降解率达到87.59%,Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）4 h后对罗丹明B的降解率则分别为65.02%、62.48%和47.48%;③在试验条件下,复合材料的光催化反应符合一阶反应动力学方程,Fe₂O₃-TEP（O₂,NH₃）、Fe₂O₃-TEP（NH₃,O₂）、Fe₂O₃-TEP（O₂）和Fe₂O₃-TEP（NH₃）相应的降解速率常数分别为0.008 3、0.004 3、0.004 3和0.002 7 min-1.研究显示,通过溶胶-凝胶法所制备的复合材料（Fe₂O₃-TEP）经煅烧后所得矿相均一;Fe₂O₃掺杂TiO₂可形成Ti—O—Fe键,减小TiO₂固有的禁带宽度;复合材料光催化性能也受到煅烧氛围的影响,先O₂后NH₃煅烧条件下所得材料的光催化性能最佳.      

TiO2光催化联合技术降解苯酚机制及动力学

主要研究了TiO2光催化体系结合H2O2或外加电催化(EC)体系对苯酚催化降解效率的影响,评价比较TiO2/UV、H2O2/UV、TiO2/UV/H2O2、TiO2/UV/EC体系下苯酚降解机制及动力学.结果表明,TiO2/UV/H2O2和TiO2/UV/EC体系下苯酚降解效率明显高于TiO2/UV体系,当苯酚溶液pH值为6,TiO2质量浓度0.2 g·L-1,紫外光照2 h,光催化降解效果达到86%,当电流密度为12 mA·cm-2,则苯酚可达到100%去除.比较了不同催化体系下的能量利用率,苯酚降解15 min,TiO2/UV/EC体系能量利用率最大为0.030 6 g·(kW·h)-1,其能量消耗为0.0640 kW·h-1,说明采用TiO2/UV/EC体系能更多地利用能量降解苯酚.通过不同催化体系下中间产物分析,建立苯酚及其中间产物对苯二酚、邻苯二酚和苯醌的拟一级降解动力学模型,通过模型验证各催化体系下苯酚的降解历程,同时也说明了TiO2/UV/EC体系有利于苯酚及其中间产物的降解.     

溴代甲烷在SO42-/TiO2上的光催化降解

采用溶胶-凝胶法制备了SO₄^2-/TiO₂催化剂,运用XRD、BET比表面测定,FTIR等技术对催化剂进行了表征,并在微型常压连续反应装置上进行CH₃Br光催化反应性能考察.结果表明,SO₄^2-引入TiO₂体系使得催化剂的结构和光催化性能得到显著改善.SO₄^2-负载量为9%,烧结温度为450℃时,SO₄^2-/TiO₂催化剂的光催化活性最高;SO₄^2-/TiO₂催化剂对反应物料中的水汽有很好的耐受性;当反应温度低于85℃时,提高反应温度,有利于改善对CH₃Br的光催化反应活性,表观活化能约为19.6kJ·mol^-1,反应温度在85℃～105℃区间时,CH3Br的光催化降解表观活化能为0.     

TiO2催化剂薄膜背光催化的研究

利用TiO₂催化剂薄膜进行光催化反应时,根据光照方式的不同可分为正光催化和背光催化.两者相比,背光催化可以避免光在溶液中的衰减而造成的光能损失.本文研究了背光催化时薄膜的厚度,光源波长的选择,及其非均掺杂V对催化效率的影响,同时与正光催化的情况作了比较.结果表明:与正光催化明显不同,背光催化时催化剂薄膜厚度对应于光源波长有一个最佳值,光源波长也只能选择大约在30 0～388nm之间;非均匀掺杂情况与正光催化相同,能提高薄膜的催化效率.     

BiOCl/TiO2的氯化改性及其新式光生自由基催化反应

采用溶胶凝胶法制备了BiOCl/TiO₂复合催化剂,透射电镜（TEM）照片显示,两种半导体分布均匀、相互连接,形成的异质结可以为电子传导提供有效通道.经过氯化处理的复合材料具备更强的光催化能力,在紫外光条件下对苯的降解率达到90%,是原BiOCl/TiO₂的2倍、纯TiO₂的10倍.本文利用X射线光电子能谱、红外光谱和电子顺磁共振,对表面氯化的机理进行研究.结果表明,氯元素以Ti—Cl的方式吸附在催化剂表面,在光照条件下光生空穴夺取一个电子,使其生成氯自由基,进而配合超氧、羟基,构成一种新型的三自由基光催化体系,使催化降解能力大幅提升.最后,利用实验方法得到了光生氯自由基的直接证据,并构建了该体系的光催化反应机理.     

Synthesis of TiO2 nanoparticles in different thermal conditions and modeling its photocatalytic activity with artificial neural network

Titanium dioxide (TiO₂) nanoparticles were prepared by sol gel route. The preparation parameters were optimized in the removal of 4-nitrophenol (4-NP). All catalysts were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). An artificial neural network model (ANN) was developed to predict the photocatalytic removal of 4-NP in the presence of TiO₂ nanoparticles prepared under desired conditions. The comparison between the predicted results by designed ANN model and the experimental data proved that modeling of the removal process of 4-NP using artificial neural network was a precise method to predict the extent of 4-NP removal under different conditions.     

TiO2光催化氧化苯酚动力学研究

以中压汞灯为光源,研究了苯酚在ＴｉＯ２水悬浮液中降解动力学,考察了苯酚在起始浓度,气相氧浓度,催化剂投加量（ＴｉＯ２）光强度以及催化剂煅烧温度对苯酚光解速率的影响,揭示了苯酚多相光催化氧化反应的特点,反应过程符合表现一级动力学规律,气相氧的影响为一级,苯酚初始浓度的影响为负一级,在一定光强度下,催化剂的投加量存在一最值值,说明有效光强度,气相氧以及催化剂投加量是光催化氧化反应的关键因素,适当地热处     

FeTiO3/TiO2纳米异质结的制备和可见光催化性能

采用水热法和溶胶凝胶法制备了新型FeTiO3/TiO2纳米异质结复合材料,并明确了最优的掺杂比例(0.5%).随后利用X射线衍射能谱(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)和透射电镜(TEM)等手段对该复合材料进行表征,证实了其结晶度、吸光度随掺杂量的规律性变化.电镜照片显示,该复合材料具有蓬松多孔的微观结构,且晶格条纹清晰、分散度高,有利于光电子的传导.对苯的降解实验表明,相比于纯TiO2,该催化剂的气相可见光催化能力大幅提高,降解率提升了3倍,达到40%,而CO2生成量提升了5倍,超过300 ppm.同时,电化学测试和电子顺磁共振谱(ESR)等均证实,FeTiO3的窄能带能够提高TiO2的光响应,实现可见光激发;而二者的能带相互匹配,有助于转移光生载流子,实现电子-空穴的高效分离,进而其光生电子和自由基生成能力大幅增强,因此,表现出了较强、较稳定的光催化活性.     

SiO2纳米颗粒内嵌强化介孔TiO2单晶光催化降解盐酸四环素

吸附性能和光生载流子的分离效率是决定光催化降解抗生素的主要因素.为提高介孔TiO_2单晶(MSCs)的吸附性能和光生载流子的分离效率,在MSCs内部构建SiO_2纳米颗粒吸附结构.同时,利用表面光电压谱、氮气等温吸附-脱附、X射线衍射等研究其结构特性.最后,以盐酸四环素为抗生素代表,通过控制SiO_2纳米颗粒比表面积,考察SiO_2对复合材料吸附及光催化性能的影响.结果表明,SiO_2纳米颗粒与TiO_2单晶复合显著提高了材料的吸附性能,表面保护蚀刻进一步提升了材料的比表面积.实验条件下,高比表面积SiO_2-TiO_2单晶复合材料(KSiO_2@TiO_2)对盐酸四环素的平衡吸附量、降解效率、降解速率常数和矿化率分别达到了0.96 mg·g-1、90.2%、0.0079 min-1、54.4%,分别是MSCs的4.4、1.5、2.6和3.1倍.副产物分析表明,SiO_2复合介孔单晶材料更易将盐酸四环素降解为小分子物质.     

Effect of TiO2 calcination temperature on the photocatalytic oxidation of gaseous NH3

Carbon-modified titanium dioxide(TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation(PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400℃ had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range( 300℃). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400℃ contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light.     

Pd/TiO2光催化苯甲酸水溶液产氢性能研究

为了探讨在光催化分解水(下称光解水)制氢反应中含苯有机废水作为牺牲剂的可行性,以光沉积法制备了Pd/TiO₂〔w(Pd)为0.5%〕模型催化剂,并且通过XRD(X射线衍射)、BET(N₂物理吸附)、TEM(透射电镜)、XPS(X射线光电子能谱)和UV-vis DRS(紫外-可见漫反射吸收光谱)等表征手段考察了催化剂的微观结构及性质, 使用泊菲莱Labsolar-Ⅲ AG系统评价了苯甲酸、邻苯二甲酸、间苯三甲酸作为牺牲剂的光催化性能. 结果表明:引入的Pd以Pb0和Pb2+高度分散在TiO₂基底表面,未改变TiO₂的晶体结构;与TiO₂相比,Pd/TiO₂具有更大的比表面积、更小的孔径和更强的光吸收性能. 苯甲酸、邻苯二甲酸、间苯三甲酸光解水产氢速率分别为4.264、6.429和5.400 mmol/(g·h),分别为空白处理〔无牺牲剂,0.733 mmol/(g·h)〕的5.8、8.8、7.4倍. 依据乙酸和三氟乙酸的光解水产氢速率数据及结构特征,初步探讨了苯甲酸参与价带空穴氧化反应的机理,发现光解水产氢速率的大小与苯甲酸牺牲剂的还原性强弱、羧基个数以及空间位阻有关,表现为牺牲剂发生photo-Kolbe脱羧反应越容易、羰基数目越多、空间位阻越小,其光解水产氢速率越高. 未来应进一步探寻高效、稳定的模型牺牲剂,以应用于氢能源生产研究.      

煅烧结合光辐照提高纳米AgI/TiO2的可见光响应

为提高AgI/TiO₂的可见光响应能力,采用煅烧结合光辐照的工艺对其进行改性.紫外-可见光吸收分析表明,改性AgI/TiO₂的敏感光谱范围覆盖了整个可见区,吸收边带从465 nm红移至800 nm,在500 nm处的吸光度提高了近3倍.X-射线衍射分析结果指出,煅烧提高了金红石型TiO₂的相对含量,导致禁带宽度从2.89 eV降到2.81 eV,氙灯辐照进一步增加了锐钛型TiO₂、金红石型TiO₂和AgI的相对含量,并生成了新的晶体AgCl,使其禁带宽度又降至1.55 eV左右.AgCl的产生、AgI和金红石型TiO₂相对含量的增加是降低改性材料禁带宽度和增强可见光响应能力的主要原因.研究还表明,只有煅烧后的AgI/TiO₂才能通过光辐照来拓宽可见光敏感范围,而且,光辐照中起作用的主要是紫外光,可见光的作用甚小.研究最后提出将2种或2种以上的卤化银负载在纳米TiO₂上,更能有效地增强TiO₂的可见光响应能力.     

有机物多相光催化降解反应中催化剂固定化技术研究

以ＴｉＣｌ４和异丙醇为原料,通过化学反应将钛组分以键合方式引入载体多孔硅胶颗粒的表面,经高温处理提高活性,制备出的催化剂以甲基检溶液的脱色反应有很好的光催化活性,与相同量的粉末ＴｉＯ２作用相比,活性升高,经分析测定催化剂颗粒上有３１．０５％的钛成分且表面仍保持硅胶颗粒的骨架结构,具有大比表面和高分散性的优点,利用该方法即可以制备大颗粒载体型ＴｉＯ２催化剂,也可能进一步解决用于实际太阳光废水处理装置     

基于氯化BiOBr/TiO2的新式臭氧转化反应

利用溶胶凝胶法制备了BiOBr/TiO₂复合型光催化剂并进行氯化改性,紫外照射下表现出了较高的臭氧转化能力.随后利用XRD、UV-Vis DRS、TEM、EPR、电化学等方法对催化材料进行表征,分析其光催化反应原理.结果表明,BiOBr/TiO₂对臭氧的转化率提升至61%,这是由于二者形成了半导体异质结,光生电子传递降低了载流子复合率,羟基自由基生成量增加;氯化材料的转化率进一步大幅提升至99%,这是由于氯元素在光照条件下生成氯自由基,进而驱动了一种效率更高的链式传递反应.该反应体系在较高湿度下未见明显失活,优于传统α-MnO₂,具有应用潜力.     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.