掺铁TiO2纳米管阵列模拟太阳光光电催化降解双酚A的研究

双酚A(BPA)是一种典型的内分泌干扰物,其处理技术的开发对环境治理和人类健康都非常重要.以氙灯为模拟太阳光光源,掺铁Ti O2纳米管阵列(Fe/TNA)为光阳极,对BPA进行光电催化降解实验研究.通过场发射扫描电镜、X射线衍射以及紫外-可见漫反射表征Fe/TNA的形貌、物相和光吸收性能.结果表明,与纯Ti O2纳米管阵列(TNA)相比,Fe/TNA光吸收边界发生红移,在可见光区的吸收增强.考察Fe掺杂量、电流密度、不同阴极材料下曝气速率等因素对光电催化降解BPA的影响.结果表明,降解反应符合准一级反应动力学方程,在以0.9 mol·L-1Fe(NO3)3浸渍改性的Fe/TNA为光阳极、钛箔为阴极,电流密度为1.15 m A·cm-2的条件下反应4 h,10 mg·L-1BPA降解率可达72.3%,反应速率常数为5.32×10-3min-1,分别是以TNA为光阳极时的1.24倍和1.52倍;曝气可提升光电催化降解BPA的效果,以钛箔为阴极,曝气速率为1.0 L·min-1和以碳布为阴极,曝气速率为0.2 L·min-1条件下降解4 h,BPA的降解率分别可达82.7%和94.1%,反应速率常数分别为7.20×10-3min-1和11.6×10-3min-1.     

Fe(Ⅲ)-oxalic acid对水体中邻苯二甲酸二甲酯的光降解

Fe(III)-oxalic acid配合物是天然水体中广泛存在的光活性物质。系统考查了pH值、oxalic acid及投加方式等因素对DMP降解的影响。导致DMP的降解活性物种·OH来自Fe(III)-oxalic acid络合物、Fe(III)的光致激发以及由此引发的Fenton反应过程。当Fe(III)和oxalic acid的浓度比为1∶10时,pH=3.0为最佳酸度;在此酸度下,Fe(III)和oxalic acid的浓度比为1∶9~1∶20时达到最高降解效率。说明了pH和Fe(III)物种存在形式对·OH产生机制的影响。最后对比讨论了体系中oxalic acid对Fe(III)/Fe(II)变化规律的影响。     

Fe/Cu催化还原降解饮用水中溴氯乙腈的性能研究

为了降低饮用水在氯消毒过程中产生的消毒副产物(DBPs)溴氯乙腈(BCAN)对人体带来的健康危害,采用Fe/Cu催化还原的方法降解饮用水中低浓度的BCAN,考察了BCAN的降解效果和其影响因素,探讨了其降解机制及动力学规律.结果表明,Fe/Cu具有更强的还原降解BCAN的能力,与零价铁相比,Fe/Cu(质量比为10∶1)的降解效率是其1.5倍.随着Fe/Cu投加量的增加,BCAN的去除率有明显的提高,对于初始浓度为20μg·L-1的BCAN溶液,当Fe/Cu(质量比为10∶1)投加量由5g·L-1增加到10 g·L-1,反应150 min后,去除率由51.1%增加到89.5%.BCAN降解效率随着温度的升高逐渐提高,BCAN初始浓度的变化对Fe/Cu去除BCAN的去除效果影响不大,Fe/Cu降解BCAN符合一级反应动力学规律.     

有机酸-铁改性活性炭去除饮用水中的砷

利用有机酸(柠檬酸和EDTA)螯合铁加载来改性活性炭,采用动态活性炭小柱进行吸附穿透实验来检测改性后活性炭对砷的吸附能力.研究表明,加载到活性炭上的铁的量随着有机酸和铁浓度增加而增加,在EDTA和铁的浓度分别为0.1mol/L时,活性炭上的铁含量从未加载时的0.24%升至6.18%.改性后的活性炭对砷吸附能力有显著增加,EDTA-Fe改性后的活性炭对As(V)和As(III)穿透时,运行的床体积达到未改性活性炭的10倍.一般情况下,低pH对As(V)的吸附有利.在水体常见pH值范围内(pH 6~9),As(III)的吸附受到影响较小.活性炭上用有机酸螯合法加载的铁大部分以不定形的形式存在,且晶体化效果不明显.     

铁-草酸盐配合物光分解降解对硝基苯酚的研究

研究了铁(Ⅲ)-草酸盐配合物在可见光及太阳光照射下,对对硝基苯酚的光解降解作用。结果表明,在pH=4.0、Fe(Ⅲ)/H_2C_2O_4=0.080mmol/L/0.96mmol/L(分4次加入)、光照4h的条件下,20mg/L对硝基苯酚的降解率为89％。溶液pH值,铁与草酸盐浓度比和对硝基苯酚浓度均对降解效果产生影响。     

TiO2及负载Fe(Ⅲ)可见光催化H2O2降解扑草净的协同效应

以TiO2P25(TIO-P25)及Fe(NO3)3为前驱物制备TiO2负载Fe3+多相催化剂Fe/TIO-P25,研究Fe/TIO-P25可见光催化H2O2降解扑草净的协同效应.XRD、XPS、EDS及SEM结果表明,Fe元素以Fe2O3形式高度分散于TiO2表面,负载量约1.5%(wt%),未对TIO-P25的粒径及形貌产生明显影响,Fe/TIO-P25的粒径约20~40nm;光催化结果表明,Fe/TIO-P25能可见光催化H2O2降解扑草净,反应30min降解率达100%,远大于TIO-P25的催化活性,负载Fe与TIO-P25之间存在明显的协同效应;通过对反应体系的荧光光谱分析显示,扑草净的降解涉及较单纯羟基自由基(·OH)过程更为复杂的反应机理.     

铁-草酸配合物光分解降解活性染料的研究

研究了铁（Ⅲ)-草酸配合物在可见光及太阳光照射下，对活性染料的光解降解作用。结果表明，在pH=4．0、Fe(Ⅲ)／H2E2O4=0．060mmol／L／2．88mmol／L(草酸分2次加入)、光照3h的条件下，20mg／L的活性红的降解率为97．5％。溶液pH值、铁与草酸浓度比和活性染料浓度均对降解效果产生影响。     

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.     

纳米与微米级零价铁降解2,4,6-三氯酚动力学比较

研究了在反应表面积相近条件下,纳米与微米级零价铁(Fe0)降解水相中2,4,6-三氯酚(TCP)的动力学差异.结果表明,纳米与微米级Fe0降解TCP过程均符合准一级反应动力学,表观反应速率常数Kobs分别为0.0165h-1和0.0046h-1,其比值(3.6)接近纳米与微米级Fe0对TCP的初始吸附量比值(2.9).造成2种Fe0降解与吸附效率差异的主要原因在于颗粒表面点位单元活性不同.Fe0对TCP的作用可分为2个阶段:前一阶段非反应点位主导的吸附作用高于反应点位主导的降解作用,后一阶段刚好相反.反应过程中,纳米与微米级Fe0反应组体系pH值从初始的5.7分别升至10.5和8.2,体系pH值处于酸性范围时可提高TCP降解速率.纳米Fe0在反应过程中表面氧化不断增加,其中大部分铁氧化物沉积在颗粒表面,少量以离子态存在于水相中.     

Fe3O4硅烷化改性聚合物的制备及可见光光催化性能研究

利用水热法制备了Fe3O4纳米粒子(Fe3O4NPs),并对其进行改性制备了改性聚合物Fe3O4MMPs.同时,利用X射线衍射(XRD)、扫描电镜(SEM)和紫外可见漫反射(DRS)等手段对所制备的材料进行表征.通过比表面积(BET)测定发现,Fe3O4MMPs的比表面积较Fe3O4NPs增大约9倍.在可见光照射下(λ420 nm),以H2O2为氧化剂,比较研究了以Fe3O4NPs和Fe3O4MMPs为光催化剂降解罗丹明B(Rhodamine,RhB)的催化特性,并探讨了Fe3O4改性对催化活性的影响.结果表明,改性聚合物Fe3O4MMPs的稳定性增加,对底物RhB的降解活性提高,120 min时对RhB的脱色率在98%以上;此外,Fe3O4MMPs对水杨酸(Salicylic Acid,SA)也具有很好的降解效果.利用电子自旋共振技术(ESR)测定氧化物种的结果表明,降解过程涉及羟基自由基(·OH)和超氧自由基(·O-2)氧化机理.     

Heterogeneous Fenton degradation of azo dyes catalyzed by modified polyacrylonitrile fiber Fe complexes：QSPR (quantitative structure peorperty relationship) study

The amidoximated polyacrylonitrile (PAN) fiber Fe complexes were prepared and used as the heterogeneous Fenton catalysts for the degradation of 28 anionic water soluble azo dyes in water under visible irradiation. The multiple linear regression (MLR) method was employed to develop the quantitative structure property relationship (QSPR) model equations for the decoloration and mineralization of azo dyes. Moreover, the predictive ability of the QSPR model equations was assessed using Leave-one-out (LOO) and cross-validation (CV) methods. Additionally, the effect of Fe content of catalyst and the sodium chloride in water on QSPR model equations were also investigated. The results indicated that the heterogeneous photo-Fenton degradation of the azo dyes with different structures was conducted in the presence of the amidoximated PAN fiber Fe complex. The QSPR model equations for the dye decoloration and mineralization were successfully developed using MLR technique. MW/S (molecular weight divided by the number of sulphonate groups) and NN=N (the number of azo linkage) are considered as the most important determining factor for the dye degradation and mineralization, and there is a significant negative correlation betweenMW/S or NN=N and degradation percentage or total organic carbon (TOC) removal. Moreover, LOO and CV analysis suggested that the obtained QSPR model equations have the better prediction ability. The variation in Fe content of catalyst and the addition of sodium chloride did not alter the nature of the QSPR model equations.     

Mineralogical characteristics and photocatalytic properties of natural sphalerite from China

Different natural sphalerites have a range of photocatalytic properties that can potentially be exploited for environmental remediation purposes. To develop value in the exploitation of sphalerite, samples were collected from 19 ore deposits in China and characterized for their mineralogical and photocatalytic properties. X-ray diffraction (XRD) and electron probe micro analysis (EPMA) measurements indicated that all the natural sphalerites from various localities crystallized in cubic phases with various chemical compositions. The substitution of Fe for Zn ranged from 0.235% to 14.826% by weight, Mn from 0.004% to 4.868%, Cu from 0.009% to 5.529% and Cd from 0.133% to 1.576%. As Fe became more abundant, the color of natural sphalerite darkened, becoming almost black; and higher Fe content was associated with stronger visible light absorption. Photoluminescence spectra showed emission mainly related to S-vacancies and progressively decreasing fluorescence intensity with increasing Fe content. Tests of the photocatalytic degradation of methyl orange indicated that the sample with the highest Cd content but moderate Fe content had the highest photocatalytic activity. Specifically, the degradation of Methyl Orange (30 mg/L) attained 82.11% efficiency under visible light irradiation for 4 hr of natural sphalerite with 4.262% Fe and 1.576% Cd. Overall, the Fe content in sphalerite was found to contribute to the visible light absorption ability and the recombination rate of photo-generated electrons and holes, while substitution by Cd was observed to have a greater effect on the photocatalytic properties. These findings provide a scientific basis for the profitable utilization of base metal resources like sphalerite.     

Fe(Ⅲ)/苹果酸/H_2O_2体系对有机物的光降解特性研究

系统研究了可见光照射下染料橙黄Ⅱ在Fe(Ⅲ)/苹果酸/H2O2体系中的脱色情况,考查了光源、pH值、Fe(Ⅲ)、苹果酸、H2O2及染料初始浓度等因素对橙黄Ⅱ脱色效率的影响.结果表明,Fe(Ⅲ)/苹果酸/H2O2体系在可见光照射下能有效实现橙黄Ⅱ的脱色,在pH为5.0的条件下仍然具有较强的降解有机物的能力.该体系对橙黄Ⅱ的脱色率高于Fe(Ⅲ)/H2O2体系或Fe(Ⅲ)/苹果酸体系,光反应符合表观一级反应动力学规律.随着光强的增加,橙黄Ⅱ的脱色率增大.太阳光是该体系的有效光源,本体系具有利用太阳光的潜力.     

银-铋修饰TiO2纳米材料可见光催化剂制备及降解甲醛性能分析

预防和控制低浓度气态甲醛(HCHO)仍是室内环境污染所面临的巨大挑战之一,设计合成吸附能力强、催化氧化性能高、稳定性好的催化剂具有重要的实际应用价值。采用水热法和溶胶-凝胶法制备了一系列Ag-Bi共掺杂的纳米结构Ag/Bi-TiO₂光催化剂,用于在可见光、无动力条件下催化降解室内低浓度气态甲醛。并采用XRD、SEM、BET、H₂-TPR、UV-vis、XPS等技术对所制催化剂进行表征分析,考察了制备方法、Ag-Bi掺入量、煅烧温度等条件对催化剂可见光催化氧化性能的影响。结果发现：水热法制得的Ag/Bi-TiO₂-H催化剂降解甲醛效果最佳,其48h降解率可达到94.1%,可将浓度为1.076 mg/m³的甲醛降低至0.093 mg/m³,显著提升了TiO₂的催化氧化性能,其Ag₂O/Ag、Bi³⁺和TiO₂间的协同耦合作用改善了催化剂的微观结构,增强其对可见光的吸收,促进了光生电子的形成及转移...     

钴掺杂铁酸铋活化过硫酸盐降解水中四溴双酚A的研究

采用溶胶凝胶法制备了钴掺杂的铁酸铋(xCo-BFO),以此作为多相催化剂,活化过硫酸盐(PMS),产生硫酸根自由基,在水相降解溴代阻燃剂四溴双酚A(TBBPA).研究了钴掺杂量、催化剂用量、PMS初始浓度对降解反应过程的影响.结果表明,在xCo-BFO中Co掺杂量(Co/Fe摩尔比)为0.1,用量为0.5 g.L-1,PMS浓度为2.5 mmol.L-1时,60 min内对40 mg.L-1的TBBPA的去除率可达95%以上.所得催化剂在反应中稳定,反应60 min后Co溶出量仅占总Co的0.27%,经4次重复使用仍具有较高催化活性;具有磁性,回收方便,在污水处理领域具有良好的应用前景.     

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.     

Activated carbon supported TiO2-photocatalysis doped with Fe ions for continuous treatment of dye wastewater in a dynamic reactor

Fe-doped TiO2 coated on activated carbon (Fe-TiO2/AC, FTA) composites were prepared by an improved sol-gel method and characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray di ractometry, inductively coupled plasma mass spectrometry and BET surface area analysis. Obtained FTA composites were applied to the continuous treatment of dye wastewater in a dynamic reactor. The e ects of Fe ion content, catalyst content, UV-lamp power and flowrate of the continuous treatment of dye wastewater on degradation e ciency were analyzed to determine the optimum operating conditions of dye wastewater degradation. Continuous photocatalytic experiments provided interesting results that FTA had a high chemical oxygen demand (COD) removal rate compared with TiO2, Fe doped TiO2 (FT) and TiO2 coated on activated carbon (TA). In particular, when using the FTA catalyst with a Fe ion content of 0.33%, the kinetic content (k = 0.0376) of COD removal was more than the sum of both TA (0.0205) and 0.33% FT (0.0166). FTA showed a high photoactivity because of a synergistic e ect between Fe ions and AC on TiO2, which is higher than the individual e ects of AC or Fe ions on TiO2. Additionally, for the photocatalytic degradation of dye wastewater, the optimum Fe ion content, catalyst content, UV-lamp power and flowrate were 0.33%, 6 g/L, 60 W (two lamps) and 300 mL/hr, respectively. An investigation of catalyst reuse revealed that the 0.33% FTA showed almost no deactivation in photocatalytic degradation of naturally treated wastewater.     

金属泡沫镍负载纳米TiO2光催化降解甲醛和VOCs

采用溶胶-凝胶法制备了3种掺杂金属离子的纳米TiO₂光催化剂,并将其负载于泡沫镍板上,以室内空气典型污染物甲醛和VOCs为模型反应物,研究了对甲醛和VOCs气体的光催化作用并讨论了La³⁺的最佳掺杂比例以及环境因素对光催化效率的影响.结果表明:该TiO₂催化剂具有良好的锐钛矿型结构;负载掺La 1.5%TiO₂的泡沫镍板90min对甲醛和VOCs的降解率分别为94%和87%,远高于未掺:83%和72%,掺Fe     

金属-有机骨架MIL-88A(Fe)及其复合物的合成与高级氧化降解水体有机污染物的研究进展

本文综述了MIL-88A(Fe)及其复合物的合成方法、形貌调控及其作为异相催化剂实现光芬顿、活化PS(persulfate, 过硫酸盐)和催化臭氧氧化等高级氧化过程去除水体有机污染物的研究进展. 系统介绍了利用水/溶剂热法、超声法、微波法、室温搅拌法、机械化学法、重结晶法和光化学还原法制备MIL-88A(Fe)及其复合物的反应条件和产物形貌特征. MIL-88A(Fe)具有环境友好、能被可见光激发及稳定性好等特点,其表面Fe(Ⅲ)不饱和位点丰富且均匀,利于作为催化剂用于高级氧化. MIL-88A(Fe)受光激发产生的光生电子-空穴容易复合,导致其光催化性能较差. 但在类芬顿、激发PS和催化臭氧氧化等体系中,添加的氧化剂作为电子受体快速消耗电子,有效克服了光生电子-空穴复合问题. 此外,将MIL-88A(Fe)与其他功能材料复合可进一步改善其光生电子-空穴分离效率、提高光吸收能力及水稳定性. 总之,MIL-88A(Fe)及其复合物在光芬顿、活化PS和催化臭氧氧化降解有机污染物方面具有较大的实际应用潜力.