饮用水中卤氧化物离子色谱分析方法研究

直接大体积进样,建立生活饮用水中卤氧化物溴酸盐(BrO3-)、亚氯酸盐(ClO2-)、氯酸盐(ClO3-)含量的离子色谱(IC)法。优化的色谱条件为:Metrosep A Supp 7(250 mm)色谱柱配以Metrosep A Supp1保护柱,淋洗液为3.6 mmol/L Na2CO3与1.0 mmol/L NaHCO3;流速为0.6mL/min;进样量为100μL,抑制型电导检测器。方法结果显示:卤氧化物与常见共存阴离子完全分离,标准曲线在(5.0～400)μg/L范围内具有良好的线性关系(r>0.999),精密度高(相对标准偏差RSD<5.0%),样品加标平均回收率在90.8%~105%之间。按S/N=3,BrO3-、ClO2-、ClO3-的检出限分别为(0.9、0.7、1.0)μg/L。该方法操作简单、分离效果好,可与常见阴离子实现同时分析,灵敏度高,重现性好,适合于饮用水中消毒副产物中溴酸盐、亚氯酸盐、氯酸盐的同时测定。     

氯代十六烷基吡啶缔合微粒光度法测定二氧化氯

在pH3.49的NaAC-HCl介质中,ClO2与过量的KI反应生成I3-,I3-在350nm处有一吸收峰;当阳离子表面活性剂(CS)氯代十六烷基吡啶(CPCM)等存在时,形成淡黄色的较稳定的缔合微粒(CPCM-I3)n,在354nm处产生一个吸收峰,在470nm和520nm处产生2个共振散射峰。ClO2浓度C在0.0149～1.524mg/L范围内符合朗伯比耳定律,回归方程为△A=0.1136C+0.0001,相关系数R为0.9988,检测限为0.007mg/L。据此,建立了一种痕量ClO2光度分析新方法,用于样品分析,结果令人满意。     

共振散射光谱法测定部分水解聚丙烯酰胺的水解度

在1.0 mol/L醋酸介质中,部分水解聚丙烯酰胺(HPAM)与次氯酸钠溶液作用生成疏水性的氯酸胺微粒,该微粒体系在480nm处产生强的共振散射峰。HPAM的酰胺基团浓度在1.12~56.0 mg/L范围内与480nm处共振散射光强度成线性关系,检出限为0.21 mg/L。研究了共存物质对共振散射光谱法测定HPAM酰胺基浓度的影响,该方法的选择性较好,应用于样品中HPAM水解度的测定,结果满意。     

氯离子活化过氧乙酸对罗丹明B的降解性能及机理研究

为解决传统H₂O₂(过氧化氢)体系对高盐特性染料废水去除效率低的问题,筛选合适的氧化剂迫在眉睫. PAA(过氧乙酸)因具备氧化还原电位较高、裂解所需键能较低、对pH适应范围更广等优点具有巨大的应用潜力. 因此,采用高浓度梯度Cl-活化PAA用于去除RhB(罗丹明B),通过对比不同体系的降解效果、控制Cl-浓度和PAA投加量等反应条件,探究Cl-/PAA体系降解RhB的催化性能及反应机理. 结果表明:①Cl-/PAA体系对RhB的氧化能力远高于Cl-/H₂O₂体系,并且RhB降解过程符合拟一级反应动力学模型,提高氧化剂PAA的投加量和催化剂Cl-的浓度、降低初始RhB浓度均有利于目标污染物的去除. ②在初始RhB浓度为10 mg/L、PAA投加量为2.0 mmol/L、Cl-浓度为400 mmol/L后续处理条件下,10 min内RhB的降解率达到96.2%. ③pH对RhB的降解影响微弱, Fe3+促进了RhB的降解,K+对降解过程轻微抑制,NO₂-、CO₃2-、HCO₃-则表现出非常显著的抑制作用,脱色率分别降低了70.8%、83.8%和90.8%,而Mn2+、SO₄2-对RhB降解无显著影响. ④RhB在超纯水、自来水及反渗透水不同水源中的降解率无明显变化,具有良好的应用前景;结合自由基捕获试验及电子自旋共振证明,Cl-/PAA体系中产生的乙酰氧基、乙酰过氧基及单线态氧是在RhB降解中起主导作用的活性物质. 研究显示,Cl-活化PAA对去除罗丹明B具有较高的催化活性,通过模拟实际废水证明Cl-/PAA是一种可行的高级氧化技术.      

A novel co-catalyzed system between persulfate and chlorite by sonolysis for removing triphenylmethane derivative

Triphenylmethane (tpm) derivatives (e.g. tpm_CV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite (US/S₂O₈²⁻/ClO₂⁻) oxidation process was developed for the effective removal of tpm_CV in wastewater. The apparent non-integer kinetics (n around 1.20) of tpm_CV degradation under different factors (R²_Adj > 0.990) were investigated, respectively. Inhibiting effects of anions were greater than those of cations (except Fe(II/III)). The adding of micromolecule organic acids could regulate degradation towards positive direction. The double response surface methodology (RSM) was designed to optimize tpm_CV removal process, and the acoustic-piezoelectric interaction was simulated to determine the propagation process of acoustic wave in the reactor. The possible degradation pathway was explored to mainly include carbonylation, carboxylation, and demethylation. The estimated effective-mean temperature at the bubble-water interface was calculated from 721 to 566 K after introducing the ClO₂⁻, however, the adsorption or partitioning capacity of tpm_CV in the reactive zone was widened from 0.0218 to 0.0982. The proposed co-catalysis of US/S₂O₈²⁻/ClO₂⁻ was based on the determined active species mainly including ClO₂, SO₄⋅⁻, and ⋅OH. Compared with other US-based processes, the operating cost (3.97 $/m³) of US/S₂O₈²⁻/ClO₂⁻ with the EE/O value (16.8 kWh/m³) was relatively reduced.     

Mo源改性石墨相氮化碳(g-C3N4)活化过一硫酸盐可见光降解罗丹明B的性能研究

分别以钼酸钠（MA）和乙酰丙酮钼（MC）作为钼（Mo）源,采用热聚合法合成不同类型Mo-C₃N₄材料（MACN和MCCN）,并通过XRD、SEM、XPS、UV-Vis DRS等表征技术探究不同Mo源的引入对g-C₃N₄晶体结构和光学性质的影响.结果表明,Mo的引入增大了g-C₃N₄的晶格间距,以MC为Mo源合成的MCCN催化剂具有更大的比表面积、更宽的可见光响应范围和更低的能带宽度.将所合成的催化剂应用于耦合过一硫酸盐（PMS）可见光催化降解罗丹明B （RhB）研究,发现在催化剂浓度为0.5 g·L^-1、PMS浓度为1 mmol·L^-1、罗丹明B浓度为10 mg·L^-1的条件下,MCCN-4/PMS/Vis催化体系在25 min内对RhB的降解率高达94.1%,分别是MCCN-4/Vis和单独PMS催化体系的5.6和19.2倍,并且RhB光催化降解过程符合一级动力学方程.为进一步探索MCCN/PMS/可见光（Vis）催化体系的最佳工艺条件,系统考察了Mo的掺杂量、催化剂投加量、PMS浓度、污染物浓度、pH值等实际因素对RhB降解效果的影响.同时,循环实验表明,MCCN-4复合催化剂具有良好的稳定性和可重复性,3次循环之后仍保持89.1%的RhB降解率.此外,捕获实验和电子自旋共振测试（ESR）结果表明,在MCCN/PMS/Vis催化体系下,光生空穴（h⁺）和超氧自由基（·O₂^-）作为主要活性物种参与了RhB的降解.     

亚铁盐对二氧化氯杀藻副产物亚氯酸盐去除的研究

实验研究亚铁盐对来自于供水水库的含藻原水二氧化氯杀藻过程中产生的无机副产物亚氯酸盐去除的效果及亚铁盐的投加量,同时考察亚铁盐在去除亚氯酸盐的过程中的除浊作用。实验结果表明,FeSO4能完全去除二氧化氯杀藻的无机副产物亚氯酸盐。FeSO4在去除亚氯酸盐的同时也与二氧化氯反应而使二氧化氯的浓度降低。FeSO4的用量是亚氯酸盐和二氧化氯与FeSO4反应的理论用量的总和。在二氧化氯预氧化杀藻与投加FeSO4的时间间隔较短的情况下,FeSO4的投加量按照初始投加量70%的二氧化氯与FeSO4反应的化学计量关系计算确定,此时亚氯酸盐能完全被去除。FeSO4在去除亚氯酸盐的同时具有除浊作用,在饮用水的净化中可以减少常规混凝剂的用量,当浊度为23.3 NTU或24.3 NTU时,不需再投加常规混凝剂。FeSO4的絮凝作用对除藻有协同作用。     

红土镍矿基材料吸附及有氧降解水体污染物

以红土镍矿为研究对象,考察了原矿（HT）及改性矿（HT-FeNi）去除水体中罗丹明B （RhB）的效果.借助XRD、BET、IR等表征手段,结合吸附动力学和等温吸附模拟研究了HT吸附RhB的过程及机制.结果表明：HT的孔隙结构较为丰富,有良好的RhB吸附性能.当HT添加量为0.2g/L时,RhB去除率为39.03%,吸附量达到93.80mg/g.HT添加量增加,RhB去除效果增强,平衡吸附量减小.HT吸附RhB的过程更符合准二级动力学,包含表面扩散及颗粒内扩散两个步骤.等温吸附模型拟合发现Freundlich能够准确描述HT吸附RhB的过程.1/n<0.5,表明吸附过程较易进行.HT经5次循环实验后,吸附量仍能达到39.67mg/g,表明HT有较好的循环使用性能.HT吸附RhB主要归因于Si-O吸附位点.通过气基还原制备得到改性矿（HT-FeNi）.采用SEM、XRD、BET、XPS等手段对HT-FeNi进行表征分析,并考察了HT-FeNi降解RhB的效果.结果表明：HT-FeNi比表面积小（14.374m²/g）,主要成分为铁镍双金属.HT-FeNi不能通过吸附作用去除RhB,而HT-FeNi/Air/pH=3体系在40min内RhB降解效率为94%.捕获活性氧物种的实验证明,HT-FeNi/Air/pH=3体系去除RhB过程中起主要作用的活性氧物种是羟基自由基（·OH）.在酸性条件下,HT-FeNi通过活化O₂生成·OH,Ni⁰诱导的Fe²⁺/Fe³⁺循环促使HT-FeNi/Air/pH=3体系生成更多的·OH.将HT-FeNi/Air/pH=3体系应用于去除水体中甲基橙（MO）和二硝基氯苯（DNCB）,去除效率分别为47%、78%.     

响应面法优化水力空化强化二氧化氯降解罗丹明B研究

利用响应面法的中心组合设计方法对水力空化强化二氧化氯降解罗丹明B实验进行设计,建立了二次多项式模型,并且模型拟合性较好。对实验条件进行优化,结果表明最佳实验条件为:入口压力为0.44 MPa,反应时间为100 min,二氧化氯浓度为33.74 mg/L。在最佳条件下,罗丹明B的实际降解率为92.2%,与预测值仅差0.3%。     

Microwave photocatalytic degradation of Rhodamine B using TiO2 supported on activated carbon： Mechanism implication

The photocatalytic degradation of Rhodamine B (RhB) was carried out using TiO2 supported on activated carbon (TiO2-AC) under microwave irradiation. Composite catalyst TiO2-AC was prepared and characterized using X-ray di raction (XRD), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET). In the process of microwave-enhanced photocatalysis (MPC), RhB (30 mg/L) was almost completely decoloured in 10 min, and the mineralization e ciency was 96.0% in 20 min. The reaction rate constant of RhB in MPC using TiO2-AC by pseudo first-order reaction kinetics was 4.16 times of that using Degussa P25. Additionally, according to gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS) identification, the major intermediates of RhB in MPC included two kinds of N-de-ethylation intermediates (N,N-diethyl-N’-ethyl-rhodamine (DER)), oxalic acid, malonic acid, succinic acid, and phthalic acid, maleic acid, 3-nitrobenzoic acid, and so on. The degradation of RhB in MPC was mainly attributed to the destruction of the conjugated structure, and then the intermediates transformed to acid molecules which were mineralized to water and carbon dioxide.     

赤铁矿光助类Fenton降解有毒有机污染物

可见光照射下(λ>420 nm)采用天然赤铁矿为催化剂降解罗丹明B(rhodamine B,RhB)和无色小分子2,4-二氯苯酚(2,4-dichlorophenol,DCP),探讨了溶液pH、催化剂用量、溶液中溶铁量对降解反应的影响,通过紫外-可见分光光度计、红外光谱仪、苯甲酸荧光光度法以及COD等跟踪降解过程,并对反应机制做了初步探讨.结果表明,Cata/RhB/H2O2/vis体系能有效地降解RhB,降解最佳条件为:催化剂用量0.6 g.L-1、pH为3.0、H2O2浓度1.5×10-3mol.L-1,反应180 min可完全脱色,且溶铁对催化体系的贡献较小;对2,4-DCP的降解,24 h后,降解率达56%.且该催化剂具有良好的稳定性,循环使用6次,催化剂活性无明显变化.苯甲酸荧光光度法检测到反应体系中产生了高活性氧化物种.OH,反应机制主要是.OH的异相类Fenton过程.     

C3N4/BiOBr复合可见光催化剂的性能及其作用机制

利用水热合成法制备了C_3N_4/BiOBr复合可见光催化剂,通过XRD、FT-IR、SEM、DRS、PL等手段对催化剂的物相组成和光化学性能进行了系统表征,利用对罗丹明B(RhB)的降解实验评价了催化剂在可见光照下的光催化降解活性和稳定性并通过ESR分析和自由基捕获实验探究了RhB的光催化降解机制.结果表明,水热合成法可成功制备结晶性能良好的C_3N_4/BiOBr复合可见光催化剂;C_3N_4的复合降低了BiOBr光催化剂的电子-空穴的复合,提高了光催化降解活性,其中15%C_3N_4/BiOBr的活性最佳,可见光照18 min后RhB的脱色率达100%,较纯BiOBr提高了1.5倍,且重复使用5次后仍具有较高的光催化降解活性;复合催化剂光催化降解RhB过程中参与降解的主要活性物种为空穴(h~+)和超氧自由基(·O_2~-),其中h~+影响更为显著.     

g-C_3N_4/石墨烯复合材料的制备及光催化活性的研究

以三聚氰胺和氧化石墨烯颗粒为原料,通过研磨负载、氮气气氛下煅烧的方法制备了石墨相氮化碳/石墨烯(g-C_3N_4/r GO)复合光催化剂.主要采用TEM、XRD、PL等对其进行表征,研究了其在模拟太阳光下对罗丹明B(Rh B)的光催化性能.PL分析结果显示,相比单一的g-C_3N_4,g-C_3N_4/r GO的光生电子-空穴对的复合几率大大降低.光催化结果表明,和单一g-C_3N_4相比,首次使用研磨负载、氮气保护气氛下煅烧制备的g-C_3N_4/r GO(2%)光催化反应180min后对Rh B的降解率提高了43.2%.这是因为石墨烯为g-C_3N_4提供了电子转移场所,实现光生电子-空穴的有效分离,从而提高了光催化效率.本文还考察了添加叔丁醇(TBA)和三乙醇胺(TEOA)后对g-C_3N_4/r GO光催化的影响,实验结果表明:光生空穴是g-C_3N_4/r GO光催化体系中的主要活性物质之一.     

三维有机LDH的制备及其对有机物的普适性吸附

以表面活性剂十二烷基硫酸钠(SDS)为软模板剂,制得有机三维花状层状双金属氢氧化物(3D-SLDH).采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱仪(EDS)和N2吸附-脱附等表征手段对3D-SLDH的结构进行表征,确定最佳合成尿素浓度,并通过静态吸附实验考察了3D-SLDH对金橙Ⅱ(AO7)、罗丹明...     

硫氯共掺杂g-C3N4纳米片光催化降解染料

采用气泡模板法制备了硫氯共掺杂的g-C₃N₄纳米片,通过XRD、FT-IR、XPS、SEM、UV-vis DRS和PL等手段对样品进行了表征,利用可见光照射下光催化降解罗丹明B（RhB）来评价其催化性能.结果表明,改性后的硫氯共掺杂的g-C₃N₄纳米片具有更大的比表面积,电子-空穴的分离效率提高,并且掺杂引起了能带结构的改变,使降解RhB的氧化基团从单一的·O₂^-变为·O₂^-和·OH双氧化基团,极大地提高了降解能力,制备的硫氯共掺杂g-C₃N₄纳米片对RhB的降解速率常数达到了0.01683min^-1,是纯氮化碳的5.5倍.     

Detection of intermediates in the TiO2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.     

Impact of combining chlorine dioxide and chlorine on DBP formation in simulated indoor swimming pools

The main objective of this study was to assess the combined use of chlorine dioxide (ClO2) and chlorine (Cl2) on the speciation and kinetics of disinfection by-product (DBP) formation in swimming pools using synthetic pool waters prepared with a body fluid analog (BFA) and/or fresh natural water. At 1:25 (mass ratio) of ClO2 to Cl2, there was no significant reduction in the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) for both BFA solution and natural water compared to the application of Cl2 alone. When the mass ratio of ClO2 to Cl2 increased to 1:1, substantial decreases in both THMs and HAAs were observed in the natural water, while there was almost no change of DBP formations in the BFA solution. Haloacetonitriles and halonitromethanes levels in both water matrices remained similar. In the presence of bromide, the overall DBP formation increased in both BFA solution and natural water. For the DBP formation kinetics, after 72 hr of contact time, very low formation of THMs and HAAs was observed for the use of ClO2 only. Compared to Cl2 control, however, applying the 1:1 mixture of ClO2/Cl2 reduced THMs by > 60% and HAAs by > 50%. Chlorite was maintained below 1.0 mg/L, while the formation of chlorate significantly increased over the reaction time. Finally, in a bench-scale indoor pool experiment, applying ClO2 and Cl2 simultaneously produced less THMs compared to Cl2 control and kept chlorite at < 0.4 mg/L, while HAAs and chlorate accumulated over 4-week operation period.     

抗坏血酸改性Br掺杂g-C3N4光催化降解污染物

以尿素和溴化铵分别作为前驱体和溴源,同时利用抗坏血酸对g-C₃N₄进行改性,通过二次焙烧法成功制备了抗坏血酸改性的Br掺杂g-C₃N₄-AA-Br纳米片光催化剂.利用XRD、TEM、XPS、UV-Vis DRS、PL、N₂吸附-脱附等测试手段对催化剂的结构、形貌、光学性能进行了表征.结果表明g-C₃N₄-AA-Br具有较大的比表面积、拓宽的可见光吸收范围以及较低的电子-空穴复合率.在可见光下考察了不同催化剂对RhB、甲基橙、活性蓝染料降解的光催化性能,结果表明g-C₃N₄-AA-Br-2在可见光下在180min内对RhB降解率为72%,其速率常数k=0.00847min^-1,是纯g-C₃N₄的5.6倍.通过活性物种捕获剂实验发现降解RhB的主要活性物种为羟基自由基（·OH）和超氧自由基（·O₂^-）,并推测了可能的反应机理.     

Study on the removal of NOx from simulated flue gas using acidic NaClO2 solution

The study on the removal of NOx from simulated flue gas has been carded out in a lab-scale bubbling reactor using acidic solutions of sodium chlorite. Experiments were performed at various pH values and inlet NO concentrations in the absence or presence of SO2 gas at 45℃. The effect of SO2 on NO oxidation and NO2 absorption was critically examined. The oxidative ability of sodium chlorite was investigated at different pH values and it was found to be a better oxidant at a pH less than 4. In acidic medium, sodium chlorite decomposed into C102 gas, which is believed to participate in NO oxidation as well as in NO2 absorption. A plausible NOx removal mechanism using acidic sodium chlorite solution has been postulated. A maximum NOx removal efficiency of about 81% has been achieved.     

MnO2@ Graphite电极类电Fenton降解有毒有机污染物

制备了二氧化锰复合石墨(MnO2@graphite)电极,通过XRD,TEM对电极材料进行表征,并通过电化学工作系统(循环伏安法,线性扫描伏安法,计时电量法)对MnO2@graphite电极的电催化机理进行了研究.以有机染料罗丹明B( RhodamineB,RhB)和2,4-二氯苯酚(2,4-DCP)为对象,探讨了 p...