Photocatalytic degradation of C. I. Reactive Red 24 solution with K6SiW11O39SnⅡ

Environmental friendly materials, K₆SiW₁₁O₃₉Sn (SiWSn), was synthesized. SiWSn photocatalytic decomposition of C. I. Reactive Red 24 (RR24) with the UV-lamp (253.7 nm, 20 W), Xenon lamp filtered less than 390 nm light (500 W) and sun light was investigated. The results showed that RR24 solution could be effectively decolorized with the SiWSn photocatalyst. The photocatalytic degradation efficiency of RR24 with SiWSn was affected by the initial concentration of RR2 solution, the amount of SiWSn and the photolysis time. It is demonstrated that the process of photodegradation of RR24 with SiWSn is a pesudo first-order reaction, which can be described by Langmuir-Hinshelwood equation. Hydroxyl radicals and holes are both the main oxidants in the photocatalytic reaction of RR24 with SiWSn.     

Synthesis and characterisation of potassium polytitanate for photocatalytic degradation of crystal violet

Potassium titanate nanostructures were synthesised by hydrothermal treatment of TiO2 （P25） in KOH and H2O2. As-produced powders were characterised by scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, and nitrogen adsorption-desorption methods. Longitudinally-oriented-wire-like structures with a length up to several micrometres and diameters ranging from 10 to 30 nm were obtained. Larger size fibrous nanowires resulting from the hydrotherrnal treatment showed high affinity in adsorbing crystal violet （CV）, which was mainly due to their high surface area. The photocatalytic bleaching of CV solution revealed that the wires are photoactive under ultraviolet light irradiation. Macroporous nanowires are considered as effective adsorbents of CV, capable of photocatalvtic degradation, and they can be easily separated from the solution by settling.     

锐钛矿型TiO2光催化降解异噻唑啉酮废水研究

本文制备了自然光照条件下能有效降解异噻唑啉酮模拟废水(主要成分MI和CMI)的锐钛矿型TiO2光催化剂,并通过电镜分析(TEM、HRTEM)和XRD手段对其进行表征,优化了光催化处理异噻唑啉酮模拟废水的反应条件,并分析了异噻唑啉酮的降解产物情况和自然光照条件下羟基自由基的产生情况.结果表明,合成的锐钛矿型TiO2主要暴露面为{101}面,具有较好的异噻唑啉酮去除效果.在500 W氙灯照射下,12~53 mg·L-1异噻唑啉酮模拟废水在催化剂投加量为677 mg·L-1的条件下反应4 h,异噻唑啉酮去除率可以达到97%~100%;当异噻唑啉酮模拟废水浓度升高为141 mg·L-1时,其去除率为77%~80%,最佳反应时间4 h.对异噻唑啉酮降解产物的分析显示,在光催化反应结束时,MI为主要的残留物质,CMI脱氯转化为氯离子和MI,并发现未知有机产物.     

氧化剂增强TiO2纤维光催化降解DMF研究

研究TiO₂纤维光催化降解DMF水溶液的结果表明:氧化剂增强了TiO₂纤维对DMF的降解能力,在其它反应条件相同情况下,O₃/TiO₂(F)对DMF降解率是air/TiO₂(F)和H₂O₂/TiO₂(F)的1.5倍左右,且降解速率提高2倍左右,COD分析表明DMF几乎完全矿化.同时实验过程中确定了DMF光催化降解中间产物仲胺的存在.以二甲胺为仲胺代表物进行光催化降解研究表明,中间产物仲胺的迅速降解是O₃增强TiO₂纤维降解效应的主要因素.     

巯基改性高岭土负载CeO2-CdS光催化降解结晶紫

为获得高效催化活性的光催化材料,实现偶氮类染料的高效降解,试验以巯基乙酸钠作为硫源和高岭土改性剂合成了巯基高岭土/CeO₂-CdS催化剂,并以降解结晶紫为模板反应,优化确定了巯基高岭土/CeO₂-CdS催化剂的制备条件.采用XRD（X射线衍射）、SEM（扫描电子显微镜）、TEM（透射电子显微镜）、FTIR（傅里叶红外光谱）和UV-Vis（紫外-可见光漫反射光谱）对催化剂进行了表征.结果表明:①催化剂是由巯基高岭土、立方相结构的CdS和萤石结构的CeO₂组成;②CdS和CeO₂的负载破坏了巯基高岭土的层状结构;③最优催化剂和巯基高岭土/CeO₂的可见光的响应范围分别为550和450 nm;④当CeO₂:CdS（摩尔比,下同）为4:6,巯基高岭土:CeO₂-CdS（质量比,下同）为1:3时,催化剂具有最优的光催化活性;⑤在50 mL结晶紫浓度为10 mg/L的溶液中,添加0.1 g最优催化剂后,采用350 W氙灯对其光照150 min时,结晶紫的降解率为95.1%;⑥最优催化剂具有良好的重复使用性能,重复使用5次时,对结晶紫的降解率为90.4%.研究显示,结晶紫降解的最终产物为CO₂和H₂O,催化剂对结晶紫的降解机理是以羟基自由基氧化为主和超氧基氧化为辅的共存氧化机理.      

BiVO4表面氧缺陷调控及其光催化氧化三价砷

以乙二醇为溶剂,采用溶剂热-煅烧法制备缺陷型BiVO₄光催化剂,通过控制溶剂热反应时间调控BiVO₄表面氧缺陷以增强对As （III）的光催化氧化性能.同时,借助各种表征手段如XRD、SEM和XPS等分析样品的晶型结构、形貌特征及化学组成等性质,考察其在可见光下对As（III）的光催化氧化性能,并研究其氧化机理.结果表明,溶剂热反应时间对BiVO₄的晶粒尺寸和光吸收性能没有影响,但能通过影响比表面积调控BiVO₄的表面氧缺陷浓度.经优化得到,反应时间为14 h时制备的BiVO₄光催化剂（BiVO-14）对As（III）（6 mg·L^-1）的氧化效率高达95.7%,并具有良好的光催化稳定性.BiVO₄氧化As （III）的主要途径是光生空穴（h⁺）的直接氧化作用.表面氧缺陷能增强导电性能,促进电荷分离和迁移,强化h⁺的氧化作用,从而提高BiVO₄的光催化氧化性能.BiVO-14能有效促使As（III）转化为低毒的As（V）,在饮用水源As污染去除方面具有广阔应用前景.     

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     

光催化剂Bi3.84W0.16O6.24在模拟太阳光下对双酚A的降解

采用水热合成法在pH12的条件下合成圆片状Bi3.84W0.16O6.24催化剂.通过XRD、FESEM、TEM、UV-vis漫反射等表征分析Bi3.84W0.16O6.24的物相、形貌和吸光性能.以双酚A(BPA)为目标污染物,研究了Bi3.84W0.16O6.24在模拟太阳光辐射下的光催化反应活性.设计L18(37)正交试验研究了BPA初始浓度、催化剂投入量、反应溶液pH值以及光催化反应时间对Bi3.84W0.16O6.24光催化降解BPA的影响.正交试验的极差和方差分析结果表明,BPA初始浓度和反应时间影响非常显著,催化剂用量影响显著,反应溶液pH值影响不显著,初始浓度和催化剂量的交互作用很小.在BPA初始浓度为20mg/L、催化剂量2g/L、反应溶液pH7、反应时间为90min的条件下Bi3.84W0.16O6.24对BPA去除率达99.5%,TOC去除率为86.0%,BPA的降解符合一级反应动力学.     

Photocatalytic activity of Fe-doped CaTiO3 under UV-visible light

The photocatalytic degradation of methylene blue（MB） over Fe-doped CaTiO3 under UV-visible light was investigated. The as-prepared samples were characterized using X-ray diffraction（XRD）, scanning electron microscope（SEM） equipped with an energy dispersive spectrometer（EDS） system, Fourier transform infrared spectra（FT-IR）, and UV-visible diffuse reflectance spectroscopy（DRS）. The results show that the doping with Fe significantly promoted the light absorption ability of CaTiO3 in the visible light region. The Fe-doped CaTiO3 exhibited higher photocatalytic activity than CaTiO3 for the degradation of MB.However, the photocatalytic activity of the Fe-doped CaTiO3 was greatly influenced by the calcination temperature during the preparation process. The Fe-doped CaTiO3 prepared at500°C exhibited the best photocatalytic activity, with degradation of almost 100% MB（10 ppm）under UV-visible light for 180 min.     

BiOCl-(NH4)3PW12O40复合光催化剂制备及其光催化降解污染物机制

光生电子和空穴的分离效率是影响光催化性能的重要因素.氯氧铋是典型的层状纳米光催化剂,却因光生电子和空穴的快速复合所表现出的低量子效率而受到使用限制.本文通过两步的水热法合成了BiOCl-(NH_4)_3PW_(12)O_(40)复合光催化剂.以甲基橙(MO)为模拟污染物进行光催化活性测试.结果表明,在氙灯模拟的太阳光照射下,Bi与W的原子比为1∶1时,其催化效果最佳.通过自由基猝灭实验对催化剂光降解MO的催化机制进行了研究,发现BiOCl是由空穴,羟基自由基和超氧自由基共同作用来对MO进行降解;而复合催化剂则主要以羟基自由基和超氧自由基为活性物种来降解MO.通过对反应前后的催化剂进行XPS分析,证明了磷钨酸铵可以接收BiOCl产生的光生电子.通过光电流测试,表明复合光催化剂的光生电子的转移和分离效率有了较大的提高,从而提高了光催化活性.     

CuO-TiO2/导电聚合物纤维复合材料的制备及其光催化性能

利用高压静电纺丝技术,制得含羧基的导电聚合物纤维(聚偏氟乙烯/苯乙烯-马来酸酐共聚物/纳米石墨).水热条件下在纤维表面原位合成了纳米级的TiO2,再通过水热法在TiO2表面制备了微米级的球形CuO颗粒,得到CuO-TiO2/导电聚合物纤维复合材料.运用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、紫外-可见吸收光谱仪(UV-Vis)和热失重分析(TGA)对复合材料的结构与性能进行表征,并利用氙灯模拟太阳光进行光催化降解次甲基蓝实验.结果发现,CuO-TiO2/导电聚合物纤维复合材料的降解效率高于CuO-TiO2/非导电聚合物纤维、CuO-TiO2粉体和Degussa P25,光催化降解3.5h时,次甲基蓝的残留率为4.7％.     

静电纺丝法制备CaIn2O4-In2O3纳米带及其光催化性能

利用静电纺丝技术原位制备了准一维结构CaIn_2O_4-In_2O_3纳米带.采用XRD、SEM、TEM、EDS、UV-vis DRS、N_2吸附-脱附曲线等对合成的光催化剂进行表征,并以对苯二甲酸(TA)为分子探针物质,结合荧光技术探讨了光催化反应过程中·OH自由基的变化.以亚甲基蓝(MB)为降解目标物,考察了CaIn_2O_4-In_2O_3纳米带的光催化活性,并研究了溶液pH及MB初始浓度对其光催化活性的影响.研究结果表明,宽度约为(663±75) nm的CaIn_2O_4-In_2O_3纳米带由直径约为80 nm的纳米颗粒组成,且纳米颗粒之间有一定的孔隙.模拟太阳光辐照120 min,MB的降解率为76%,且降解过程服从一级动力学模型.CaIn_2O_4-In_2O_3纳米带在酸性环境中显正电性,且光催化反应体系中·OH自由基的生成量随反应时间线性增加.CaIn_2O_4与In_2O_3的耦合使得合成的光催化剂在模拟太阳光下具有良好的光催化活性.     

Triton X-100 induced cuboid-like BiVO4 microsphere with high photocatalytic performance

A highly active visible light-induced BiVO₄ photocatalyst was prepared by a simple co-precipitation method using ammonia solution as a pH adjustor and Triton X-100 (TX100) as a structure directing agent. The physical properties of the prepared BiVO₄ photocatalyst were investigated by several techniques such as X-ray diffractometer (XRD), Brunauer–Emmett–Teller (BET) surface area measurement, scanning electron microscopy (SEM), energy dispersive analysis (EDS), Fourier-transformed infrared spectroscopy (FT-IR), photoluminescence (PL), and UV–Vis diffused reflectance spectroscopy (DRS). XRD results revealed the existence of a monoclinic scheelite structure in both the unmodified and the modified samples. The TX100 played a crucial role to control the cuboid-like shape morphology of BiVO₄. The DRS results showed that the as-prepared cuboid BiVO₄ possessed enhanced visible light absorption range compared with that of the unmodified BiVO₄. The photocatalytic activity was evaluated via indigo carmine (IC) degradation under visible light irradiation. The modified BiVO₄ showed higher photocatalytic efficiency than the unmodified BiVO₄ and the commercial P25-TiO₂ which could be ascribed to the better charge separation efficiency.     

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.     

Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors

A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.     

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.     

Bi掺杂In2TiO5纳米带的制备及其光催化性能

以Bi(NO_3)_3、Ti(OC_4H_9)_4、In(NO_3)_3和聚乙烯吡咯烷酮(PVP-K30)为原料,采用静电纺丝法和沉淀法相结合,成功制备了Bi掺杂In_2TiO_5(Bi-In_2TiO_5)纳米带.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能量色散谱(EDS)、紫外-可见漫反射光谱(UV-vis DRS)和氮气吸附-脱附等温线(BET)等技术对样品进行表征.结果表明,Bi的掺杂未引入新的杂相,样品均为正交晶系结构,掺杂前后样品的形貌未发生明显变化.适量的Bi掺杂,在In2Ti O5晶格中形成杂质能级,降低了In_2TiO_5的带隙能.当掺杂量为2%时,制备的Bi-In_2TiO_5纳米带的光催化活性最高.在氙灯(150 W)辐照下,150 min,对罗丹明B的降解率达95.8%,且该催化剂对氟喹诺酮类抗生素左氧氟沙星(LEV)也表现出优良的光催化降解性能.     

上转换发光剂掺杂纳米TiO2的制备及可见光降解乙基紫的研究

合成了一种新型含有稀土金属Er的上转换发光剂40CdF₂·60BaF₂·1.6Er₂O₃,此上转换发光剂在488 nm可见光的激发下,产生了5个波长均小于387 nm的上转换紫外光发射峰.采用超声波分散的方法制备出了上转换发光剂掺杂的纳米TiO₂可见光光催化剂.利用X-射线衍射(XRD)及透射电镜(TEM)对催化剂进行了表征.以乙基紫染料为研究对象,研究了在(三基色灯下发出的)可见光的照射下该可见光光催化剂的催化降解性能,并与未掺杂的纳米TiO₂粉末的催化性能进行了对比.结果表明,作为掺杂成分的上转换发光剂可有效地将可见光转化为紫外光并被纳米TiO₂粉末吸收利用,在可见光照射12.0 h后乙基紫降解率达到了99.68%,大大高于未掺杂纳米TiO2时的降解率.     

超薄g-C3N4在可见光下协同PDS降解双氯芬酸钠的机理研究

运用一步热聚合法成功制备出二维超薄g-C_3N_4(UCN)纳米片,通过透射电子显微镜、比表面测定仪、紫外可见漫反射光谱、荧光光谱对UCN的形貌及光学性能进行表征,并利用g-C_3N_4对水相中的双氯芬酸钠(DCF)进行了光催化降解实验.结果表明,UCN具有二维超薄纳米片结构,且具有较高的比表面积、较强的可见光吸收能力及空穴-电子转移能力.UCN的光催化活性优于块状g-C_3N_4,过硫酸盐(PDS)的加入对双氯芬酸钠的降解有促进作用,UCN/PDS体系中对双氯芬酸钠降解起主导作用的活性物种为O【math203z】,经过150 min的反应,双氯芬酸钠的矿化率达到78%.双氯芬酸钠在UCN/PDS体系下的光催化降解符合一级动力学规律和Langmuir-Hinshelwood模型,DCF的光催化降解在偏酸和偏碱性的情况下具有较快的反应速率.DCF在河水中的反应速率是超纯水中的3.4倍.循环实验表明,UCN具有很好的光催化稳定性.     

Synergistic photocatalytic degradation of pyridine using precious metal supported TiO2 with KBrO3

A series of precious metals catalysts （M/TiO/, M = Ru, Rh, Pd, Ag, Ir, Pt or Au） were prepared by a light deposition method and the synergistic photocatalytic degradations of pyridine （20 mg/L） under UV irradiation （365 nm） using M/TiO2 with electron capture agent KBrO3 have been investigated. The results show that KBrO3 has a greatly synergistic role on M/TiO2 and the photocatalytic activity of M/TiO2 is closely related to its work function. Ag could greatly enhance the activity of TiO2 due to the binding characteristics of pyridine on Ag. Under the conditions of 0.5 wt.% Ag loading, Ag/TiO2 concentration of 0.1 g/L, KlrO3 concentration of 10 mmol/L and reaction liquid pH value at 9, the pyridine can be degraded by 64% within 3 hr, doubled than TiO2 photocatalytic system. The degradation kinetics of pyridine follows first-order kinetics and k = 5.53 × 10-3 min^-1.