氯化和臭氧预氧化处理对污水中溶解性有机物发光细菌急性毒性的影响

考察了氯化和臭氧预氧化对污水中DOM 的发光细菌急性毒性的影响. 结果表 明, 臭氧预氧化处理后发光细菌的急性毒性显著增强. 利用树脂吸附将臭氧预氧化前后 的DOM 分离为疏水性和亲水性等6 种组分, 对DOM 的6 种组分分别氯化, 考察了氯化 前后各组分的发光细菌急性毒性. 结果发现, 亲水性组分的比例在臭氧预氧化后明显增 加, 且亲水性有机物的急性毒性显著强于疏水性有机物. 结合电位滴定和傅立叶红外分 析发现, 与疏水性有机物相比, 亲水性有机物具有较高含量的ph-OH 官能团.     

复合功能树脂对水体中天然有机酸的吸附

合成了胺基修饰复合功能树脂WJN-07, 研究了富里酸、单宁酸和没食子酸在树脂上的吸附行为. 与去除DOM的商品树脂XAD-7相比, 树脂WJN-07对3种天然有机酸有较高的吸附容量, 这是由于新型树脂表面具有修饰的化学官能团和丰富的微孔结构所致. 选择单宁酸作为吸附质进行吸附热力学研究, 结果表明, 树脂WJN-07对单宁酸的吸附为吸热过程, 以化学吸附为主导. 溶液中重金属离子Pb²⁺作为影响树脂吸附性能的重要因素在实验中得到证实, 其作用机理也得到合理解释.     

三维有序大孔氨基功能化材料的制备及其对Cr(Ⅵ)的吸附性能

以聚苯乙烯胶晶为模板,3-氨基-丙基-三乙氧基硅烷和正硅酸乙酯为前驱物,合成了三维有序大孔(3DOM)氨基功能化SiO2-NH2材料. SEM观察表明,合成的3DOM材料具有规则整齐的大孔通孔结构,平均孔径在535～596 nm之间,孔径收缩率为4.8%～14.5%. FTIR分析表明,材料中含有氨基等有机基团. BET分析表明,材料的比表面积为10.2 m2/g. 合成的3DOM SiO2-NH2材料对Cr(Ⅵ)离子的吸附能力随着材料中氨基含量的增加而增大,最大吸附量为4.31 mmol/g.     

可溶性有机质对污染土壤中铊迁移行为的影响

目的 为了查明可溶性有机质（DOM）对土壤中污染元素铊赋存形态的影响,方法 采用形态分级提取方法,将土壤中的铊重金属分成酸可交换态、铁锰氧化物结合态、有机质结合态和残留态4组分,并采用Elan 6100型ICP-MS质谱仪测定各组分中铊的质量浓度.结果 DOM可降低酸可交换态的Tl,增加铁锰氧化物结合态和有机质结合态Tl的百分含量,但对残留态Tl的百分含量没有明显影响.因此,DOM可降低铊在土壤中的活动性,从而改变了铊在土壤中的迁移行为.结论 可溶性有机质（DOM）自身的络合（螯合）能力及其吸附特性是改变重金属铊形态分布的主要因素.     

羧甲基壳聚糖吸附废水中锌离子工艺的优化

研究羧甲基壳聚糖吸附废水中锌离子,通过考察羧甲基壳聚糖质量浓度、处理温度和处理时间等影响因素,以吸附率为响应指标,采用响应面法进行工艺优化.结果表明,吸附最佳工艺条件为羧甲基壳聚糖质量浓度5g·L-1、处理温度70℃和反应时间4.37h.在此优化条件下羧甲基壳聚糖对废水中锌离子的吸附率为92.45%,与模型预测值(92.30%)非常吻合.     

新型树脂基水合锰氧化物对水体中磺胺嘧啶的降解去除

以大孔强碱阴离子交换树脂D201为载体, 采用离子交换和氧化还原方法制备了一种新型树脂基水合锰氧化物材料HMO-201. 考察了不同pH、 离子强度和溶解性有机质(DOM)含量条件下, 该材料对水体中磺胺嘧啶(SD)的去除能力. HPLC-MS分析表明, SD的高效去除是通过HMO-201的降解而非吸附方式实现的. 实验结果表明, pH为1.0时HMO-201在120 min内对0.01 mmol/L SD的去除效率为99.9%, 反应符合表观一级动力学模型; 体系的离子强度和DOM含量变化对SD的去除效率均无显著影响. 模拟环境离子强度和DOM浓度, 连续10批次实验中SD废水的去除效率在240 min内均大于99%; HMO-201的柱动态降解装置连续处理SD溶液2000床体积, 依然未检出SD. 表明HMO-201材料具有较稳定的重复利用性, 对环境中普遍存在的磺胺类抗生素药物具有着高效的降解去除效果, 具有广泛的应用前景.     

Degradation and Removal of Suifadiazine from Waters by a Novel Polymer-supported Hydrous Manganese Dioxide(HMO)

以大孔强碱阴离子交换树脂D201为载体,采用离子交换和氧化还原方法制备了一种新型树脂基水合锰氧化物材料HMO-201.考察了不同pH、离子强度和溶解性有机质(DOM)含量条件下,该材料对水体中磺胺嘧啶(SD)的去除能力.HPLC-MS分析表明,SD的高效去除是通过HMO-201的降解而非吸附方式实现的.实验结果表明,pH为1.0时HMO-201在120 min内对0.01 mmol/L SD的去除效率为99.9％,反应符合表观一级动力学模型；体系的离子强度和DOM含量变化对SD的去除效率均无显著影响.模拟环境离子强度和DOM浓度,连续10批次实验中SD废水的去除效率在240 min内均大于99％；HMO-201的柱动态降解装置连续处理SD溶液2000床体积,依然未检出SD.表明HMO-201材料具有较稳定的重复利用性,对环境中普遍存在的磺胺类抗生素药物具有着高效的降解去除效果,具有广泛的应用前景.     

活性炭负载纳米TiO_2光催化降解甲醛废水研究

甲醛对人和温血动物的毒性很强,如果人类长期饮用被甲醛污染的水源,会引发头昏、贫血以及各种神经系统疾病.为此,研究学者对甲醛废水的处理进行了很多的试验研究.目前处理甲醛废水的主要方法有:芬顿法、光催化氧化法、湿式氧化处理等高级氧化技术,二氧化氯法,蒸汽吹脱法,氧化吸附法,SBR工艺等.     

松散接触下 Au-Ce强相互作用对 Au/CeO2/3DOM Al2O3催化剂催化柴油炭烟燃烧活性的影响

与汽油发动机相比,柴油发动机具有热效率高、CO2排放低、寿命长、续航距离远和经济性好等优点,可大大缓解能源短缺,降低 CO2排放量.因此,机动车柴油化是当前发展趋势.然而,柴油发动机在使用过程中会排放大量炭烟颗粒物,对人体危害极大.因此,控制炭烟颗粒排放成为环境催化研究的重点之一.
　　炭烟颗粒物催化燃烧反应是典型的固(炭烟颗粒)-固(催化剂)-气(O2)多相催化反应.三维有序大孔氧化物(3DOM)具有大孔径和内部贯通的孔道结构,能有效提高炭烟颗粒与催化活性中心的接触性能.同时,纳米 Au颗粒在大孔氧化物表面的负载可有效提高催化剂本征活性,但纳米 Au颗粒催化剂热稳定性较差. CeO2具有较好的储放氧性能,可与贵金属活性组分发生相互作用,从而提高贵金属纳米颗粒的分散度和稳定性.因此,本文从柴油炭烟颗粒物催化燃烧反应本质出发,设计制备了高炭烟燃烧催化活性的3DOM氧化物担载 Au基催化剂,研究了 Au与 CeO2强相互作用对炭烟燃烧活性的影响.
　　采用胶体晶体模板法制备3DOM Al2O3载体,由微孔膜氨沉淀法制备 CeO2/3DOM Al2O3催化剂,以还原-沉积法制备 Au/3DOM Al2O3和 Au/CeO2/3DOM Al2O3催化剂,并利用扫描电镜、N2物理吸附-脱附、X射线衍射、透射电镜、紫外漫反射光谱、H2程序升温还原和 X射线光电子能谱等手段对催化剂形貌、比表面积、物理化学性质和氧化还原性进行了表征.结果表明,在 CeO2/3DOM Al2O3中, Al3+可进入到氧化铈晶格内,形成 Al-Ce-O固溶体,产生氧空位,这有利于氧物种转移.此外, Au/CeO2/3DOM Al2O3催化剂中 Au和 CeO2之间的强相互作用能增加 Au纳米颗粒表面活性氧物种数量,从而促进柴油炭烟燃烧反应.纳米颗粒 Au的担载使得催化柴油炭烟燃烧的起燃温度明显降低,其中 Au/CeO2/3DOM Al2O3催化剂表现出最高的催化活性,T10,T50和T90分别为273,364和412oC.     

蛭石对Cd(Ⅱ)的动态吸附研究

新型价廉的吸附材料的开发应用是目前废水处理的研究重点 [1,2 ] ,粘土矿物由于具有储量丰富、价格低廉、吸附容量大、对环境无毒无害等优点 ,在废水处理方面有着广阔的应用前景 [3,4 ]。目前 ,有关粘土矿物处理重金属废水的研究工作多采用静态的搅拌吸附方法。该法用于实验室的试验研究是行之有效的 ,但难以在工业上推广应用。本文报道了利用蛭石作为吸附剂装填吸附柱用于连续处理含镉溶液的动态吸附实验方法 ,并探讨了蛭石的改性处理方法和再生情况 ,为蛭石用于工业废水的处理提供了一定的理论和实验基础。1　材料与方法1 .1　实验材料1 .…     

Three-dimensionally ordered macroporous metal oxide–silica composite for removal of mercaptan

A series of 3DOM and non-3DOM metal oxide–silica composites were prepared and tested dynamically in a packed-bed reactor at room temperature to remove ethanethiol from a gas stream containing ethyl mercaptan in moist N_2.The obtained sorbents were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption techniques. The experimental results showed that the adsorption ability of different kinds of metal oxide–silica composites with 3DOM structure decreased in the sequence: 3D-CuO/SiO₂ > 3D-NiO/SiO₂ > 3D-Co₃O₄/SiO₂ > 3D-ZnO/SiO₂. The best ratio of CuO to SiO₂ of 3DOM copper–silicon oxide sorbents for ethanethiol removal was found to be 1:2. The 3DOM structure could improve the removal activity of sorbents remarkably because of the high porosity with ordered interconnected macropores as well as the large surface area and high dispersion of CuO. It was also found that a moist atmosphere greatly benefited the adsorption of ethanethiol at ambient condition.     

Effect of dissolved organic matter from Guangzhou landfill leachate on sorption of phenanthrene by montmorillonite

To investigate the effect of dissolved organic matter (DOM) on the adsorption of phenanthrene (PHE) by montmorillonite (MMT), organic clay complex was prepared by associating montmorillonite with DOM extracted from landfill leachate. Both the raw MMT, DOM, and MMT complex (DOM-MMT) were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), X-ray photo-emission spectroscopy (XPS), and scanning electron microscope (SEM). Batch adsorption studies were carried out on the adsorption of PHE as a function of contact time, temperature, and adsorbent dose. The sorption of PHE on complex was rapid, and the kinetics could be described well by the Pseudo-first-order model (R(2)>0.99), with an equilibrium time of 120 min. The adsorption isotherm was in good agreement with the Henry equation and Freundlich equation. Also, thermodynamic studies showed that the adsorption process was exothermic and spontaneous in nature. Compared with MMT, the adsorption capacity of DOM-MMT complex for PHE was greatly enhanced. The effects of DOM on PHE sorption by MMT may be attributed to the changes in the surface structure, the specific surface area, the hydrophobic property, and the average pore size of MMT. A series of atomistic simulations were performed to capture the structural and functional qualities observed experimentally.     

Polydisperse adsorbability composition of several natural and synthetic organic matrices

The polydisperse composition of nine dissolved organic materials (DOMs) from two river water sources, one ground water source, two biologically treated wastewater sources, and two commercial sources was analyzed based on their adsorbabilities by activated carbon. For each DOM, batch adsorption isotherms measured for both TOC and UV260 were analyzed using an overall isotherm model derived from the IAST-Freundlich expression. By accounting for the heterogeneity of each DOM with a log-normal distribution of the Freundlich parameter (K), its adsorption behavior was characterized with only four parameters (including three fitting ones). The average adsorptive strength (KM) and heterogeneity (sigma) determined for all DOMs, which were defined by the mean value and the standard deviation of the log-normal distribution of the Freundlich K, changed over the ranges 2.5-62.2 and 0.22-0.97 (mg/g)/(mg/l)(1/n), respectively, when the TOC index was used. Among all DOMs studied, a river water DOM at the upper stream was found least heterogeneous: the Freundlich K of its organic constituents varied in the range 10.8-190 (mg/g)/(mg/l)(1/n), as compared to a commercial humic acid that exhibited the broadest Freundlich K distribution of 0.01-1494.3 (mg/g)/(mg/l)(1/n). KM and sigma, along with other two parameters (the Freundlich exponent 1/n and the nonadsorbable organic fraction parameter Cnon/CT0), changed with both indices of TOC and UV260 in a regular manner, indicating that UV-absorbing organic molecules possessed adsorbabilities different from non-UV-absorbing ones. Also based on HPSEC chromatograms measured for solutions before adsorption, the molecular weight composition of all DOMs was also assessed and the molecular size impacts on adsorption characteristics of DOMs were briefly discussed.     

Comparison between DAX-8 and C-18 solid phase extraction of rainwater dissolved organic matter

Rainwater is a very low concentrated matrix and, for dissolved organic matter (DOM) characterization, an efficient extraction procedure is essential. Isolation procedures based on the adsorption onto XAD-8 and C-18 sorbents have been used in the literature for rainwater DOM isolation, but a comparison between these procedures is lacking. In this work, UV-visible and molecular fluorescence spectroscopies highlighted differences between rainwater DOM isolated by DAX-8 (replacement for XAD-8) and by C-18. It was possible to recover higher rainwater DOM percentage by the C-18 based procedure than by the DAX-8 one. Rainwater protein-like compounds were better concentrated by the C-18 procedure than by the DAX-8 one, while humic-like compounds were similarly concentrated by both procedures. Furthermore, rainwater DOM extracted by the C-18 procedure was more representative of the global matrix, while DAX-8 preferentially extracted humic-like compounds.     

三维有序大孔杂化SiO2的制备、表征及应用

本研究将有机-无机杂化功能材料与有序大孔材料独特的有序开孔结构相结合,在制备的三维有序大孔二氧化硅（3DOM SiO₂）孔壁上可控接枝带有功能基团的聚合物链段,制备3DOM杂化材料。采用表面引发原子转移自由基（SI-ATRP）接枝技术在3DOM SiO₂孔壁上可控接枝聚甲基丙烯酸缩水甘油酯（PGMA）链段,讨论了接枝条件对接枝量及接枝链段分子量的影响,并利用FT-IR、SEM、TGA、GPC等对接枝过程进行了表征。PGMA接枝链段上环氧基团可进一步与亲核试剂（二乙醇胺,浓硫酸和二乙烯三胺）发生开环反应,得到一系列带有不同官能团的具有较高接枝密度的功能杂化多孔材料,同时,利用该种材料对水中的水杨酸进行了吸附实验,吸附结果表明经二乙烯三胺开环后得到的功能化多孔材料对水杨酸具有很高的吸附量。本研究对于发展新型杂化多孔材料提供了新的方法。     

三维有序大孔杂化SiO2的制备、表征及应用

将有机-无机杂化功能材料与有序大孔材料独特的有序开孔结构相结合,在制备的三维有序大孔二氧化硅(3DOM Si O2)孔壁上可控接枝带有功能基团的聚合物链段,制备3DOM杂化材料。采用表面引发原子转移自由基(SI-ATRP)接枝技术在3DOM Si O2孔壁上可控接枝聚甲基丙烯酸缩水甘油酯(PGMA)链段,讨论了接枝条件对接枝量及接枝链段分子量的影响,并利用FTIR、SEM、TGA、GPC等对接枝过程进行了表征。PGMA接枝链段上环氧基团可进一步与亲核试剂(二乙醇胺,浓硫酸和二乙烯三胺)发生开环反应,得到一系列带有不同官能团的具有较高接枝密度的功能杂化多孔材料,同时,利用该种材料对水中的水杨酸进行了吸附实验,吸附结果表明经二乙烯三胺开环后得到的功能化多孔材料对水杨酸具有很高的吸附量。     

Investigating sorption-driven dissolved organic matter fractionation by multidimensional fluorescence spectroscopy and PARAFAC

Soil organic matter is involved in many ecosystem processes, such as nutrient supply, metal solubilization, and carbon sequestration. This study examined the ability of multidimensional fluorescence spectroscopy and parallel factor analysis (PARAFAC) to provide detailed chemical information on the preferential sorption of higher-molecular-weight components of natural organic matter onto mineral surfaces. Dissolved organic matter (DOM) from soil organic horizons and tree leaf tissues was obtained using water extracts. The suite of fluorescence spectra was modeled with PARAFAC and it was revealed that the DOM extracts contained five fluorescing components: tryptophan-like (peak location at excitation <255 nm:emission 342 nm), tyrosine-like (276 nm:312 nm), and three humic-substance-like components (<255 nm:456 nm, 309 nm:426 nm, <255 nm:401 nm). In general, adsorption onto goethite and gibbsite increased with increasing DOM molecular weight and humification. PARAFAC analysis of the pre- and post-sorption DOM indicated that the ordering of sorption extent was humic-like components (average 91% sorption) > tryptophan-like components (52% sorption) > tyrosine-like components (29% sorption). This differential sorption of the modeled DOM components in both the soil organic horizon and leaf tissue extracts led to the fractionation of DOM. The results of this study demonstrate that multidimensional fluorescence spectroscopy combined with PARAFAC can quantitatively describe the chemical fractionation process due to the interaction of DOM with mineral surfaces.     

三维有序大孔锂离子筛的制备及其交换性能研究

由110 nm聚苯乙烯(PS)微球组装晶体胶体模板,并用此模板合成三维有序大孔(3-dimensionally ordered macroporous,3DOM)锂离子筛前驱体Li4Ti5O12,用1.0 mol.L-1的盐酸改型制得锂离子筛H4Ti5O12(LiTi-H)。用XRD、SEM、饱和交换容量、pH滴定曲线等表征了材料的形貌、结构和离子交换性能。同时测定了25℃时LiTi-H在0.05 mol.L-1Li+体系吸附锂的动力学数据,并采用吸附动力学Bangham方程和Elovich方程关联离子筛LiTi-H对Li+的离子交换动力学数据。结果表明:PS胶体晶体模板和3DOMLi4Ti5O12锂离子筛前驱体均排列规则有序,大孔直径约90 nm,Li4Ti5O12为尖晶石结构;3DOM Li4Ti5O12酸稳定性好,锂离子筛LiTi-H对Li+具有较高的选择性,对Li+的饱和交换容量达56.70 mg(Li+).g-1;动力学模型用Elovich模型关联较好,离子筛对Li+的离子交换动力学方程是Q=-26.510 4+11.977 4lnt(25℃)。     

Equilibrium ion exchange method: methodology at low ionic strength and copper(II) complexation by dissolved organic matter in a leaf litter extract

The equilibrium ion exchange method (EIM) is a powerful tool for the investigation of metal cation complexation by dissolved organic matter (DOM) in natural systems. Tests with different ion exchange resins demonstrated that under low ionic strength conditions (0.01 mol/kg) and in the presence of DOM, equilibration times of at least 24 h are required for experiments with Cu(II). The classical approach to the EIM was modified by using nonlinear reference adsorption isotherms in order to expand the method to a broader range of experimental conditions. For Cu(II) at low ionic strength (0.01 mol/kg), the reference isotherms between pH 4 and 6 were identical and were mathematically modeled in terms of Langmuir adsorption parameters. The EIM using nonlinear reference isotherms was validated between pH 4 and 6 by the correct determination of the stability constants for the complexes CuOxalate and Cu(Oxalate)(2). Then the method was used to quantitatively characterize the Cu(II) complexation behavior of DOM in an aqueous chestnut leaf litter extract between pH 4 and 6. In contrast to the classical approach to the EIM, data were analyzed by using plots [Cu](bound)/[Cu](free)vs. [Cu](bound). This allowed the determination of both, conditional stability constants and metal binding capacities for two different binding site classes. The logarithmic values of the stability constants were about 8 for the strong binding sites and 5.5-6 for the weak binding sites. The total Cu(II) binding capacity increased from 0.22 mol/(kg C) at pH 4 to 2.85 mol/(kg C) at pH 6.     

Promotion of oxidative desulfurization performance of model fuel by 3DOM Ce-doped HPW/TiO2 material

Phosphotungstic acid (HPW) supported on Ce-doped three-dimensional ordered macroporous (3DOM) TiO₂ catalysts are studied in catalytic oxidation desulfurization (ODS) of model oil. The structural and textural of as-synthesized catalysts are characterized by N₂ adsorption, XRD, Raman spectroscopy, SEM-EDS, TEM, FT-IR, XPS, UV–Vis and ICP. These results upheld the existence of periodically arranged macroporous structure of catalyst, with Keggin-type of HPW dispersed homogeneously on TiO₂ matrix. Among these 3DOM Ce-doped HPW/TiO₂ materials, catalyst with 15 wt.% cerium dosage exhibits best ODS performance, which oxidized 99.8% of dibenzothiophene (DBT) into corresponding sulfone within 40 min. The excellent ODS performance of 3DOM Ce-doped HPW/TiO₂ catalyst is related to the common influence of more oxygen vacancies produced by electron transformation between Ce³⁺ and Ce⁴⁺. The chemisorbed oxygen on the surface catalyst will facilitate the selective oxidation of sulfides to sulfones. Moreover, the 3DOM structure of catalyst will further promote the mass transfer of reactants and products on the pore channel. The as-prepared catalyst shows excellent reusability in the ODS system, no obviously decrease in catalytic activity even after 6 runs.