Photocatalytic removal of NO and NO2 using titania nanotubes synthesized by hydrothermal method

In this study, the photocatalysts of titania nanotubes(TNTs) were synthesized at different calcination temperatures using commercial Degussa TiO2(P25) as a precursor. The materials were then characterized by BET, SEM, TEM, and XRD analyses. The photocatalytic reactions with NO and NO2 under UV-A irradiation were both performed. The results showed that the photocatalytic reaction rate of NO was much faster than that of NO2, and the conversion of NO2 to nitrate was the rate-limiting step for photocatalytic removal of NOx if the nitrate produced cannot be removed continuously from the photocatalyst surface. For TNTs calcined at different temperatures, a significant enhancement was observed on the total NOx removal efficiency by TNT calcined at 500°C for both NO and NO2 photocatalytic reaction, which could be attributed to its high anatase crystallinity as well as high surface area. These two factors affect primarily on the NO2conversion step in which the high anatase crystallinity could be responsible for the high efficiency at the beginning, while the high surface area could be accounted for retaining this high efficiency from nitric acid poisoning during the test period.     

TiO2电极光电催化氧化处理水体中的蒽

为了探究光电催化体系对水体中多环芳烃（PAHs）的降解效果,采用TiO₂电极在紫外光照射下进行了光电催化氧化处理多环芳烃——Ant（蒽）的研究.分别比较了光电催化（PEC）、光催化（PC）和电化学氧化（EC）体系对Ant的降解效果.并探究了电流密度、初始pH、初始ρ（Ant）和腐植酸（HA）等对Ant降解效果的影响;同时,采用伪一级动力学对降解反应速率进行了拟合分析并对中间产物的含量及Ant的降解机理进行了研究.结果表明:在相同电流密度和反应时间等条件下,PEC体系对Ant的降解率均高于PC和EO体系;电流密度对Ant降解影响不大,在电流密度为0.05 mA/cm2条件下,反应30 min后,Ant的降解率能达到98.5%,体系中中间产物有蒽酮（AT）、蒽醌（AQ）等物质,其浓度呈现先增加后降低的趋势;初始pH对中间产物AQ的生成影响较大;初始浓度对反应速率影响较大,初始浓度增加3倍,反应速率降低了近44%,但Ant的降解率相差不到1%;HA的存在使得Ant降解率降低了7.5%,反应速率降低了近83%.      

Fe3+、Ce3+掺杂TiO2光催化降解气相二苯并呋喃

以气相二苯并呋喃为研究对象,考察了在TiO2、Ce3+/TiO2和Fe3+/TiO2 3种不同光催化剂作用下,反应物初始浓度、湿度、气体循环速率和光强等因素对间歇式光催化反应速率的影响,并建立了估算和测定二苯并呋喃光催化反应常数和Langmuir吸附常数的数学模型和方法.结果表明,Fe3+和Ce3+掺杂修饰TiO2光催化剂后,提高了对二苯并呋喃的光催化降解活性,其中Fe3+/TiO2光催化活性最高;随着二苯并呋喃初始浓度的增大,其光催化降解速率也随之增大;适量的水蒸气存在可以促进二苯并呋喃的降解,但当水蒸气过量后,反而阻碍二苯并呋喃光催化降解;随着气体循环速率加快和光强的增大,二苯并呋喃光催化降解初始速率也随之增大;TiO2、Ce3+/TiO2和Fe3+/TiO2光催化降解二苯并呋喃反应速率常数k分别为34.54×10-5、36.23×10-5和37.95×10-4mg.(min.m2)-1.     

Removal of elemental mercury by photocatalytic oxidation over La2O3/Bi2O3 composite

La₂O₃/Bi₂O₃ photocatalysts were prepared by impregnation of Bi₂O₃ with an aqueous solution of lanthanum precursor followed by calcination at different temperatures. The composite materials were used for the first time for the photocatalytic removal of Hg⁰ from a simulated flue gas under UV light irradiation. The results showed that the sample containing 6 wt.% La₂O₃ and calcined at 500°C has the highest dispersion of the active sites, which was promoted by the strong interaction with the support (i.e., the formation of Bi-O-La species). Since they are fully accessible on the surface, the material also exhibits excellent optical properties while the heterojunction formed in La₂O₃/Bi₂O₃ promotes the separation and migration of photoelectron-hole pairs and thus Hg⁰ oxidation efficiency is enhanced. The effects of the various factors (e.g., the reaction temperature and composition of the simulated flue gas (i.e., O₂, NO, H₂O, and SO₂)) on the efficiency of the Hg⁰ photocatalytic oxidation were investigated. The results demonstrated that O₂ and SO₂ enhanced the efficiency of the reaction while the reaction temperature, NO, and H₂O had an inhibitory effect.     

Evaluation of Virus Reduction by Ultrafiltration with Coagulation–Sedimentation in Water Reclamation

The evaluation of virus reduction in water reclamation processes is essential for proper assessment and management of the risk of infection by enteric viruses. Ultrafiltration (UF) with coagulation–sedimentation (CS) is potentially effective for efficient virus removal. However, its performance at removing indigenous viruses has not been evaluated. In this study, we evaluated the reduction of indigenous viruses by UF with and without CS in a pilot-scale water reclamation plant in Okinawa, Japan, by measuring the concentration of viruses using the real-time polymerase chain reaction (qPCR). Aichi virus (AiV) and pepper mild mottle virus (PMMoV) were targeted in addition to the main enteric viruses of concern for risk management, namely, norovirus (NoV) genogroups I and II (GI and GII) and rotavirus (RoV). PMMoV, which is a plant pathogenic virus and is present at high concentrations in water contaminated by human feces, has been suggested as a useful viral indicator. We also investigated the reduction of a spiked model virus (F-specific RNA bacteriophage MS2) to measure the effect of viral inactivation by both qPCR and plaque assay. Efficiencies of removal of NoV GI, NoV GII, RoV, and AiV by UF with and without CS were >0.5 to 3.7 log₁₀, although concentrations were below the detection limit in permeate water. PMMoV was the most prevalent virus in both feed and permeate water following UF, but CS pretreatment could not significantly improve its removal efficiency (mean removal efficiency: UF, 3.1 log₁₀; CS + UF, 3.4 log₁₀; t test, P > 0.05). CS increased the mean removal efficiency of spiked MS2 by only 0.3 log₁₀ by qPCR (t-test, P > 0.05), but by 2.8 log₁₀ by plaque assay (t-test, P < 0.01). This difference indicates that the virus was inactivated during CS + UF. Our results suggest that PMMoV could be used as an indicator of removal efficiency in water reclamation processes, but cultural assay is essential to understanding viral fate.     

Combined effects of adsorption and photocatalysis by hybrid TiO2/ZnO-calcium alginate beads for the removal of copper

The use of nanosized titanium dioxide(TiO_2) and zinc oxide(ZnO) in the suspension form during treatment makes the recovering and recycling of photocatalysts difficult.Hence,supported photocatalysts are preferred for practical water treatment applications.This study was conducted to investigate the efficiency of calcium alginate(CaAlg) beads that were immobilized with hybrid photocatalysts,TiO_2/ZnO to form TiO_2/ZnO-CaAlg.These immobilized beads,with three different mass ratios of TiO_2:ZnO(1:1,1:2,and 2:1) were used to remove Cu(Ⅱ) in aqueous solutions in the presence of ultraviolet light.These beads were subjected to three cycles of photocatalytic treatment with different initial Cu(Ⅱ) concentrations(10-80 ppm).EDX spectra have confirmed the inclusion of Ti and Zn on the surface of the CaAlg beads.Meanwhile,the surface morphology of the beads as determined using SEM,has indicated differences of before and after the photocatalytic treatment of Cu(Ⅱ).Among all three,the equivalent mass ratio TiO_2/ZnO-CaAlg beads have shown the best performance in removing Cu(Ⅱ) during all three recycling experiments.Those TiO_2/ZnO-CaAlg beads have also shown consistent removal of Cu,ranging from 7.14-52.0 ppm(first cycle) for initial concentrations of10-80 ppm.In comparison,bare CaAlg was only able to remove 6.9-48 ppm of similar initial Cu concentrations.Thus,the potential use of TiO_2/ZnO-CaAlg beads as environmentally friendly composite material can be further extended for heavy metal removal from contaminated water.     

氢气还原海绵铁去除水体中硝酸盐的研究

利用小球烧结和氢气还原工艺制备了粒径1mm～5mm的多孔性球形海绵铁,对球形海绵铁去除水体中硝酸盐的效率及去除动力学进行了研究。结果表明:溶液初始pH值对硝酸盐去除效率的影响显著,初始pH值小于3时,硝酸盐的去除率随溶液初始pH的增加而逐渐降低;初始pH值大于3时,硝酸盐的去除率又随之升高。硝酸盐浓度低于10mgN/L时,硝酸盐去除率随着硝酸盐初始浓度的增加而增加,硝酸盐的残余量保持在0.4mgN/L左右;硝酸盐浓度高于20mgN/L时,硝酸盐的去除率随初始硝酸盐浓度的增加而略有降低。球形海绵铁去除硝酸盐为一级动力学反应,反应级数为0.970～1.378,表观反应速率常数为0.314h-1～0.536h-1。海绵铁还原硝酸盐的主要产物为氨氮,随着还原反应的进行,溶液pH值快速增加,氨氮以分子态氨的形式从水中逸出。进行归纳总结和对比,并以多环芳烃的提取为例列举了各方法的应用步骤,从而为其他环境样品其他有机物分析预处理提供参考。     

锰离子掺杂纳米二氧化钛的制备及在造纸废水处理中的应用

以无机盐无水四氯化钛为原料,采用溶胶-凝胶法制备的锰离子掺杂型纳米TiO2作为光催化剂,在高压汞灯的光源照射下对河北省某造纸厂废水进行光催化降解。考察Mn2+/TiO2光催化剂的热处理温度、掺杂量、用量及溶液pH值、光照时间等因素对废水COD降解率的影响。实验结果表明:经460℃热处理1h的Mn2+/TiO2光催化效果较好,在进水ρ(COD)为400 mg/L,初始pH值为4.0、光催化剂用量1.5g/L、光照时间9h条件下,COD去除率可达80.3%。经深度处理的造纸废水,可实现达标排放。     

TiO2/多孔硅胶对乙烯光催化降解的研究

在可见光或紫外光照的非循环体系中,进行了氧化钛基的催化剂光催化降解乙烯的研究.考察了不同的乙烯初始浓度、不同温度、不同光源和负载贵金属对光降解效率的影响.结果表明,乙烯浓度在38～188 mg/m³范围时,光降解效率随乙烯初始浓度升高而缓慢地线性下降;温度升高有利于光降解;负载的贵金属不仅抑制电子空穴对复合,而且扩大了氧化钛对可见光的吸收,几十倍地提高了氧化钛在可见光的光催化效率.     

负载多壁碳纳米管的多孔Ti/SnO2-Sb-Ni电极电催化氧化双酚A

为发展废水中双酚A（BPA）的处理技术和保护水环境安全,采用“电沉积-热分解”法制备负载多壁碳纳米管（MWCNTs）的多孔Ti/SnO₂-Sb-Ni电极,研究了电极对BPA的去除能力、动力学特征和矿化效率,初步分析了BPA的降解途径.结果表明,当浸渍液中n（Sn）∶n（Sb）∶n（Ni）为100∶10∶1、ρ（MWCNTs）为0.8g·L^-1时,制备的电极对BPA的去除效果最好;负载MWCNTs使得电极表面的晶体尺寸更小,可增大电极的比表面积,为电催化反应提供更多的活性位点,进而提高电极的电催化效率.当c（Na₂SO₄）为10mmol·L^-1、反应液初始pH为5和电流密度为50 mA·cm^-2时,对50 mg·L^-1的BPA降解60 min时去除效率达到99.76%;去除过程符合一级反应动力学方程,速率常数为0.096 min^-1;电解120 min时,TOC去除率达到67.01%.采用液相色谱-串联质谱分析法（...     

TiO2/GO复合材料紫外光催化降解水中腐植酸

采用溶胶凝胶法在最优煅烧温度（350℃）下,制备不同石墨烯（GO）负载比例的TiO₂/GO复合光催化材料,通过SEM、XRD、Raman、FT-IR、TGA、BET等技术表征并分析材料的表面形貌、晶相结构、官能团与化学键合等特征,进而探究该复合材料在紫外光下对水中腐植酸（HA）的降解性能和机理。结果表明:随着石墨烯（GO）负载比例的增大,TiO₂/GO复合催化剂粒径变小,比表面积增大,有层次的形貌空隙有效减小了团聚,提升了光生载流子迁移效率;Raman光谱中1350 cm-1和1600 cm-1的2处特征峰验证GO成功负载,且晶型仍以锐钛矿相为主;3%GO负载量的TiO₂/GO光催化性能最优。当TiO₂/3%GO投加量为0.5 g/L,水中HA初始浓度为10 mg/L时,在紫外光下催化反应1 h后降解率达到84.7%,其降解速率常数为0.0313 min-1。     

纳米TiO2-光催化灭活水中噬菌体MS2

提出了一种简易的水中病毒灭活方法,以噬菌体MS2为模式病毒,探讨了紫外光照射时间、TiO2浓度、紫外光强度对自来水中MS2灭活效率的影响;评价了太阳光代替紫外光用于光催化灭活病毒的可行性.研究结果表明,聚乙烯(PE)材质的样品袋能更好地透过紫外光;紫外光照射6h,50mg/L的TiO2可以灭活自来水中7.95Log的MS2;紫外光强度在45μW/m2以下时,灭活率随强度的提高而增加;在溪水中,50mg/L的TiO2仅有4.87Log的灭活效率. 在太阳光下,50mg/L的TiO2在自来水和溪水中对MS2的灭活效率差异不明显,都达到了6.1Log以上,表明太阳光-TiO2灭活水中的病毒可行且高效.     

纳米TiO2催化臭氧化对松花江水中氨氮的影响

研究了以负载于陶粒、硅胶、沸石表面的纳米TiO₂作为催化剂时,催化臭氧化松花江水过程中氨氮浓度的变化.结果表明,在单独臭氧化过程中,氨氮浓度先升高后下降,反应30 min后的氨氮浓度与初始浓度相近.在以TiO₂/陶粒、TiO₂/硅胶为催化剂的催化臭氧化过程中,氨氮浓度也是先升高后下降,但反应过程中氨氮的平均浓度要高于单独臭氧化过程.以TiO₂/沸石为催化剂时,催化臭氧化过程中氨氮浓度先下降,然后略有升高,继而又下降,30 min时对氨氮的去除率接近80%.单独臭氧化和催化臭氧化过程中,增大臭氧投量,氨氮浓度最大值出现的时间提前,并且反应过程中氨氮浓度平均值降低.增大催化剂TiO₂/陶粒、TiO₂/硅胶的投量,催化臭氧化过程中氨氮浓度平均值升高.增大TiO₂/沸石投量,有利于氨氮的去除,但投量增大到50g以上时,对氨氮的去除效果影响很小.温度从10℃升高到30℃,对TiO₂/陶粒、TiO₂/硅胶催化臭氧化过程中氨氮浓度的变化影响不大.而以TiO₂/沸石为催化剂时,温度升高有利于催化臭氧化过程中氨氮的去除.     

AgCl/ZnO/GO光催化降解甲基橙的性能研究

为了提高ZnO对偶氮染料污染物的光催化降解效率,以AgCl和GO（氧化石墨烯）作为改性剂,通过水热法和化学沉积法制备了AgCl/ZnO/GO光催化材料,采用XRD、SEM、XPS、UV-Vis方法对材料的物相组成、微观形貌及光学特性进行表征;以MO（甲基橙）为目标污染物,探究其在可见光下的催化降解性能,考察AgCl含量、催化剂投加量、pH对其可见光催化活性的影响.结果表明:①AgCl的沉积和GO的负载增强了ZnO对可见光的响应能力,提高了光生电子-空穴产生、分离效率,同时增加了材料的分散性及其对MO的吸附率,因此AgCl/ZnO/GO光催化材料对MO有良好的可见光催化降解效率.②AgCl/ZnO/GO对MO的催化降解效率随着AgCl含量的增加而增加,随着催化剂投加量的增加呈先增后降的趋势,溶液pH对其降解效果有一定影响,但不显著.③当AgCl/ZnO（二者物质的量的比）为2:1、AgCl/ZnO/GO投加量为70 mg、pH为7、室温下经过可见光照射50 min后,AgCl/ZnO/GO对质量浓度为10 mg/L的MO的降解率可达98.93%;此外,该催化剂重复使用4次对MO仍具有88%的去除率,显示出良好的稳定性.因此,AgCl/ZnO/GO是一种高效、稳定的可见光光催化剂,在废水净化方面具有良好的应用前景.      

负载型催化剂光催化氧化五氯苯酚钠的效果

研究以TiO₂ 为基本活性组分、空心玻璃珠为载体、硅酸钠为粘合剂的负载型催化剂的制备技术 .选取五氯苯酚钠 (PCP-Na)为处理对象 ,结合对催化剂比表面和晶型结构的表征 ,对制备的催化剂进行筛选评价 .实验结果表明 :在适当的条件下 (二氧化钛、空心玻璃珠、40%硅酸钠溶液重量比为 4∶20∶2,650℃下烧 3h)所制备的C3型催化剂不仅光催化活性高 ,且负载牢固 ,易与水分离 .对初始COD_Cr=400mg·L^-1,PCP-Na=10mg·L^-1的反应液 ,在光照强度为 30kW·m^-2下 2hCOD_Cr去除率大于 65% ,PCP-Na去除率大于 92%.试验进一步探讨C3型催化剂投加量、反应液初始浓度、供氧量对催化反应的影响 .     

电晕放电与络合催化联合同时去除烟气中SO_2、NO实验研究

采用电晕放电与液相络合催化协同同时去除烟气中SO2和NO,电压、水流量、乙二胺合钴浓度、pH、SO2和NO初始浓度以及气流量对同时去除SO2和NO效率的影响进行了实验研究.结果表明:NO去除率随着放电电压、水流量、乙二胺合钴浓度、pH的增加而增加,而随SO2和NO初始浓度、烟气流量的增大而减小;SO2去除率也随放电电压,水流量的增加而增加,随烟气流量的增加而下降,但溶液pH,SO2和NO初始浓度和乙二胺合钴浓度对其影响很小.溶液中加入Mn2+和尿素能分别增强SO2和NO的去除效果.最佳条件为:电压25 kV、水流量80 L·h-1,乙二胺合钴浓度0.02 mol·L-1,烟气流量1.0 m3·h-1、尿素浓度0.02 mol·L-1,Mn2+浓度为0.02 mol·L-1时,NO和SO2去除率分别可达68%和94%,对应能量消耗分别为22.2 g·k Wh-1和75.2 g·k Wh-1.     

Rubber sheet strewn with TiO2 particles:Photocatalytic activity and recyclability

A new method for the preparation of rubber sheet strewn with titanium dioxide particles (TiO₂-strewn sheet) is presented. This simple and low cost method is based on the use of TiO₂ powder (Degussa P25) being strewn onto the sheet made from rubber latex (60% HA) through a steel sieve. The characteristic of the TiO₂-strewn sheet was studied by using scanning electron microscopy/energy dispersive X-ray spectrometer (SEM/EDS) and X-ray diffractometer (XRD) techniques. The photocatalytic activity of TiO₂-strewn rubber sheet was evaluated using Indigo Carmine (IC) dye as a model for organic dye pollutant in water. The results showed that the TiO₂-strewn sheet could degrade IC dye solution under UV light irradiation. The effects of pH, initial concentration, and the intensity of UV light on the photodegradation were also investigated. Kinetics of the photocatalytic degradation was of the first-order reaction. The used TiO₂-strewn sheet can be recovered and reused. The recycling uses did not require any cleaning between successive uses and no decline in the photodegradation efficiency was observed compared with freshly prepared TiO₂-strewn sheet.     

贵金属负载TiO_2光催化降解甲苯研究

采用Degussa P25 TiO2粉末,利用光沉积法制备贵金属负载光催化剂M/TiO2(M分别为Pt、Pd、Ag和Au)。通过气相甲苯光催化降解实验考察M/TiO2的光催化活性。实验结果表明:负载1.0 wt%的Pt、Pd、Ag和Au四种贵金属均可提高TiO2光催化降解甲苯的效率,其中Pt/TiO2的光催化活性最佳。循环伏安法(CV)、塔菲尔(Tafel)和Mott-Schottky电化学测试证明Pt的负载抑制光生电子和空穴的复合,提高载流子浓度,进而增强TiO2光催化活性。     

新型磁性聚谷氨酸吸附剂对水中Pb2+的吸附去除

德岛大学安澤幹人首次利用γ-PGA在Fe3O4磁性纳米颗粒上进行涂层,制得了γ-聚谷氨酸-Fe3O4磁性纳米颗粒（PG-M）.本实验利用透射电镜以及扫描电镜对PG-M吸附剂的形貌进行了分析,发现PG-M与未涂层的Fe3 O4具有相似的形状以及大小,均为不规则的层状结构,且晶粒直径在120～320 nm之间;实验中针对性地对水溶液中Pb2＋进行了吸附探讨.在振荡实验中,通过主要参数的变化（pH值、吸附时间、竞争离子浓度、腐殖酸浓度）,得到如下结果：吸附最佳pH值为7.0;吸附量随着吸附时间的延长而增长,吸附平衡时间为45 min;Na＋对PG-M去除Pb2＋没有很强的干扰性,而Ca2＋则显示出一定的干扰作用;腐殖酸对吸附效果的影响是复杂的,表现为先增强吸附效果,随后降低吸附效果;最佳条件时Pb2＋的最大吸附量为93.3 mg/g.PG-M对Pb2＋的吸附均能较好地符合Freundlich和Langmuir等温吸附模型,其中Langmuir方程能更好地描述PG-M的吸附特征,说明PG-M在水溶液中对金属离子的吸附为单分子层吸附.PG-M吸附符合准二级动力学模型（r2〉0.99）.不同浓度的HCl和HNO3溶液的再生实验发现,0.1 mol/L的HCl溶液作为吸附再生液,可取得较好的再生效果.表明PG-M是可再生的,具有较好的经济性和可持续性.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.