固体超强酸SO_4~(2-)/TiO_2-Fe_2O_3光催化降解含酚废水

采用固体超强酸SO42-/TiO2-Fe2O3为光催化剂,苯酚的光催化降解为模型反应,考察了pH值、苯酚初始浓度、催化剂投加量、光照距离、光照时间、助催化剂H2O2对光催化降解过程的影响。结果表明,苯酚初始浓度为50mg/L,催化剂投加量5g/L,光照距离11cm,光照时间为150min,降解率达61.29%,添加助催化剂H2O2后,反应60min,苯酚降解率达到85.12%。     

Cu/MgAlO活化过硫酸氢盐降解橙黄Ⅱ

采用浸渍-煅烧法制备Cu/MgAlO,利用扫描电镜、傅里叶红外光谱仪、比表面积测定仪、X射线衍射仪对其进行表征,并用Cu/MgAlO催化过硫酸氢盐(PMS)对橙黄Ⅱ进行催化降解,探索橙黄Ⅱ浓度、Cu/MgAlO投加量、PMS投加量、溶液初始pH、温度、常见离子和水质条件的影响.结果 表明:当溶液初始pH为7,温度为25...     

基于油菜花粉模板制备Fe基复合材料及其催化特性

以油菜花粉为生物模板，采用共沉淀-焙烧法制备了Fe基复合材料活化过硫酸盐降解苯酚。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和比表面积分析仪(BET)对Fe基复合材料进行表征分析。以苯酚为目标污染物，考察了催化剂投加量、过硫酸盐投加量、初始pH和苯酚浓度对苯酚降解效果的影响。结果表明，Fe基复合材料活化过硫酸盐降解苯酚性能优良。在最佳反应条件(25℃,苯酚初始浓度为200 mg/L,催化剂投加量为3 g/L,过硫酸盐投加量为8.4 mmol/L)下，反应60 min苯酚的降解率可达91%。Fe基复合材料可通过磁性分离，易于回收，在较宽pH范围内均可活化过硫酸盐降解苯酚，重复使用三次后，苯酚的降解率仍可达81%,稳定性良好。Fe基复合材料通过Fe²⁺及花粉模板残留的C及其官能团共同活化过硫酸盐产生SO₄·^-和HO·降解苯酚。     

TiO_2/改性硅藻土对LAS废水COD_(Cr)的降解性能

采用Sol-gel法制备了纳米TiO_2/改性硅藻土复合材料,并用于处理直链烷基苯磺酸钠(LAS)废水,以COD_(Cr)为评价指标,考察了催化剂的投加量、水温、催化时间、废水初始pH值和初始浓度等因素对降解性能的影响,分析了催化降解的动力学。结果表明,初始COD_(Cr)为425.9mg/L的LAS废水,当调节废水pH=5.0,催化剂投加量为4.0g/L时,10W紫外光催化反应6h废水中COD_(Cr)降解率达到84.46%;水温升高不利于降解率的提高,废水初始浓度的降低或稀释后COD_(Cr)降解率明显提高,在酸性条件下催化效果要优于中性和碱性;添加1mL 30%H_2O_2,COD_(Cr)降解率可提高10%~15%;LAS废水降解COD_(Cr)的反应符合Langmuir-Hinshelwood动力学模型。     

多孔α-Mn2O3的制备及其催化过一硫酸盐降解亚甲基蓝溶液的性能

采用草酸盐热分解法制得由微米板堆垛而成的呈无规则颗粒状形貌的多孔α-Mn₂O₃,探索其作为催化剂活化过一硫酸盐（PMS）降解模拟染料废水亚甲基蓝（MB）溶液的性能。系统考察催化剂的煅烧温度、催化剂投加量、PMS用量和阴离子种类等工艺参数对锰氧化物催化PMS降解MB溶液的影响。结果表明：450℃煅烧温度下所获产物表现出最为优异的活化PMS的能力,α-Mn₂O₃/PMS体系对MB的降解率达75.88%,而单一PMS或α-Mn₂O₃对MB的降解率仅为22.19%和5.72%。该催化体系降解500 mL浓度为10 mg/L的MB溶液的优化实验参数为：PMS（0.1 mol/L）用量为3 mL,催化剂投加量为0.05 g,反应50 min后MB的降解率可达83.55%。反应体系中引入C₂O₄^2-或PO₄^3-后会对MB溶液的降解产生抑制作用,抑制率分别为49.11%和10.27%,但Cl^-的存在对MB降解无影响。此外,借助淬灭实验和电子顺磁共振技术（EPR）对反应体系中存在的活性物种进行鉴定,α-Mn₂O₃催化PMS可产生·OH,SO₄^-·,·O₂^-和单线态氧（¹O₂）,且¹O₂是参与直接氧化降解MB的最主要活性中间体。动力学分析表明,α-Mn₂O₃催化活化PMS对MB溶液的降解为二级反应,反应速率常数为3.53 L·mmol^-1·min^-1。     

BiOI/Fe_3O_4光催化耦合过一硫酸氢盐降解酸性橙Ⅱ研究

采用水热/共沉淀法合成新型磁性纳米可见光光催化材料BiOI/Fe_3O_4,通过X射线衍射仪和扫描电镜对材料进行表征分析。采用氙灯模拟太阳光照射,构建可见光照射下BiOI/Fe_3O_4催化剂耦合过一硫酸氢盐(PMS)催化氧化水环境中残留的水溶性偶氮染料酸性橙Ⅱ的体系。考察了催化剂投加量、PMS浓度等因素对酸性橙Ⅱ降解效果的影响,并通过自由基淬灭实验初步探讨了催化作用机理。结果表明:磁性纳米颗粒Fe_3O_4均匀地负载在花球状的BiOI上;在催化剂投加量为0.5g/L、PMS浓度为0.25mmol/L的优化条件下,浓度为20mg/L的酸性橙Ⅱ在1h内降解率可达到99.2%,并符合拟一级动力学模型;材料循环使用3次后,酸性橙Ⅱ降解率仍可达到98%以上;实验证明体系中主要的活性物种为羟基自由基(·OH)和硫酸根自由基(·SO_4~-)。     

Mn-TiO2粉体的制备及催化降解孔雀石绿废水的研究

采用溶胶-凝胶法制备了纳米Mn-TiO_2粉体,通过X射线衍射(XRD)和扫描电镜(SEM)对其结构和形貌进行表征,研究了Mn-TiO_2粉体对孔雀石绿染料废水的光催化降解性能。探讨了孔雀石绿初始浓度、Mn-TiO_2催化剂投加量、体系pH等条件对催化效果的影响。结果表明:溶胶-凝胶法合成的Mn-TiO_2粉体为锐钛矿型结构,物相纯净,当孔雀石绿初始浓度为10mg/L,Mn-TiO_2催化剂添加量为1.0g/L,pH=7.0时,紫外光照射120min后MnTiO_2粉体对孔雀石绿的降解率可达87%。     

印染废水的光催化氧化的研究

本文通过光催化作用,废水的结构发生了根本变化,由有机大分子变成小分子,最终形成无机矿化物,如CO2等。本研究以曙红C20H6O5Br4Na2染料溶液的光催化降解为模型反应,探讨了曙红溶液的初始浓度、催化剂投加量、pH值、通气量等因素对光催化脱色降解效果的影响。研究结果表明,曙红染料在pH为2．23左右时降解较为适宜,染料初始浓度对脱色率的影响符合线性递减的规律,适宜的催化剂添加量为0．07g／L,通气量为0．6L／min左右。     

ZnFe_2O_4的制备及其对亚甲基蓝的催化降解性能研究

以Zn(NO_3)_2·6H_2O和FeCl_3·6H_2O为原料,NaOH为沉淀剂,采用化学共沉淀法合成了纳米ZnFe_2O_4。经XRD、FT-IR、SEM、BET比表面测试等技术手段对样品进行了表征。以亚甲基蓝溶液为模拟污染物废水,采用多相Fendon氧化技术,考察了ZnFe_2O_4投加量、水体pH值、H2O2用量、实验温度以及催化剂的重复使用次数对亚甲基蓝催化脱色的影响。结果显示,该反应体系下,ZnFe_2O_4对酸性、近中性和碱性亚甲基蓝溶液均有着很好的催化降解效果。催化剂经4次重复使用亚甲基蓝脱色率仍可达83.1%。     

凹凸棒土负载CeO2催化氧化处理亚甲基蓝染料废水

采用均相沉淀法,以Ce(NO3)3·6H2O为原料,HMT为沉淀剂,制备了ATP/CeO2纳米复合材料.并以H2O2为氧化剂,利用该复合材料对亚甲基蓝(MB)染料模拟废水进行了催化氧化处理,分别考察了催化剂的投加量及CeO2的负载量对MB降解的影响规律.研究结果表明,负载CeO2凹凸棒土纳米复合催化剂的催化活性明显高于相同条件下制备的纯的CeO2,CeO2负载量及ATP/CeO2的投加量分别为40%和0.2g时,最大降解率可达96%,对亚甲基蓝表现出较强的催化活性.     

Scalable and facile preparation of Fe3O4/2D-MoS2 and its application in peroxymonosulfate-based advanced oxidation processes for tetracycline degradation

In this paper, a magnetic ferrosoferric oxide/two-dimensional molybdenum disulfide (Fe₃O₄/2D-MoS₂) composite material was successfully prepared by combining liquid phase exfoliation and in-situ liquid phase co-precipitation methods with scalable and facile characteristics and applied to catalyze the degradation of tetracycline (TC) during the peroxymonosulfate-based advanced oxidation processes (PMS-AOPs), which is a typical and widely used antibiotic. The morphology and crystallinity of the composites were determined by scanning electron microscopy, transmission electron microscope and X-ray diffraction, respectively. And its BET surface area was tested by N₂ adsorption and desorption curves. For the PMS-AOPs, the effects of iron loading, different systems, initial concentration of pollutants, dosage of the composites, concentration of peroxymonosulfate (PMS) and solution initial pH on the removal of TC were researched in details. The results showed that it could reach 89.0% degradation efficiency within 90 min for 50 mg/L TC with the as-prepared composites as catalyst, showing good catalytic performances. In addition, the mechanisms of the reaction were deduced by quenching experiments and X-ray photoelectron spectroscopy analysis. It was turned out that the as-synthsized material has a broad applying prospect in PMS-AOPs.     

纳米CuFe_2O_4催化硫酸铜热分解及机理研究

通过硫酸铜的热分解行为研究了纳米铁酸铜的催化机理。采用共沉淀法制备不同物质的量比的纳米CuFe2O4催化剂,并测定了不同成分和用量的催化剂对硫酸铜热分解温度及热分解表观活化能的影响。通过X射线衍射和扫描电镜对铁酸铜晶体进行表征,用差热分析(TG-DSC)法测定硫酸铜的分解热变化量以衡量催化剂活性。结果表明:Cu2+、Fe3+物质的量比为1∶1,质量分数为20%的CuFe2O4对CuSO4的催化效果最佳,该条件下CuSO4的高温分解峰与低温分解峰重合,分解峰温度向低温方向移动了29.5℃,表观分解热吸热量降低了112.1 J/g。     

可见光下磷钨酸盐光催化降解分散蓝130的研究

用磷钨酸分别与可溶性盐反应合成了三种磷钨酸盐(磷钨酸钾、磷钨酸铵和磷钨酸铯),采用XRD及TG对样品进行表征,结果表明,磷钨酸盐保持着Keggin结构的稳定性,且热稳定性能良好。考察了制备得到的磷钨酸盐在可见光照射下对分散蓝130的光催化降解性能,实验表明,磷钨酸钾的最佳活化温度为300℃,而磷钨酸铵和磷钨酸铯则无需活化即具有较好的光催化降解性能。在三种磷钨酸盐中,磷钨酸铵的光催化降解性能最好,其中,当磷钨酸铵的最佳投加浓度为6g/L、双氧水最佳浓度为0.048%时,无需活化的磷钨酸铵对阴离子染料分散蓝130的光降解率可达55%以上,回收重复使用5次后,光降解率仍可达到56.5%,催化剂可以循环使用且性能良好。     

Degradation of sodium dodecyl sulphate in water using solar driven Fenton-like advanced oxidation processes

Synthetic wastewater samples containing a model surfactant were treated using two different Fenton-like advanced oxidation processes promoted by solar radiation; the photo-Fenton reaction and Co/PMS/UV processes. Comparison between the different experimental conditions was performed by means of the overall surfactant degradation achieved and by obtaining the initial rate in the first 15 min of reaction (IR15). It was found that, for dark Fenton reaction, the maximum surfactant degradation achieved was 14% under low iron and oxidant concentration. Increasing Fenton reagents by one magnitude order, surfactant degradation achieved 63% in 60 min. The use of solar radiation improved the reaction rate by 17% under same conditions and an additional increase of 12.5% was obtained by adjusting initial pH to 2. IR15 values for dark and irradiated Fenton reactions were 0.143 and 0.154 mmol/min, respectively, for similar reaction conditions and this value increased to 0.189 mmol/min when initial pH was adjusted. The use of the Co/PMS system allow us to determine an increase in the degradation rate, for low reaction conditions (1 mM of transition metal; 4 mM oxidant) similar to those used in dark Fenton reaction. Surfactant degradation increased from 3%, for Fenton reaction, to 44.5% in the case of Co/PMS. When solar irradiation was included in the experiments, under same reaction conditions described earlier, surfactant degradation up to 64% was achieved. By increasing Co/PMS reagent concentration by almost 9 times under irradiated conditions, almost complete (>99%) surfactant degradation was reached in 5 min. Comparing IR15 values for Co/PMS and Co/PMS/UV, it allow us to observe that the use of solar radiation increased the degradation rate in one magnitude order when compared with dark experiments and further increase of reagent concentration increased reaction rate twice.     

Zn2SiO4-ZnO-生物炭复合物的制备及其可见光催化H2O2降解甲硝唑

以松木碱解液代替NaOH溶液作为锌盐沉淀剂, 采用水热法制备了Zn₂SiO₄-ZnO-生物炭三元复合材料(SOB-x-y, x代表松木粉的用量, y代表NaOH浓度), 通过不同手段对样品进行表征, 研究了光催化H₂O₂降解甲硝唑的性能。结果表明, 制备的催化剂由枣核状硅锌矿型Zn₂SiO₄介晶、多边形六方晶相ZnO和松木生物炭构成; 与纯六方晶相ZnO相比, 它具有更大的比表面积与孔容、更小的带隙能和更弱的荧光发射, 因而具有更好的光催化活性。Zn₂SiO₄-ZnO-生物炭对甲硝唑的光催化H₂O₂降解过程符合准一级动力学方程, 其催化活性随NaOH浓度的增大而提高, 随松木粉用量的增加先增加后减小, 以SOB-3-4的性能最优。SOB-3-4的速率常数(k)和降解率(η)随pH的降低而增大, 随H₂O₂浓度的升高而增大, 随催化剂用量的增加先增大后减小; 甲硝唑的降解率随其初始浓度的升高逐渐越低。当初始pH为3、催化剂用量为0.4 g/L、H₂O₂投加浓度为80 mmol/L及甲硝唑初始浓度为300 mg/L时, k为2.68×10 ^-2 min ^-1, 反应3 h后η达到99.70%。本研究结果对处理难降解制药废水提供了重要的实验依据。     

Degradation of trichloroethylene by Fenton reaction in pyrite suspension

Degradation of trichloroethylene (TCE) by Fenton reaction in pyrite suspension was investigated in a closed batch system under various experimental conditions. TCE was oxidatively degraded by OH in the pyrite Fenton system and its degradation kinetics was significantly enhanced by the catalysis of pyrite to form OH by decomposing H(2)O(2). In contrast to an ordinary classic Fenton reaction showing a second-order kinetics, the oxidative degradation of TCE by the pyrite Fenton reaction was properly fitted by a pseudo-first-order rate law. Degradation kinetics of TCE in the pyrite Fenton reaction was significantly influenced by concentrations of pyrite and H(2)O(2) and initial suspension pH. Kinetic rate constant of TCE increased proportionally (0.0030 ± 0.0001-0.1910 ± 0.0078 min(-1)) as the pyrite concentration increased 0.21-12.82 g/L. TCE removal was more than 97%, once H(2)O(2) addition exceeded 125 mM at initial pH 3. The kinetic rate constant also increased (0.0160 ± 0.005-0.0516 ± 0.0029 min(-1)) as H(2)O(2) concentration increased 21-251 mM, however its increase showed a saturation pattern. The kinetic rate constant decreased (0.0516 ± 0.0029-0.0079 ± 0.0021 min(-1)) as initial suspension pH increased 3-11. We did not observe any significant effect of TCE concentration on the degradation kinetics of TCE in the pyrite Fenton reaction as TCE concentration increased.     

Enhanced photocatalytic degradation of organic contaminants over CaFe_2O_4 under visible LED light irradiation mediated by peroxymonosulfate

A simple sol-gel approach is proposed herein to fabricate CaFe₂O₄for the degradation of various organic pollutants(rhodamine B(RhB),tetracycline hydrochloride,humic acid,and methylene orange)under LED light irradiation mediated by peroxymonosulfate(PMS).The results indicate that the calcination temperature can significantly influence the performance of CaFe₂O₄for PMS activation,and the CaFe₂O₄sample obtained at 800℃(CaFe₂O₄-800)exhibits the best efficiency in degrading RhB,which is much higher than that of Fe_2o₃-800.This can be attributed to the efficient separation of photogenerated electrons(e^-)and holes(h⁺)by PMS,which is validated by transient photocurrent response and photoluminescence measurements.Results from density functio nal theo ry calculations indicate that the valence band of CaFe₂O₄-800 exhibits a high concentration of carriers and weak localization of electrons,which are favorable for PMS activation.Radical scavenging results confirm that h⁺and O₂^·-are the dominant reactive species.Moreover,CaFe₂O₄-800 not only demonstrated a stable performance during eight cycling runs with negligible iron leaching but also exhibited excellent degradation efficiency under natural water and sunlight.Finally,the mechanism and pathway of RhB degradation by the CaFe₂O₄-800/PMS/LED system are also proposed.This work presents the enormous prospect of CaFe₂O₄as an environmentally benign photocatalyst for PMS activation.     

可磁分离回收多孔CoFe_(2)O_(4)的制备及其催化过一硫酸盐降解亚甲基蓝溶液的性能EI北大核心CSCD

采用草酸盐热解法制得Fe_(2)O_(3),Co_(3)O_(4)以及CoFe_(2)O_(4)三种过渡金属氧化物多孔材料。借助XRD,SEM,BET,VSM和XPS等测试手段对材料的晶体结构、微观形貌、比表面积、磁学性能以及表面化学状态进行分析。选择典型的阳离子型染料亚甲基蓝(MB)作为降解模型,对三种样品催化活化过一硫酸盐(PMS)降解处理模拟印染废水的性能进行评价。结果表明:三种材料均具有分级微/纳米纤维状多孔结构,CoFe_(2)O_(4)因具有最大的比表面积以及Fe,Co元素间的协同效应比Fe_(2)O_(3)和Co_(3)O_(4)表现出更为优异的催化PMS降解MB溶液的性能。通过单因素实验,确定出CoFe_(2)O_(4)/PMS体系降解500 mL浓度为10 mg·L^(-1)MB溶液的优化条件为:PMS用量3 mL(0.1 mol·L^(-1)),催化剂添加量0.07 g,反应时间50 min。在此条件下,MB的降解去除率为89.77%。考察几种阴离子对CoFe_(2)O_(4)/PMS催化氧化体系的影响,发现Cl^(-),PO_(4)^(3-),C_(2)O_(4)^(2-)的存在均对MB的降解有一定的抑制作用。活性物种猝灭实验和电子顺磁共振(EPR)鉴定结果证实,^(1)O_(2)是CoFe_(2)O_(4)/PMS催化氧化体系中产生的最主要活性物种。循环使用实验结果表明,CoFe_(2)O_(4)具有较好的稳定性,且可磁分离回收特性使其可作为活化PMS降解印染废水的候选催化材料。     

Diatomite supported nano zero valent iron with 3D network for peroxymonosulfate activation in efficient degradation of bisphenol A

Diatomite supported nano zero valent iron (nZVI) catalyst (NDA) with complex network structure was prepared via a mild reduction precipitation method in this work.The pore structure and pore distribu-tion of NDA can be regulated and controlled through adjusting the loading amount of nZVI.In general,the nano three-dimensional network formed by nZVI and diatomite channels greatly increase the specific surface area and pore volume of NDA,and further formed more active sites,which made NDA have better performance in activating PMS to degrade BPA than pure nZVI.The pseudo-first-order reaction rate con-stant of 50-NDA (50％-nZVI/diatomite) is almost 3 times higher than that of pure nZVI.Besides,the elec-tron paramagnetic resonance (EPR) and radical quenching experiments showed that the activation process was dominated by the sulfate radical (SO4·-) and hydroxyl radical (OH) produced by Fe0 oxidation.The generated electrons promote the self-decomposition of PMS to produce singlet oxygen (1O2),and then the valence state of iron changes to produce free radicals.In addition,the possible degradation pathway of BPA was inferred from the intermediate products identified by liquid chromatograph-mass spectrom-eter (LC-MS).This study provides a novel strategy for the design and preparation of three-dimensional composite catalysts derived from natural mineral.