H2O2、金属离子等对Cr(Ⅵ)离子光催化还原及对敌敌畏农药光催化氧化的影响

以Cr(Ⅵ)离子、敌敌畏农药作为污染物的代表,研究了H₂O₂、金属离子等对Cr(Ⅵ)离子光催化还原及对敌敌畏农药光催化氧化的影响.结果表明,加入少量的H₂O₂对Cr(Ⅵ)离子的光催化还原起阻碍作用,对敌敌畏农药的光催化氧化起促进作用;加入少量的Cu²⁺对Cr(Ⅵ)离子光催化还原及对敌敌畏农药的光催化氧化均起促进作用;加入Zn²⁺、Na⁺对Cr(Ⅵ)离子及敌敌畏农药的光催化降解均无明显的影响;加入甲醇、甲苯对Cr(Ⅵ)离子的光催化还原起促进作用,对敌敌畏农药的光催化氧化起阻碍作用.探讨了H₂O₂、金属离子等对Cr(Ⅵ)离子光催化还原及对敌敌畏农药光催化氧化影响的机理.     

SO2－4/Ce-TiO2光催化降解二甲基二氯乙烯基磷酸酯

纳米;超强酸;SO2－4/Ce-TiO2光催化降解二甲基二氯乙烯基磷酸酯     

NiFe2O4对刚果红的光催化降解性能研究

采用水热法合成了尖晶石型NiFe₂O₄,并利用X射线粉末衍射仪对其物相进行了表征,利用紫外-可见分光光度计对其光催化降解刚果红的性能进行了研究。以刚果红为光催化降解底物,探究了刚果红初始浓度、催化剂用量、溶液pH、不同光源等因素对NiFe₂O₄光催化降解刚果红活性的影响。结果表明,当刚果红溶液浓度为20 mg/L、催化剂NiFe₂O₄的用量为0.065 g、pH 2~10、在太阳光下照射480 min时,刚果红的降解率高达99%以上,催化剂性能稳定,适合处理刚果红类有机污染物。     

空心玻璃微球附载TiO2光催化降解有机磷农药

有机磷农药废水的处理目前大多采用生化法,但是处理后的废水中有机磷的含量仍远远高于国家关于废水的排放标准。近年来,利用半导体粉末作为光催化剂降解有机污染物的研究已有许多报道^[1,2].文献[3-5]报道了利用光催化剂的悬浮体系降解有机磷化合物的研究,结果表明,有机磷在短时间内可被完全光催化降解至无机磷(PO₄^3-).但是由于半导体粉末甚细,采用悬浮体系既造成光催化剂的二次回收困难,又易造成浪费.本文在先前工作的基础上,将TiO₂附载在空心玻璃微球上形成TiO₂/beads光催化降解有机磷农药,探讨了多种因素对光催化降解的影响.     

Keggin型铬取代的磷钨杂多阴离子/二氧化钛纳米膜光催化剂的制备及可见光催化性能

以钛酸四丁酯Ti(OC₄H₉)₄为TiO₂前驱体,Keggin型铬取代的杂多阴离子PW₁₁Cr为可见光活性组分,采用溶胶-凝胶提拉法在玻片表面制备了PW₁₁Cr/TiO₂纳米膜光催化剂,并用UV-Vis DRS、IR、XRD、SEM和TEM等技术手段对催化剂的光吸收性质、化学组成、晶相和表面结构形貌等进行了表征;讨论了膜中PW₁₁Cr和TiO₂相互作用的方式;以染料模型污染物RhB的可见光催化降解为探针,评估了PW₁₁Cr/TiO₂光催化剂的可见光催化活性,讨论了光催化反应机理,并与TiO₂的光催化反应机理进行了比较;考察了焙烧温度、PW₁₁Cr剂量和溶液pH值对光催化活性的影响;最后用RhB的循环降解实验评估了催化剂的光催化稳定性。 实验结果表明,PW₁₁Cr/TiO₂光催化剂对可见光有明显吸收,较低焙烧温度(100 ℃)下得到的膜为无定形结构,而较高焙烧温度(500 ℃)为纳晶结构;前者的光催化活性较高,在200 W金卤灯照射下降解10 μmol/L RhB,120 min的降解率为95%,4 h的COD去除率为72%;羟基自由基是导致RhB降解的主要氧活性物质;低的膜处理温度,高的PW₁₁Cr负载量和溶液酸性有利于提高PW₁₁Cr/TiO₂膜的光催化活性;经循环重复使用10次,PW₁₁Cr/TiO₂膜的光催化活性仅有较少损失。     

超声波-二氧化钛光催化耦合法降解高效氯氰菊酯

采用超声波-TiO2光催化耦合法降解高效氯氰菊酯,考察了高效氯氰菊酯初始浓度、降解时间、溶液pH、催化剂用量等对高效氯氰菊酯农药残留的降解效果,并利用水果进行了实物模拟.结果表明:利用超声波-TiO2光催化耦合法能够有效地降解高效氯氰菊酯农药残留.在弱酸环境中,当纳米TiO2投放量为1.2g/L时,经2h超声催化降解,不同浓度的高效氯氰菊酯农药稀释液均被有效降解,降解率最高可达98.3%.     

强电离放电气体洗消DMMP机理研究

利用强电离放电气体对神经性化学战剂模拟剂甲基磷酸二甲酯(DMMP)进行洗消. 强电离放电气体可以迅速降解DMMP, TOC也有明显下降. 自由基促进剂和抑制剂对DMMP的降解效率有明显影响, 降解以自由基反应为主. 活性极高的羟基自由基可以无选择地攻击DMMP中的CH₃—P、P—OCH₃、O—CH₃等基团, 生成磷酸酯类、甲基磷酸酯类、甲基磷酸、、CO₂等中间产物, DMMP最终可能被矿化. 推测强电离放电气体洗消DMMP主要有四条反应路径.     

铕掺杂TiO2的制备及其可见光光催化性能研究

采用溶胶-凝胶法制备了不同铕(Eu)掺杂量的TiO₂纳米颗粒(Eu-TiO₂),利用透射电镜(TEM),X射线光电子能谱(XPS),X射线衍射(XRD)及紫外可见漫反射(UV-Vis DRS)等方法对Eu-TiO₂进行了物理特性的初步表征.结果表明:与未掺杂纳米TiO₂比较,Eu-TiO₂禁带宽度变窄,具有可见光光催化活性.在可见光下(λ≥420 nm)照射下,以光催化降解染料罗丹明B(Rhodamine B,RhB)为目标反应,探讨了Eu-TiO₂不同制备条件对RhB降解光催化活性的影响,优化得到制备高活性Eu-TiO₂最佳pH为3、掺杂比例(n_Eu/n_Ti)为0.05%、煅烧温度为500 ℃.研究了可见光照射下Eu-TiO₂降解RhB和无色有机小分子水杨酸(SA)光催化反应条件及降解特性,RhB的12 h深度氧化矿化率为60.2%,SA的8 h降解率达到100%.通过跟踪测定可见光下Eu-TiO₂光催化反应过程中氧化物种的变化,研究了可见光激发Eu-TiO₂光催化反应机理,表明其光催化反应主要涉及羟基自由基(·OH)历程.     

光催化微反应器中水样光催化降解及Cd2+在线检测

本文以粉末法制备TiO₂涂层的玻璃微流控芯片作为光催化反应器,采用UV-LED点光源为紫外光源,实现了水样中EDTA的光催化降解,并用铋膜电极差分脉冲溶出伏安法在线检测微量水样中的重金属离子Cd²⁺。水样中的Cd²⁺由于EDTA的络合作用无法在铋膜电极上产生电流信号,而当水样在光催化微反应器中经紫外光催化后,由于EDTA与Cd²⁺的配合物结构遭破坏,因此释放出游离的Cd²⁺,从而使Cd²⁺的电流信号得到一定程度的恢复。Cd²⁺的电流恢复程度越大,表明EDTA被光催化降解的程度越高。本文考察了光照强度、反应液流速和氧气流速、pH等因素对EDTA光催化降解效率的影响。在光照强度为120 mW/cm²、反应液流速为50 μL/h、氧气流速为850 μL/h、pH为4.4条件下,水样中EDTA的光催化降解率效果最佳,水样中Cd²⁺的电流恢复程度可达92.6%。反应液流速为300 μL/h时,Cd²⁺的电流恢复率为60.0%,重复光催化反应5次的RSD为5.2%,具有较好的重现性。本文建立了水样EDTA光催化降解及Cd²⁺在线检测的微分析系统,在线检测所需的样品体积仅为0.3 mL,完成一个水样分析的时间约为60 min。     

类金属WO2/g-C3N4复合光催化剂的构造及其优异的光催化性能(英文)

随着化石燃料快速消耗和环境污染日益严峻,高效光催化产氢技术作为最有前景的绿色能源技术之一而备受关注.作为典型的2D纳米片,g-C₃N₄具有很多适合应用在光催化领域的特性,如可见光效应、大比表面积和环境友好等,但单一g-C₃N₄的载流子复合率高,光催化性能不佳.研究者尝试负载贵金属(如Pt,Ag,Au等),利用贵金属功函数较高,可以快速捕获g-C₃N₄表面的光生电子,从而有效抑制光生载流子的复合;但其成本较高,限制了该技术的产业化.目前类金属材料(MoO₂,NbO₂,WO₂等)不仅表现出类似贵金属的特性,且价格低廉,有望替代贵金属.因此,引入类金属助催化剂是实现高载流子浓度和宽光谱照射下强光子吸收的好方法.本文设计并制备了类金属WO₂/g-C₃N₄纳米复合物,其表现出了较好的光催化性能:在可见光照射2h,4 wt%WO_...     

Investigation of the photocatalytic degradation of organochlorine pesticides on a nano-TiO2 coated film

The photocatalytic degradation of organochlorine pesticides including -, β-, γ-, δ-hexachlorobenzene (BHC), dicofol and cypermethrin were carried out on a nano-TiO₂ coated films under UV irradiation in the air. The photocatalytic conditions, including the amount of TiO₂, irradiation time and the intensity of light were optimized. The pesticides were most effectively degraded under the condition of 2.24 mg/cm² on TiO₂ film and a 400 W UV irradiation of high-pressure mercury lamp with a wavelength of 365 nm. A typical organochlorine pesticide, 20 μg -BHC, was dipped onto the TiO₂ film surface and degraded completely within 20 min. In addition, the photocatalytic degradation pathways on the nano-TiO₂ coated film were discussed.     

Photocatalytic Degradation of 4-Chlorophenol by Gd-Doped β-Bi2O3 Under Visible Light Irradiation

Chlorophenols are known as persistent organic pollutants.Therefore,research on the removal of chlorophenols has attracted widespread attention.Hereto,the photocatalytic degradation of 4-chlorophenol by Gd-doped β-Bi2O3 under visible light irradiation was studied.The results showed that Gd-doped β-Bi2O3 materials are efficient catalysts for the photocatalytic degradation of chlorophenols,and 2%(atomic traction)Gd-doped β-Bi2O3 exhibits the highest photocatalytic activity for 4-chlorophenol degradation,because doping an appropriate amount of Gd^3+ions can effectively reduce the recombination rate of the photogenerated e^-/h^+pairs and then enhance the photocatalytic performance.When the reaction was carried out at 25 ℃ for 6 h using the 2% Gd-doped/β-Bi2O3 micro/nano materials of 200 mg and at air flow rate of 40 mL/min,the degradation rate of 4-chlorophenol reached 92.3%.Additionally based on the analysis of the products,it was speculated that the dominant photocatalytic degradation mechanism of 4-chlorophenol by Gd-doped β-Bi2O3 under visible light irradiation is an oxidative process involving an attack by the hydroxyl radical.     

可见光辐射下活性炭-铁酸镍杂化催化剂光催化氧化氨氮(英文)

铁酸镍(NiFe2O4)中的镍原子抑制其光芬顿催化活性.然而,活性炭(AC)能激活其光芬顿催化活性,结果导致复合催化剂AC-NiFe2O4在过氧化氢存在时可见光辐射下也可催化氧化氨氮.用X射线衍射(XRD),透射电镜(TEM),傅里叶变换红外(FTIR)光谱,紫外-可见漫反射光谱(UV-Vis DRS),比表面积和振动样品磁强计对催化剂进行了表征.光催化降解氨氮的实验表明,该复合催化剂在10 h内氨氮的降解率可达到91.0%,而同样条件下没有催化剂时氨氮的去除率只有24.0%.对照实验表明,裸铁酸镍在可见光辐射下,氨氮的降解率只有30.0%.这表明活性炭加速了氨氮的氧化速率.动力学研究表明,氨氮的氧化遵循一级反应动力学规律,其表观反应动力学常数为3.538×10-3min-1.机理研究表明,氨氮的氧化是通过生成HONH2中间体,然后转化为NO2-.8次循环实验表明该复合催化剂容易分离、可循环使用、且催化活性十分稳定.因此,该催化剂具有潜在的应用价值.     

Degradation of carbofuran in aqueous solution by Fe(III) aquacomplexes as effective photocatalysts

The photodegradation of carbofuran by excitation of iron(III) aquacomplexes was investigated under UV irradiation. The degradation rate was strongly influenced by the pH, and initial concentration of Fe(III). The degradation efficiency of carbofuran at the difference pH was in good agreement with the initial concentration of Fe(OH)²⁺ in the solution. An initial carbofuran concentration of 10 mg L⁻¹ was completely degraded within 50 min at pH 2.8 with original Fe(III) concentration of 8 × 10⁻⁴ mol L⁻¹. This degradation reaction was found to follow the first order kinetics law and the rate constant of 1.60 × 10⁻³ s⁻¹ was observed. The decrease of TOC content was observed during the photocatalytic process and the removal percentage obtained was about 70% after 25 h. Furthermore, ammonium ion as an end-product was detected in the solution. Therefore, this process based on the catalytic reaction of Fe(II, III) is responsible for the continuous production of hydroxyl radicals in such system. A gas chromatography-mass spectrometry analysis showed the formation of four photoproducts, such as 2,2-dimethyl-2,3-dihydro-benzofuran-7-ol, etc., revealing that the carbamate branch, C-3 and C-2 positions in furan ring were attack targets of hydroxyl radicals. Based on these results, the photocatalytic system could be useful technology for the treatment and the mineralization of compounds like carbofuran.     

正十六烷光催化降解的羟自由基测定及其反应速率常数

以5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)为自旋捕集剂,采用电子顺磁共振(EPR)方法,在光照的TiO₂磷酸缓冲水溶液(pH=7.4)中检测到羟自由基的自旋加合物(DMPO-OH),其强度随光照时间增加而加大.在1min时达到稳态,此时DMPO-OH的产生和猝灭达到平衡.根据已知的羟自由基(HO·)与DMPO结合的速率常数k0,推导出纳米级TiO₂光催化生成羟自由基氧化正十六烷(n-C_{16H34)的速率常数k=5.0×10¹¹mol^-1·L·s^-1.}     

Enhanced Charge Separation of α-Bi2O3-BiOI Hollow Nanotube for Photodegradation Antibiotic Under Visible Light

It is highly desirable to exploit semiconductor materials with high photocatalytic degradation activity, especially bismuth oxyhalide semiconductor photocatalysts with special layered structure and suitable bandgap width. The low utilization rate of visible light and high recombination rate of photogenerated electron-hole of BiOI photocatalyst severely restrict its development. Herein, a heterojunction photocatalyst of α-Bi₂O₃-BiOI hollow nanotube was prepared by electrospinning method, solvothermal method and ion-exchange method. The α-Bi₂O₃-BiOI(BB-4, the stirring time of Bi₂O₃ in KI solution was 4 h) exhibited the best photocatalytic performance towards degrading the tetracycline hydrochloride(TC) solution, which could remove 85% of TC(10 mg/L) in 2 h under visible light irradiation. The estimated k_TC of α-Bi₂O₃-BiOI(BB-4) was ca. 3.9 and 1.8 times as much as that of α-Bi₂O₃ and pure BiOI, respectively. It indicated that the formation of α-Bi₂O₃-BiOI heterojunction can significantly improve the separation efficiency of photogenerated electron-hole pairs, therefore the photocatalytic ability was enhanced. Furthermore, a corresponding photocatalytic mechanism was proposed that ^·O₂^- radical and holes are the main active components in the photodegradation through trapping experiment.     

GO/Ag3PO4复合光催化剂的制备、表征及光催化性能

以石墨粉为原料,采用Hummers氧化法合成氧化石墨烯(GO).然后在超声作用下,将不同含量的Ag₃PO₄沉积在GO上,制备了一系列4% (w,质量分数) GO/Ag₃PO₄、8% GO/Ag₃PO₄、16% GO/Ag₃PO₄和32% GO/Ag₃PO₄复合光催化剂.对所制备的光催化剂运用N₂物理吸附、X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱、傅里叶变换红外(FT-IR)光谱、紫外-可见漫反射吸收光谱(UV-Vis DRS)等手段进行了表征,并在可见光下考察了GO含量对Ag₃PO₄光催化降解甲基橙(MO)的性能.结果表明, GO能够和Ag₃PO₄实现均匀复合.复合GO提高了催化剂的比表面积,改善了催化剂的吸附性能.复合16% GO使Ag₃PO₄光催化活性提高最显著, 120 min内对MO的降解率达到83%,是纯Ag₃PO₄光催化活性的7.5倍. GO能提高催化剂的比表面积,促进光生电子-空穴(e^-/h⁺)的分离,产生更多活性自由基,从而提高Ag₃PO₄光催化的活性和稳定性.     

Photocatalytic removal of the insecticide fenitrothion from water sensitized with TiO2

The photocatalytic removal of the insecticide fenitrothion (IUPAC name: O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), C₉H₁₂NO₅PS, from water suspension of TiO₂, was investigated by following the disappearance of the original substance along with the formation and disappearance of intermediates via recording NMR (¹H and ³¹P) and UV spectra, as well as by pH measurements. Based on the obtained data, a possible reaction mechanism was proposed. It was found that ³¹P-NMR spectrometry can be successfully used to follow the kinetics of transforming organic into inorganic phosphorus in the course of the degradation (k_a=9.2×10⁻⁷ mol dm⁻³ min⁻¹, r=0.980 for the illumination period after 15 h). The rate of fenitrothion aromatic ring decomposition was followed by UV spectrometry during the illumination (k_a=3.1×10⁻⁶ mol dm⁻³ min⁻¹, r=0.989). The complete mineralization was attained after about 66 h of irradiation.     

Enhanced Visible-light Photocatalytic Activity of g-C3N4/Nitrogen-doped Graphene Quantum Dots/TiO2 Ternary Heterojunctions for Ciprofloxacin Degradation with Narrow Band Gap and High Charge Carrier Mobility

Limited visible-light absorption and high recombination rate of photogenerated charges are two main drawbacks in g-C₃N₄-based photocatalysts. To solve these problems, g-C₃N₄/nitrogen-doped graphene quantum dots (NGQDs)/TiO₂ ternary heterojunctions were facilely prepared via a one-step calcining method. The morphology, structure, optical and electrochemical properties of g-C₃N₄/NGQDs/TiO₂ were characterized and explored. The optimal g-C₃N₄/NGQDs/TiO₂ composite exhibits enhanced photocatalytic degradation performance of ciprofloxacin (CIP) compared with the as-prepared g-C₃N₄, TiO₂(P25) and g-C₃N₄/TiO₂ heterojunction under visible light irradiation. The apparent rate constant of the composite is around 6.43, 4.03 and 2.30 times higher than those of g-C₃N₄, TiO₂ and g-C₃N₄/TiO₂, respectively. The enhanced photocatalytic efficiency should be mainly attributed to the improvement of light absorption and charge separation and transfer efficiency, originating from the narrow band gap and high charge carrier mobility. The active species trapping experiments results showed that the h⁺ and ^·O₂^- were the main active species in the degradation process. A possible photocatalytic reaction mechanism of the g-C₃N₄/NGQDs/TiO₂ composite for the enhanced degradation of CIP under visible light irradiation was also proposed.     

C/Fe-Bi_2WO_6光催化氧化诺氟沙星废水的效能及其机理

采用树脂碳化和水热两步法制备C/Fe-Bi_2WO_6光催化剂,对不同光催化剂光催化降解诺氟沙星溶液的去除效果进行对比研究。考察了条件因素对诺氟沙星(NOR)溶液在模拟太阳光下光催化氧化降解的影响规律。结果表明,在实验条件下,NOR光催化氧化降解符合L-H拟一级反应动力学模型,在NOR溶液初始浓度10 mg/L、溶液p H=7.0、催化剂用量0.75 g/L、H_2O_2浓度为200 mg/L、500 W氙灯照射60 min条件下,NOR完全分解,表观速率常数K_(app)为0.0751 min-1。采用分子荧光光谱法,对C/Fe-Bi_2WO_6光催化氧化去除NOR体系中羟基自由基生成规律进行研究,并推测了反应机理。结合LC-MS的分析结果,推测了NOR可能的降解路径和中间产物。