Synthesis, properties and application research of atrazine Fe3O4@SiO2 magnetic molecularly imprinted polymer

Introduction

Magnetic Fe₃O₄ nanoparticles were prepared by coprecipitation and then were coated with SiO₂ on the surface.

Materials and methods

Fe₃O₄@SiO₂ composite microspheres were modified by KH570. Using molecular imprinting technology, atrazine magnetic molecularly imprinted polymer was prepared by using atrazine as template molecule, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linkers. The morphology, composition and magnetic properties of magnetic nanoparticles were characterized. The recognition selectivity of polymer was studied for template molecule and simulation by UV spectrophotometry. The adsorption properties and selectivity ability were analyzed by Scatchard analysis.

Results

Scatchard linear regression analysis indicated that there are two binding sites of the target molecules. The magnetic molecularly imprinted polymer has been applied to the analysis of atrazine in real samples.

Conclusion

The results show that: the recovery rates and the relative standard deviation were 94.0??98.7% and 2.1??4.0% in corn, the recovery rates and the relative standard deviation were 88.7??93.5% and 2.8??7.2% in water.     

磁性硅球对SBR活性污泥脱氮除磷性能的影响

为研究磁性硅球(Fe_3O_4@SiO_2)对序批式活性污泥反应器(SBR)污水处理系统中脱氮除磷性能的影响,建立了3个相同的SBR(编号依次为1号、2号和3号),在2号和3号反应器中分别投加0.5 g·L~(-1)的纳米Fe_3O_4和Fe_3O_4@SiO_2,1号反应器为不投加任何磁性材料的对照组。结果表明:Fe_3O_4@SiO_2对SBR中的污泥性能有显著的影响,3号反应器在运行20 d时,反应器内活性污泥结构完整,饱满密实,污泥粒径多集中分布在0.3～1.0 mm,颗粒化现象明显,而1号反应器无明显颗粒污泥,2号反应器虽能看到有少部分的颗粒污泥,但分布不均匀;Fe_3O_4@SiO_2对污泥胞外蛋白(PN)、胞外多糖(PS)的含量有促进作用,并能改善污泥的沉降性能,第70天时,3号反应器内PN和PS含量分别为318.89 mg·g~(-1)和28.51 mg·g~(-1),污泥沉降指数(SVI)为35.22 mL·g~(-1),性能优于1号和2号反应器;在除污方面,2号和3号反应器对污水总氮(TN)和总磷(TP)去除率比1号反应器分别提升了10.80%、15.20%和9.40%、12.40%,3号反应器表现出最高的脱氮除磷性能;此外,在典型周期内,3号反应器对氮素及磷的去除速率明显高于1号反应器,在240 min内,1号和3号反应器对TN去除速率分别为4.56 mg·(L·h)~(-1)和5.84 mg·(L·h)~(-1),对TP去除速率分别为0.44 mg·(L·h)~(-1)和0.51 mg·(L·h)~(-1)。由此可见,经SiO2包覆后所制备的Fe_3O_4@SiO_2,提高了其在水体的分散性,增大了与污泥的接触程度,极大促进了污泥经磁聚、吸附作用富集到其表面形成颗粒污泥,并利于脱氮除磷等微生物截留和附着,提高活性污泥反应系统的脱氮除磷效果和去除速率。以上结果可为进一步探索磁性纳米材料对SBR活性污泥脱氮除磷性能影响提供参考。     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Fe3O4纳米磁性微粒对全氟辛烷磺酸盐的吸附

采用共沉淀法合成Fe3O4纳米磁性颗粒,用透射电子显微镜（TEM）、X射线衍射仪（XRD）以及振动样品磁强计（VSM）对Fe3O4纳米磁性颗粒的粒径、形貌和磁性进行表征并研究Fe3O4纳米磁性微粒对全氟辛磺酸盐的吸附。结果表明：在PFOS初始浓度4 mg/L,pH为3,反应时间24 h,Fe3O4纳米磁性微粒投加量1.25 g/L,对全氟辛磺酸盐去除率达到90%。Fe3O4纳米磁性微粒对PFOS的吸附符合Freundlich吸附方程。     

Synthesis of magnetic CoFe2O4/ordered mesoporous carbon nanocomposites and application in Fenton-like oxidation of rhodamine B

CoFe₂O₄/ordered mesoporous carbon (OMC) nanocomposites were synthesized and tested as heterogeneous peroxymonosulfate (PMS) activator for the removal of rhodamine B. Characterization confirmed that CoFe₂O₄ nanoparticles were tightly bonded to OMC, and the hybrid catalyst possessed high surface area, pore volume, and superparamagnetism. Oxidation experiments demonstrated that CoFe₂O₄/OMC nanocomposites displayed favorable catalytic activity in PMS solution and rhodamine B degradation could be well described by pseudo-first-order kinetic model. Sulfate radicals (SO₄ ⁻·) were verified as the primary reactive species which was responsible for the decomposition of rhodamine B. The optimum loading ratio of CoFe₂O₄ and OMC was determined to be 5:1. Under optimum operational condition (catalyst dosage 0.05 g/L, PMS concentration 1.5 mM, pH 7.0, and 25 °C), CoFe₂O₄/OMC-activated peroxymonosulfate system could achieve almost complete decolorization of 100 mg/L rhodamine B within 60 min. The enhanced catalytic activity of CoFe₂O₄/OMC nanocomposites compared to that of CoFe₂O₄ nanoparticles could be attributable to the increased adsorption capacity and accelerated redox cycles between Co(III)/Co(II) and Fe(III)/Fe(II).

     

Copper-promoted heterogeneous Fenton-like oxidation of Rhodamine B over Fe3O4 magnetic nanocatalysts at mild conditions

Environmental Science and Pollution Research - Rhodamine B (RhB) is used in various industries and its effluent must be effectively treated because of its harmful and carcinogenic nature. In this...     

复合纳米Fe2O3/TiO2可见光催化降解邻甲酚溶液的研究

以复合纳米Fe2O3／TiO2作为催化剂,日光色镝灯为光源,研究了邻甲酚溶液的可见光降解。考察了催化剂制备方法、催化剂使用量、溶液pH、催化剂重复使用等条件对可见光降解的影响。实验结果表明,1％Fe2O3／TiO2（n）对邻甲酚溶液的可见光降解效果最优,比Ti02（p25）的降解率提高了2．6倍。在实验条件下,可见光降解3h,邻甲酚溶液的浓度去除率达95．4％,TOC去除率为72．3％。在较宽的浓度范围内,邻甲酚的反应服从一级动力学反应方程,随着浓度的增大,反应速率常数不断降低。     

CoFe2O4/TiO2/鳞片石墨粒子电极光电催化降解罗丹明B

采用溶胶-凝胶法制成CoFe2O4/TiO2/鳞片石墨粒子电极,用电子扫描电镜（SEM）、X-射线衍射仪（XRD）和X-射线光电子能谱仪（XPS）对该粒子电极的形貌、晶体结构和元素组成进行分析,并将其应用于罗丹明B（RhB）的光电催化实验;考察电解质浓度、粒子电极投加量、电压、pH和初始浓度等因素对罗丹明B降解的影响,并研究了罗丹明B的光电催化降解动力学。结果表明：光催化和电化学联合作用时,产生协同作用;在电解质Na2SO4溶液浓度为0.03 mol·L-1,粒子电极投加量为6.67 g·L-1,外加电压为8 V,pH为3,反应时间为45 min时,浓度为15 mg·L-1的罗丹明B的去除率达到97.6%;罗丹明B的光电催化降解反应符合假一级动力学模型。     

纳米Fe3O4磁性粒子的制备及吸附性能研究

采用共沉淀法制备了纳米Fe3O4磁性粒子。应用透射电子显微镜（TEM）、扫描电子显微镜（SEM）、X-射线衍射仪（XRD）和振动样品磁强计（VSM）等对纳米磁性粒子的粒径、结构、形貌、磁性能进行了表征,进行了磁分离沉降性能和腐殖酸吸附去除实验研究。结果表明：在未添加任何分散剂的条件下,制得的纳米Fe3O4磁性粒子主要呈球状,平均粒径约11nm,为典型的反尖晶石结构;饱和磁化强度、矫顽力和剩余磁化强度分别为73．10emu／g、159．2A／m和0．41emu／g;磁分离沉降速度为重力场的50倍;纳米Fe3O4磁性粒子对腐殖酸的吸附符合Langmuir型吸附等温线。     

聚乙烯亚胺/Fe3O4杂化磁性纳米吸附剂去除甲基橙

采用戊二醛共价交联法制备出了聚乙烯亚胺/Fe3O4杂化磁性纳米吸附剂(PEI-Fe3O4)。通过TEM、XRD、FT-IR、VSM和TGA等手段表征了材料的结构和性质。以甲基橙(MO)为吸附质,系统考察了pH值、吸附时间和染料初始浓度等因素对吸附材料性能的影响。结果表明,MO在PEI-Fe3O4上的吸附具有强烈的pH依赖性,pH为3时吸附量最大;吸附平衡仅需20 min,吸附过程符合准二级动力学模型;等温吸附过程更符合Langmuir模型,MO的最大吸附量为242.4 mg/g。重复实验表明,吸附剂经过15次吸附/解吸附循环后仍可维持最初的吸附性能,显示出良好的机械和化学稳定性。因此,该杂化吸附剂在染料废水中MO的去除方面具有良好的应用前景。     

磁性Fe3O4纳米颗粒的制备及在水处理中的应用

众所周知,纳米颗粒在去除水中污染物的过程中易团聚,还会造成水体的二次污染。磁性Fe3O4纳米颗粒因其能迅速从水中分离的特性而被广泛关注。改性之后的磁性Fe3O4纳米颗粒在水中污染物的去除方面有很好的应用。对磁性Fe3O4纳米颗粒及其载体或复合物的制备方法进行了概述,重点对水中污染物的去除从3个方面进行了阐述:磁性Fe3O4纳米材料对水中重金属的吸附、有机物的吸附及水中细菌和医疗废物的处理。     

Fe3O4／Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe3O4纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[（NH3）2]’制备出Fe3O4／Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7．0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99．7％以上,Fe3O4／Ag颗粒吸附行为符合二级动力学模型（R2〉0．99）。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe3O4／Ag在水处理方面拥有良好的应用前景。     

Recent advances in the application of magnetic Fe3O4 nanomaterials for the removal of emerging contaminants

Environmental Science and Pollution Research - Emerging contaminants (ECs) are widely distributed and potentially hazardous to human health and the ecological system. However, traditional...     

Fe3O4/ZrO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/ZrO2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,用Fe3O4/ZrO2-H2O2非均相类Fenton体系对目标污染物进行降解,考察催化剂的催化效果和温度、pH、H2O2投加量和掺杂比等因素对催化剂催化效果的影响。结果表明,以纳米Fe3O4/ZrO2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/ZrO2的催化效果不断提高;当pH降低时,催化剂的催化效果有明显提升,原始pH(pH=5.7)时反应去除效果最佳,去除率可达88.6%;催化剂用量的增加同样可以提高3,4-二氯三氟甲苯的降解效率;催化剂中Fe3O4:ZrO2的物质的量比为1:2时效果较其他掺杂比的催化剂效果更好,去除率最终可以达到96.82%;当H2O2投加量增加时,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为0.3 mL时去除效果最好,几乎可以完全去除目标有机物。以Fe3O4/ZrO2-H2O2非均相类Fenton体系处理3,4-二氯三氟甲苯时,目标污染物的降解符合一级反应动力学。     

Environmentally friendly synthesis of Fe2O3@SiO2 nanocomposite: characterization and application as an adsorbent to aniline removal from aqueous solution

Environmental Science and Pollution Research - Silica-based nanocomposite syntheses employ many harmful substances, which, in turn, demand the development of new synthetic environmental-friendly...     

TiO2/PANI/Fe3O4光催化磁流体的全流态合成及其光催化和磁回收性能

以Fe3O4磁流体为磁核,经微乳液聚合包覆聚苯胺后制成催化剂载体,再采用低温水热法合成TiO2并使其负载于载体表面,不经过烘干、研磨等步骤,在全程流态的情况下制备出具有复合结构的TiO2/PANI/Fe3O4光催化磁流体。用X射线衍射仪（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、傅里叶红外分光光度计（FT-IR）、振动样品磁强计（VSM）对样品的物相组成、形貌、表面性质和磁学性质进行了表征。以苯酚为模拟污染物,评价其光催化活性;通过自制的磁回收装置,考察其磁回收特性。结果表明：在表面活性剂以及微乳液聚合法的作用下,合成反应过程中的团聚现象得到有效的抑制。在不经过烘干、研磨的条件下,制备出了颗粒均匀、催化活性和磁回收性能良好的TiO2/PANI/Fe3O4光催化磁流体。不仅简化了合成的步骤,同时也避免了研磨等物理作用对催化剂结构的破坏,为光催化磁流体的合成提供了新的思路。     

Controllable synthesis Fe3O4@POHABA core-shell nanostructure as high-performance recyclable bifunctional magnetic antimicrobial agent

We demonstrated a method to form magnetic antimicrobial POHABA (poly-N,N′-[(4,5-dihydroxy-1,2-phenylene)bis(methylene)]bisacrylamide)-based core-shell nanostructure by free-radical polymerization of OHABA on the Fe₃O₄ core surface. The magnetic antimicrobial agent Fe₃O₄@POHABA can be used in domestic water treatment against bacterial pathogens. The thickness of POHABA shell could be controlled from 10.4 ± 1.2 to 56.3 ± 11.7 nm by the dosage of OHABA. The results of antimicrobial-activity test indicated that POHABA-based core-shell nanostructure had broad-spectrum inhibitory against Gram-negative, Gram-positive bacteria and fungi. The minimum inhibitory concentration (MIC) values of Fe₃O₄@POHABA nanostructure against Escherichia coli and Bacillus subtilis were both 0.4 mg/mL. Fe₃O₄@POHABA nanostructures responded to a permanent magnet and were easily recycled. Fe₃O₄@POHABA nanoparticles retained 100% antimicrobial efficiency for both Gram-negative and Gram-positive bacteria throughout eight recycle procedures.

     

Synthesis and characterization of magnetic Fe3O4@CaSiO3 composites and evaluation of their adsorption characteristics for heavy metal ions

A two-component material (Fe₃O₄@CaSiO₃) with an Fe₃O₄ magnetite core and layered porous CaSiO₃ shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe₃O₄@CaSiO₃ composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu²⁺, Ni²⁺, and Cr³⁺ adsorption were studied. The Fe₃O₄@CaSiO₃ composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m²/g, pore size of 16 nm, and pore volume of 0.25 cm³/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu²⁺, Ni²⁺, and Cr³⁺ by Fe₃O₄@CaSiO₃ fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe₃O₄@CaSiO₃ toward Cu²⁺, Ni²⁺, and Cr³⁺ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe₃O₄@CaSiO₃ exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

     

Fe3O4/石墨烯-H2O2预处理对污泥脱水性能的影响及其作用机理

采用共沉淀法制备四氧化三铁/石墨烯（Fe3O4/GE）材料,并对其进行表征,将其与H2O2组成非均相类Fenton体系用来预处理污泥,发现此类Fenton体系能显著降低污泥比阻（SRF）,并深入分析其作用机理。研究了pH、反应时间、反应温度以及Fe3O4/GE-H2O2投加量对污泥胞外聚合物（EPS）破解的影响。结果表明,适宜反应条件为：pH 4.0,反应时间为90 min,反应温度为50 ℃,Fe3O4/GE投加量为1 g·L-1,H2O2与Fe3O4/GE投加量之比控制在8~12之间。在该条件下,污泥上清液中的SCOD、多聚糖和蛋白质浓度分别由56.47、11.48和8.21 mg·L-1增加到498.31、406.72和286.29 mg·L-1。Fe3O4/GE-H2O2非均相类Fenton体系在有效破解EPS的同时,对于污泥的脱水性能也有明显的改善作用,促进了污泥的后续处理。     

Fast removal of heavy metals from water and soil samples using magnetic Fe3O4 nanoparticles

Environmental Science and Pollution Research - Heavy metal discharge from anthropogenic sources on open soil surfaces and in natural water bodies poses serious environmental and health concerns. In...