TiO2-石墨烯（Gn）复合材料光催化降解O3研究

通过改性Hummer法及溶胶凝胶法,制备出TiO2-石墨烯光催化复合材料.经吸附-光催化活性实验选出光催化活性最高的含C量为1.5%(质量分数)的TiO2-石墨烯复合材料,并在自行设计的模拟大型客机环境的气相光催化反应器中,进行O3光催化降解实验研究.结果表明,TiO2-石墨烯复合光催化材料在较短时间内对O3有较高的降解效率,且其光催化活性显著优于纯TiO2材料.初始O3浓度为(0.150～0.200)×10-6时,复合光催化剂受紫外光激发60 min的光催化降解率为66.12%,初始O3浓度为(0.950～1.000)×10-6时,其光催化降解率约为77%,较低浓度时((0.100～0.150)×10-6),O3去除率也能达到45.45%.此外,通过探讨光催化材料的重复使用性能,表明复合光催化剂重复使用4次以内,其对O3的光催化降解率保持基本稳定.     

TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应

以内分泌干扰物阿特拉津为模型污染物,研究了TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应.结果表明,在H2O2存在条件下,金红石TiO2经可见光激发可持续稳定地产生.OH自由基,在Fe3+协同作用下,.OH自由基生成量急剧增加;TiO2能可见光催化H2O2降解阿特拉津,金红石TiO2显示出较锐钛矿TiO2及混晶TiO2(TiO2P25)更高的催化活性,反应60 min,阿特拉津的降解率可达40%;以Fe3+协同TiO2可见光催化H2O2降解阿特拉津时,反应效率显著加快,反应5 min即对阿特拉津的降解率达到100%,而金红石TiO2显示出更为明显的协同效应.     

TiO2降解迪美唑的动力学及活性物质分析

兽类抗生素迪美唑是一种新兴的污染物质,对环境和人类健康具有潜在危害.以紫外光为光源,以TiO2为催化剂,对其进行光催化降解,考察了溶液pH值、TiO2投加量、溶液的初始浓度等影响因素对迪美唑降解效果的影响.结果表明,在TiO2投加量为1 g·L-1,迪美唑初始浓度为40 mg·L-1,溶液pH为11的最优条件下反应90 min后,迪美唑的去除率为90%,反应速率为0.025 7 min-1.反应符合伪一级动力学模型.光催化降解迪美唑有两个途径:一是·OH氧化过程,二是e-还原过程.     

Ce/TiO2/g-C3N4异质结的制备及光催化降解PFOA反应机制

采用溶胶凝胶-超声混合法制备了铈/二氧化钛/石墨相氮化碳（Ce/TiO₂/g-C₃N₄）异质结催化剂，通过透射电子显微镜（TEM）、X-射线粉末衍射仪（XRD）、傅里叶变换红外光谱仪（FTIR）和紫外-可见分光光度计（UV-Vis）等表征了复合材料的结构、晶相、活性基团和光吸收性能，并考察了可见光下该催化剂对模拟全氟辛酸（PFOA）废水的降解效果.结果表明，Ce/TiO₂/g-C₃N₄分散性好，粒径小于20 nm，金属Ce的掺入及TiO₂/g-C₃N₄异质结的生成，有效抑制了光生电子和空穴对的复合，使复合光催化剂禁带宽度减小，光吸收范围增大，光催化性能得到明显提升.在pH值为2，PFOA浓度为4 mg·L^-1，催化剂投加量为1 g·L^-1的条件下，可见光照射180 min后，可降解94.4%的PFOA，脱氟率为38.6%.降解过程符合准一级反应动力学，速率常数为0.522 h^-1.通过HPLC-MS分析降解产物，同时结合氟元素物料平衡的计算结果，认为降解机制主要是以阴离子形式存在的PFOA吸附至表面带有大量正电荷的催化剂表面后，在光生空穴和活性自由基的作用下，以自由基机理逐步脱去CF₂生成短链的PFCAs，同时生成氟离子.     

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.     

玻璃载体TiO2薄层光催化降解久效磷农药

研究了利用TiO₂薄层光催化降解久效磷农药的可行性。结果表明,0.65×10-4mol/L的久效磷经375W中压汞灯照射60min,被完全光催化降解至PO₄3-;加入微量的Fe3++或H2O2可提高久效磷农药的光解率;另外还研究了TiO₂薄层的附着量、反应液初始pH值、空气流量等因素对光催化降解的影响。光照80 h,TiO₂的光催化活性没有减弱,可连续使用。      

Combination of heterogeneous Fenton-like reaction and photocatalysis using Co-TiO2 nanocatalyst for activation of KHSO5 with visible light irradiation at ambient conditions

A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction（SR-Fenton） and visible light photocatalysis（Vis-Photo）, for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B（Rh B） degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2＋was found.     

Comparison of UV/PDS and UV/H2O2 processes for the degradation of atenolol in water

UV/H2O2 and UV/peroxodisulfate (PDS) processes were adopted to degrade a typical β-blocker atenolol (ATL). The degradation efficiencies under various operational parameters (oxidant dosage, pH, HCO3-, humic acid (HA), NO3- , and Cl-) were compared. Principal factor analysis was also performed with a statistical method for the two processes. It was found that increasing the specific dosage of the two peroxides ([peroxide]0/[ATL]0 ) ranging from 1:1 to 8:1 led to a faster degradation rate but also higher peroxide residual. Within the pH range 3-11, the optimum pH was 7 for the UV/PDS process and elevating pH benefitted the UV/H 2O2 process. The presence of HCO3- , HA, and Cl adversely affected ATL oxidation in both processes. The NO3- concentration 1-3 mmol/L accelerated the destruction of ATL by the UV/PDS process, but further increase of NO3- concentration retarded the degradation process, contrary to the case in the UV/H2O2 process. The rank orders of effects caused by the six operational parameters were pH ≈ specific dosage > [HA]0 > [NO3-]0 > [HCO3-]0 > [Cl-]0 for the UV/H2O2 process and specific dosage > pH > [HA]0 > [NO3-]0 > [HCO3-]0 >[Cl-]0 for the UV/PDS process. The UV/PDS process was more sensitive to changes in operational parameters than the UV/H2O2 process but more efficient in ATL removal under the same conditions.     

RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

Photodegradation of soluble microbial products (SMPs) from membrane bioreactor by GO-COOH/TiO2/Ag

This study aimed to explore a new degradation method - photocatalysis technology to polish membrane bioreactor (MBR) effluent, using 2,6-di-tert-butylphenol (2,6-DTBP) as a model soluble microbial product (SMP). 2,6-DTBP is one of the predominant SMPs in MBR effluent, which is refractory and difficult to biodegrade. This study developed a novel carboxylated graphene oxide/titanium dioxide/silver (GO-COOH/TiO₂/Ag) nanocomposite to photodegrade 2,6-DTBP. GO-COOH/TiO₂/Ag was successfully synthesized, using l-cysteine as the linker bonding TiO₂/Ag to GO-COOH. The structural, morphological and optical properties of the GO-COOH/TiO₂/Ag nanocomposite were characterized using various techniques. Owing to synergistic effects, the GO-COOH/TiO₂/Ag nanocomposite exhibited enhanced photocatalytic degradation performance under solar light irradiation when compared to TiO₂, Ag and GO-COOH. To remove 25 mg/L 2,6-DTBP, the reaction time for GO-COOH/TiO₂/Ag was only 30 min, faster than the 90 min required for pure TiO₂ or Ag. In addition, the 200 mg/L GO-COOH/TiO₂/Ag nanocomposite aqueous solution showed the best performance under solar light, with 99% removal of 2,6-DTBP. This enhanced capability is likely due to the surface plasmon resonance (SPR) effect contributed by Ag nanoparticles (NPs) doped onto the TiO₂. In addition, GO-COOH had a high effective surface area, which assisted in degrading the 2,6-DTBP through improved adsorption. The stability study showed that the photocatalytic activity of the GO-COOH/TiO₂/Ag was stable enough for recycling multiple times. The effective degradation performance and excellent stability demonstrates that the GO-COOH/TiO₂/Ag nanocomposite can be a promising photocatalyst in the field of effluent SMP photodegradation, which solves the problem of the difficult biodegradation of highly toxic 2,6-DTBP.     

Photocatalytic degradation of bisphenol A using an integrated system of a new gas-liquid-solid circulating fluidized bed reactor and micrometer Gd-doped TiO2 particles

A new gas-liquid-solid circulating fluidized bed photocatalytic reactor (GLSCFBPR) with internally placed multi-layered UV lamps was developed. Micrometer Gd-TiO₂ particles and commercial nanometer P25-TiO₂ were chosen as the photocatalysts, and the hazardous substance bisphenol A (BPA) was chosen as the model pollutant to investigate the performance of this new photocatalytic system. The results showed that the photocatalytic degradation efficiency of the micrometer Gd-TiO₂ particles was similar to that of the nanometer P-25 particles at their respective optimum dosage but the former could be easily separated out by gravity. After investigating the effects of process parameters on the photocatalytic BPA degradation, the response surface method (RSM) was further used for process optimization. The interactions among process parameters, i.e., TiO₂ concentration, superficial gas velocity and superficial liquid velocity were discovered and a related analysis was carried out to explore the underlying mechanism. A quadratic mathematic model was established and performed satisfactorily when used for prediction. The optimum conditions for this new process were as follows: TiO₂ concentration 4.5 g/L, superficial gas velocity 7.83 × 10^-3 m/sec and superficial liquid velocity 8.65 × 10^-3 m/sec.     

Inactivated properties of activated carbon-supported TiO2 nanoparticles for bacteria and kinetic study

The activated carbon-supported TiO₂ nanoparticles (TiO₂/AC) were prepared by a properly controlled sol-gel method. The effects of activated carbons (AC) support on inactivated properties of TiO₂ nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli. The key factors affecting the inactivation efficiency were investigated, including electric power of lamp, temperature, and pH values. The results show that the TiO₂/AC composites have high inactivation properties of E. coli in comparison with pure TiO₂ powder. The kinetics of photocatalytic inactivation of E. coli was found to follow a pseudo-first order rate law for TiO₂/AC composites, and kinetic behavior could be described in terms of a modified Langmuir-Hinshelwood model. The values of the adsorption equilibrium constants for the bacteria, K_c, and for the rate constants, k_r, were certainly depended on TiO₂ content. At 47 wt.% TiO₂ coatings with the highest rate constant, the K_c and k_r were 1.17 × 10⁻⁸L/cfu and 1.43 × 10⁶ cfu/(L·min), respectively. The variety of parameters shows significant effects on inactivation rate. The outer layer of bacteria decomposed first resulting in inactivation of cell, and with further illumination, the cells nearly decomposed.     

Ag改性石墨相氮化碳(g-C3N4)可见光辅助活化过一硫酸盐降解罗丹明B

采用煅烧法和光还原法制备出具有高活性的Ag/g-C₃N₄催化剂,并将其应用于可见光下活化过一硫酸盐（PMS）降解罗丹明B（RhB）废水.系统研究了实际因素RhB浓度、催化剂投加量、PMS剂量、pH值和可溶性无机阴离子对RhB降解效果的影响.结果表明,RhB的降解率随着催化剂投加量、PMS浓度的增加而增大,随着初始RhB浓度的增加而减小.弱酸性条件有利于反应活化PMS降解RhB,而中性或碱性条件都会减缓催化反应的进行.Ag/g-C₃N₄-2/Vis/PMS催化体系30 min内对RhB的去除率最高可达93.2%,分别是Ag/g-C₃N₄/Vis和单独PMS催化体系的4.0和3.7倍.体系催化活性的提高归因于Ag的表面等离子共振效应及基于硫酸根自由基的高级氧化技术与光催化技术的协同作用.不同阴离子对催化反应的影响不同,溶液中的Cl^-会对反应产生轻微的抑制作用,而H₂PO₄^-和HCO₃^-的出现大大抑制了催化性能.催化剂具有良好的稳定性,5次循环后仍能在30 min之内降解77.4%的RhB.此外,捕获实验和ESR测试结果表明,Ag/g-C₃N₄-2/Vis/PMS催化体系中存在·O₂^-、h⁺、¹O₂、SO₄^-·和·OH活性物种,并协同降解RhB污染物.     

TiO2光催化降解PFOA的反应动力学及机制研究

全氟辛酸(PFOA)是一种新的持久性有机污染物,其处置技术是研究的热点.以UV254 nm紫外灯为光源,采用商品TiO2(P25)对PFOA进行光催化降解实验,并考察pH、TiO2用量、初始浓度、反应气氛对降解的影响.结果表明,反应符合准一级动力学方程,pH对反应有重要影响,氧气存在下能提高反应效率.在pH为3,TiO2用量为1.5 g·L-1,通入空气条件下反应7 h实现基本降解,速率常数为0.4206 h-1.投加俘获剂实验表明,空穴(h+)是主要的活性物质,其对反应速率贡献率为66.1%;羟基自由基(·OH)也参与PFOA的降解过程;投加NaF实验表明,PFOA在TiO2上吸附是反应发生的首要条件.UPLC-QTOF/MS分析表明,PFOA光催化降解逐级生成短链全氟羧酸(PFCAs).     

In_2TiO_5纳米带的静电纺丝法制备及光催化性能

以酞酸丁酯(Ti(OC_4H_9)_4)、硝酸铟(In(NO3)3)和聚乙烯吡咯烷酮(PVP-K30)为原料,采用静电纺丝技术制备了In_2TiO_5纳米带.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-vis DRS)和氮气吸附-脱附等温线(BET)等技术对样品进行了表征.考察了In_2TiO_5纳米带在光催化降解罗丹明B(RhB)、甲基橙(MO)、亚甲基蓝(MB)和左氧氟沙星(LEV)过程中的应用性能,研究了不同离子型物质、溶液的pH和MB起始浓度对In_2TiO_5纳米带光催化活性的影响.结果表明:In_2TiO_5纳米带具有正交晶系结构,禁带宽度为3.47 eV,比表面积为20.71 m~2·g~(-1),可应用于4种不同离子型物质的光催化降解,发现光催化效果与被降解物质的表面带电性质有关.在紫外光照射下,90 min,对MB的降解率达98.1%,其降解过程服从一级动力学模型.     

TiO2复合催化剂弱光催化降解模拟海水中苯酚及其催化活性的影响

为了获得适用于海水中有机污染物光降解催化剂,分别选用纳米SiO_2粒子和氧化石墨烯GO为载体,利用吸附相反应技术并结合热处理过程制备了基于TiO_2的复合催化剂,研究了弱光(光强小于1mW·cm~(-3))激发下复合催化剂光催化降解模拟海水中苯酚.结果表明,吸附相反应技术结合焙烧得到的La~(3+)掺杂TiO_2-SiO_2,表面亲水性较强和对苯酚吸附能力较弱,难以克服盐离子的干扰并有效降解模拟海水中高浓度苯酚.而吸附相反应技术结合醇溶剂热还原处理后,La~(3+)掺杂TiO_2-SiO_2催化剂表面亲水性显著减弱,但该催化剂在模拟海水中不能形成稳定的悬浮体系.吸附相反应技术得到的TiO_2-GO和La~(3+)掺杂TiO_2-GO中,TiO_2粒子粒径小于10nm且均匀负载于GO的表面.醇溶剂热还原处理可使TiO_2形成晶型结构,从而提高其催化活性,同时还能将GO表面的含氧基团还原,降低催化剂表面亲水性.从而提升催化剂对苯酚的吸附能力和对盐离子的抗干扰能力.另外,还原GO与小粒径TiO_2粒子紧密结合,使光生电子能很快转移至还原GO表面,增大光生电荷分离率,进一步提升催化剂的光降解性能.     

WO3/TiO2复合半导体的光催化性能研究

采用Ｓｏｌ－Ｇｅｌ法制备ＷＯ３／ＴｉＯ２纳米粉末,以高压汞灯为光源,亚甲基蓝溶液的光催降为模型反应,结果表明,掺入ＷＯ３摩尔比为２％时,ＷＯ３／ＴｉＯ２的光活性最高;随着热处理温升高,ＷＯ３／ＴｉＯ光活性增强;     

UV/TiO2/H2O2体系对制药废水二级出水的处理特性研究

以某制药企业的二级出水为研究对象,对比了UV/TiO₂、UV/H₂O₂、UV/TiO₂/H₂O₂ 3种高级氧化工艺的处理效果,利用自主设计的一体化光催化装置进行了连续动态试验,并通过凝胶渗透色谱（GPC）、傅里叶变换红外光谱（FT-IR）、三维荧光光谱（EEM）、斑马鱼急性毒性试验等方法研究了处理前后有机物特性和生物毒性的变化.结果表明,与UV/TiO₂和UV/H₂O₂体系相比,UV/TiO₂/H₂O₂光芬顿体系对有机物的去除效果更好,当TiO₂投加量为1 g·L^-1,H₂O₂投加量为100 mg·L^-1时,处理效果达到最佳.一体化光催化装置能够利用UV/TiO₂/H₂O₂光芬顿技术快速高效地降解二级出水中的有机污染物,反应30 min时COD去除率达到50%以上.经UV/TiO₂/H₂O₂深度处理后,废水中的大分子有机物分解转换为小分子,有机物中的不饱和结构明显减少,腐殖质等溶解性有机物基本降解完全.毒性试验结果表明,该二级出水的生物毒性经深度处理后显著降低,对斑马鱼胚胎不存在致畸致死效应.     

g-C3N4修饰的TiO2纳米阵列光电催化氧化去除氰化物

通过水热法制备了TiO_2纳米棒(TiO_2NRs)电极,然后通过液相生长法将石墨相氮化碳(g-C_3N_4)负载到TiO_2NRs电极上制备出TiO_2NRs/g-C_3N_4电极.电极的XRD和SEM表征结果表明,g-C_3N_4成功负载到了TiO_2NRs上.将TiO_2NRs/g-C_3N_4电极作为光阳极用于光电催化体系中,并于反应体系中不断曝入O_2,结果发现,与钛片相比,碳气凝胶(CA)电极作为阴极时,反应150 min后CN~-的去除率由13.4%提高到53.1%.与PC过程和EC过程相比,PEC过程对CN~-的去除效果最好.不同光阳极的对比表明,g-C_3N_4与TiO_2的复合可以大大提高阴极H_2O_2产量从而促进CN~-的去除.实验表明,外加偏压的增大可以提高体系中H_2O_2的产量从而增强CN~-的去除效果,CN~-的去除率随CN~-初始浓度的增大而减小.体系的稳定性实验表明,制备的TiO_2NRs/g-C_3N_4电极具有较好的稳定性.最后提出了通过碳气凝胶阴极利用光生电子原位产H_2O_2,强化了TiO_2NRs/g-C_3N_4复合电极作为光阳极对水中CN~-的去除效果的反应机理.     

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.