Preparation of novel magnetic nanoparticles as draw solutes in forward osmosis desalination

Novel magnetic nanoparticles (MNPs), Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂, were prepared by loading different amounts of SiO₂ or/and PEG-(COOH)₂ onto Fe₃O₄ nanoparticles, and their feasibility to be used as forward osmosis (FO) draw solutes was investigated. The characterization of the materials showed that, compared to normal Fe₃O₄ nanoparticles, the modified MNPs exhibited enhanced dispersity and high osmotic pressure in aqueous solution. The FO experiment indicated that the synthesized draw solutes could obtain a water flux as high as 10 L·m^-2·h^-1 with an aquaporin FO membrane. The optimal concentration of the added tetraethyl orthosilicate was 30% during the synthesis. The novel MNPs could be easily recovered from draw solutions by magnetic field, and the recovery rate of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ was 83.95% and 63.37%, respectively. Moreover, after 5 recycles of reuse, the water flux of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ as draw solutes still remained 64.36% and 85.26%, respectively. The experimental results demonstrated that the synthesized core–shell magnetic nanoparticles are promising draw solutes, and the Fe₃O₄@SiO₂@PEG-(COOH)₂ was more suitable to be used as draw solute in FO process.     

多巴胺包埋磁性SiO2固定化漆酶催化去除4-氯酚

以磁性纳米颗粒为载体,通过多巴胺(dopamine,DA)聚合原位包埋制备了磁性SiO₂固定化漆酶(Fe₃O₄@SiO₂-PDA-Lac)。结果显示纳米颗粒尺寸均匀,并且保持较高的饱和磁性。通过最优条件制备出的固定化漆酶在50℃放置6 h后,活性保持在63%,而游离酶仅保留18%。将固定化酶用于催化降解4-氯酚(4-CP),探究了溶液pH、漆酶浓度和ABTS[2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸铵)]对4-CP去除率的影响。固定化漆酶在反应最适pH时,4-CP去除率为84.3%,而游离酶仅为65.7%。当漆酶浓度为1.2 U·ml^-1时,反应8 h后,4-CP去除率可达95%,而游离酶的4-CP去除率仅82%。ABTS可促进固定化漆酶降解4-CP,当体系中加入50 μmol·L^-1 的ABTS,反应10 min后,固定化酶对4-CP去除率可达99%。固定化漆酶在重复使用10次后,4-CP去除率仍可达67%。     

功能性Fe3O4@SiO2核-壳纳米复合材料应用研究进展

Fe_3O_4@SiO_2是一种研究非常广泛的核壳纳米复合材料,为了拓展其应用范围,常采用化学键合、浸渍、沉积沉淀等方法对其表面进行修饰制备功能性Fe_3O_4@SiO_2。综述功能性Fe_3O_4@SiO_2核-壳纳米复合材料在药物缓释、催化、吸附、以及传感等相关应用领域中的最新研究进展。     

磁性颗粒负载磺酸功能化离子液体催化纤维素水解的研究

采用化学修饰法将磺酸功能化离子液体[SO₃H-（CH₂）₃-HIM][HSO₄]负载在磁性纳米颗粒Fe₃O₄表面,制备了一种磁性颗粒负载磺酸催化剂Fe₃O₄@SiO₂-IL,并将Fe₃O₄@SiO₂-IL用于催化纤维素水解反应。采用FT-IR和TEM对催化剂进行了表征,并考察了反应温度、反应时间、催化剂用量和水用量对纤维素水解还原糖产率的影响。Fe₃O₄@SiO₂-IL样品在FT-IR光谱中的—SO₃H吸收峰和咪唑环的峰,说明离子液体被成功地负载到Fe₃O₄@SiO₂表面;TEM分析显示,Fe₃O₄磁核的颗粒大小约为250 nm,经过包裹和离子液体修饰的磁性颗粒表面并无明显变化。当纤维素用量为0.1 g,离子液体1-丁基-3-甲基咪唑氯盐（[Bmim]Cl）的用量为2.0 g,磁性催化剂用量为0.2 g,水用量为0.2 g,反应温度100 ℃,反应时间40 min时,纤维素水解还原糖产率可达52.5 %,并且磁性催化剂具有较好的磁性分离性能和重复使用性能,重复使用5次后,纤维素水解还原糖产率并无明显降低。     

Fe2O3对铜尾矿基CaO-MgO-Al2O3-SiO2微晶玻璃析晶行为的影响

以铜尾矿为主要原料,通过熔融法制备CaO-MgO-Al₂O₃-SiO₂(CMAS)微晶玻璃,并外掺Fe₂O₃晶核剂对细粒级铜尾矿基CMAS微晶玻璃析晶行为进行优化。利用DSC、XRD和SEM等手段研究了晶核剂用量对细粒级铜尾矿基CMAS微晶玻璃析晶行为和物理性能的影响,借助Ozawa-Chen法拟合计算了析晶动力学参数。结果表明,外掺Fe₂O₃晶核剂用量大于3.72%(质量分数)时,细粒级铜尾矿制备的微晶玻璃可以实现整体析晶。辉石相的析出是玻璃相中的Fe、Mg元素进入[Si(Al)O₄] 四面体晶格配位的结果,Fe³⁺的增加有利于辉石相的析出并降低了析晶活化能,外掺Fe₂O₃晶核剂能够较好地优化细粒级铜尾矿基微晶玻璃的析晶行为和力学性能。     

超顺磁催化剂H3PW12O40/Fe3O4@SiO2的制备、结构表征及在汽油烷基化脱硫中的应用

采用改进Stöber法制备超顺磁Fe₃O₄@SiO₂复合粒子作为催化剂载体,再通过浸渍法将H₃PW₁₂O₄₀（HPW）负载在Fe₃O₄@SiO₂载体上,制备了一系列超顺磁负载型催化剂HPW/Fe₃O₄@SiO₂。并使用X射线衍射（XRD）、傅里叶红外（FT-IR）、氨的程序升温脱附（NH₃-TPD）、扫描电镜（SEM）、N₂吸附-脱附和振动样品强磁计（VSM）对催化剂进行表征。结果表明,HPW固定并均匀分散在Fe₃O₄@SiO₂载体上,40% HPW/Fe₃O₄@SiO₂催化剂具有较高的饱和磁强度 （30.1 emu·g^-1）和较大的比表面积 （303.6 m²·g^-1）,并可用外加磁场进行分离。采用40% HPW/Fe₃O₄@SiO₂催化噻吩与1-辛烯组成的模拟汽油的烷基化脱硫反应,在160℃下反应2 h,噻吩转化率达到85.5%,有较好的催化脱硫性能,且可以多次循环利用。     

Fe3O4@TiO2@SiO2@Ag光催化剂的制备及其光催化活性研究

采用溶剂热法和溶胶-凝胶法合成了磁性Fe₃O₄@TiO₂@SiO₂复合光催化剂,再通过巯基改性,使二氧化硅表面原位合成银纳米颗粒,最终形成目标光催化剂。利用XRD、FT-IR、XPS、SEM、VSM等分析测试手段对该催化剂的组成、结构、形貌及其磁学性能进行表征。通过光催化降解40 mL罗丹明B溶液(pH 5.3,30 mg/L),催化剂按1 g/L加入反应体系,光照120 min时,罗丹明B溶液的降解率达96.22%。相同条件重复循环实验10次,罗丹明B溶液降解率仅下降4.32%,表明Fe₃O₄@TiO₂@SiO₂@Ag磁性光催化剂具有出色的光催化活性和循环使用性。     

Catalytic ozonation of thymol in reverse osmosis concentrate with core/shell Fe3O4@SiO2@Yb2O3 catalyst:Parameter optimization and degradation pathway

In this work, a novel catalyst of Fe_3O_4@SiO_2@Yb_2O_3 was prepared and the degradation of thymol in reverse osmosis concentrate using ozonation was explored. The operational parameters, such as ozone dosage(8–48 mg·min~(-1)),initial thymol concentration(20–100 mg·L~(-1)), initial pH value(3–11), and catalyst Fe_3O_4@SiO_2@Yb_2O_3dosage(0.2–1.0 g), were studied focusing on the thymol degradation and COD removal. The results indicated that the increase in ozone dosage, initial p H value, and Fe_3O_4@SiO_2@Yb_2O_3dosage accelerated the thymol degradation and COD removal, while the increase in initial thymol concentration hampered the effect of ozonation. A pathway of thymol degradation by catalytic ozonation was proposed based on the intermediates detected by gas chromatography-mass spectrometer and ion chromatography. This paper can provide basic data and technical alternative for pollutant removal from reverse osmosis concentrate by ozonation.     

Preparation and sedimentation behavior of conductive polymeric nanoparticles

A facile route to prepare Fe₃O₄/polypyrrole (PPY) core-shell magnetic nanoparticles was developed. Fe₃O₄ nanoparticles were first prepared by a chemical co-precipitation method, and then Fe₃O₄/PPY core-shell magnetic composite nanoparticles were prepared by in-situ polymerization of pyrrole in the presence of Fe₃O₄ nanoparticles. The obtained nanoparticles were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM) and laser particle size analyzer. The images indicate that the size of Fe₃O₄ particles is about 10 nanometers, and the particles are completely covered by PPY. The Fe₃O₄/PPY core-shell magnetic composite nanoparticles are about 100 nanometers and there are several Fe₃O₄ particles in one composite nanoparticle. The yield of the composite nanoparticles was about 50%. The sedimentation behavior of Fe₃O₄/PPY core-shell magnetic nanoparticles in electrolyte and soluble polymer solutions was characterized. The experimental results indicate that the sedimentation of particles can be controlled by adjusting electrolyte concentration, solvable polymers and by applying a foreign field. This result is useful in preparing gradient materials and improving the stability of suspensions.     

改性Fe3O4纳米粒子的定性及对功能菌固定化与脱氮特性

为解决水体富营养化所导致的恶臭现象, 用SiO₂和壳聚糖(CS)对Fe₃O₄纳米粒子进行改性, 再运用纳米粒子与微胶囊吸附-包埋的方法固定化功能性菌株, 进而对该体系的脱氮特性进行了研究。通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射仪(XRD)、热重分析(TGA)及振动样品磁强计(VSM)等手段对材料的形貌、结构、磁学性能等进行表征。研究结果表明, SiO₂与CS在Fe₃O₄微球表面形成的包覆层具有产物结晶度高、形态规则、磁性能优良等特点。磁性微球在20min时对菌株的吸附率达85.00%, 吸附的活菌数达(2.1～2.2)×10⁶cfu/mL。在对水体脱氮的研究中, 游离态菌株对氨氮和硝氮的去除率分别为54.13%和59.17%, 固定化菌株对氨氮和硝氮的去除率分别达到72.26%和74.56%。实验结果表明, 改性Fe₃O₄磁性微球对菌株吸附能力强, 微胶囊结构使固定化菌株比游离态菌株具有更强的脱氮性能, 且能延长Fe₃O₄磁性微球的生命周期。     

石英砂表面负载铁氧化物的方法和特性

以石英砂(0.5mm)为载体,建立流化床-Fenton系统,在pH值为3.5、Fe²⁺/H₂O₂摩尔比为2:1和进水量为试验装置设计进水量的1/3～1/2条件下,连续加入Fenton试剂,使得铁氧化物在载体表面结晶。这是因为凹凸不平的石英砂和均匀的流化状态有利于铁氧化物的覆膜,同时具有高效传质的流化床进一步强化覆膜过程。通过XRD分析可知,铁氧化物的主要成分是FeOOH、Fe₂O₃、FeO和Fe₂(SO₄)₃。同时将此系统用于处理有机硅废水和合成制药废水,在优化操作条件下,COD和TOC的去除率可达80%和85%,总铁(Fe³⁺)的消减量达26%。     

纳米Fe3O4磁性颗粒表面改性及其在医学和环保领域的应用

纳米Fe₃O₄磁性材料在生物医学、环保、催化及电子信息等领域有巨大的应用潜力,但单独的纳米Fe₃O₄颗粒存在一些弊端,难以直接使用,在生物医药领域尤其如此。对Fe₃O₄磁性纳米粒子进行表面改性,可以改善其结构与性能,因此,备受科学界关注。对近年来Fe₃O₄磁性纳米颗粒的表面改性方法及其在生物医学、环境工程两大领域中的应用做了综述,并对今后发展趋势做了初步的展望。     

非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性，将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右，分散均匀；Fc⁺A成功修饰到纳米颗粒表面，且随Fc⁺A浓度的增加，改性颗粒的接触角明显增大；Fc⁺A浓度为12.5 mmol/L，乳化剂浓度为0.3%(质量)，油水比为4∶6，搅拌速率为10000 r/min，得到的Pickering乳液具有良好的稳定性。而且，所得乳液具双重响应性，通过氧化还原和磁场可实现对乳液稳定性的可逆调控。     

磁性Fe3O4@SiO2@介孔SiO2空心微球的制备及漆酶固定化

磁性介孔二氧化硅复合材料作为酶固定化载体具有优异的酶固定化性能和良好的磁分离性能,受到国内外学术界广泛关注。本文在自制的β-FeOOH空心微球表面上包覆致密的SiO₂保护层,在酸性条件下以P123为模板剂,十六烷基三甲基溴化铵（CTAB）为辅助导向剂成功制备出了磁性β-FeOOH@SiO₂@介孔SiO₂空心复合微球,最后在还原气氛下煅烧得到Fe₃O₄@SiO₂@介孔SiO₂空心微球。结果表明,所制备的Fe₃O₄@SiO₂@介孔SiO₂微球空心结构未坍塌,具有规整的球形结构,介孔SiO₂壳层（平均厚度约为11nm）均匀地包覆在β-FeOOH@SiO₂中空微球表面。伴随着CTAB量的增加,微球的最可几孔径由4.30nm减小到3.19nm,比表面积从376m²/g升高到640m²/g,孔容从0.36cm³/g升高到0.56cm³/g。复合微球的饱和磁化强度为11.3emu/g,矫顽力为111.5Oe,外加磁场作用下可以实现样品的快速分离,且样品的再分散性良好。当介孔孔径为4.30nm时,Fe₃O₄@SiO₂@介孔SiO₂空心复合微球漆酶固定量高达234mg/g。固定化漆酶在不同pH、温度下的活性显著优于游离酶。     

单分散磁性Fe3O4纳米粒子的研究进展

具有良好的化学稳定性、生物相容性、磁响应性的单分散磁性Fe₃O₄纳米粒子,在药学、催化化学、医学和光电磁记录材料等方面都有很大的使用前景;而具有自组装光子晶体现象的Fe₃O₄磁性纳米粒子在包装、印刷、防伪等领域的应用中更展现出巨大的潜力。本文在对单分散磁性Fe₃O₄纳米粒子的制备方法进行了总结回顾,并对单分散磁性Fe₃O₄纳米粒子的光学应用领域做了简略的介绍,并对单分散磁性Fe₃O₄纳米粒子的发展趋向进行了展望,并总结分析现阶段大多数Fe₃O₄纳米粒子的合成方法在非极性溶液中分散性差,使其在实际应用中受到很大的限制,未来Fe₃O₄纳米粒子表面进行修饰将成为该领域的研究热点之一。     

Pd/Fe3O4 supported on bio-waste derived cellulosic-carbon as a nanocatalyst for C–C coupling and electrocatalytic application

The current work describes the synthesis of a new bio-waste derived cellulosic-carbon supported-palladium nanoparticles enriched magnetic nanocatalyst (Pd/Fe₃O₄@C) using a simple multi-step process under aerobic conditions. Under mild reaction conditions, the Pd/Fe₃O₄@C magnetic nanocatalyst demonstrated excellent catalytic activity in the Hiyama cross-coupling reaction for a variety of substrates. Also, the Pd/Fe₃O₄@C magnetic nanocatalyst exhibited excellent catalytic activity up to five recycles without significant catalytic activity loss in the Hiyama cross-coupling reaction. Also, we explored the use of Pd/Fe₃O₄@C magnetic nanocatalyst as an electrocatalyst for hydrogen evolution reaction. Interestingly, the Pd/Fe₃O₄@C magnetic nanocatalyst exhibited better electrochemical activity compared to bare carbon and magnetite (Fe₃O₄ nanoparticles) with an overpotential of 293 mV at a current density of 10 mA·cm^–2.     

Preparation of Fe3O4/MnOOH core-shell nanoparticles by a high-frequency impinging stream reactor☆

Well-defined Fe3O4/MnOOH nanoparticles with 61.1 emu·g?1 in magnetization intensity and 90.53 m2·g?1 in surface area have been synthesized by a new-style of high-frequency impinging stream (HFIS) reactor. In this reactor, two streams first collided together to form nano Fe3O4 suspension, which subsequently flew through an S-shaped maln channel to generate high-frequency reversing high-gravity fields. At the same time, 24 thin liquid sheets impinged into the maln channel at the frequencies higher than 100 Hz to create nano Fe3O4/MnOOH colloids. The obtalned powders were characterized by transmission electron microscopy/energy dispersive spectrometer (TEM/EDS), X-ray diffraction (XRD), Brunner–Emmet–Teller (BET) and vibrating sample magnetometer (VSM). Experimental results indicated that low coating ratio prolonged the induction period of heterogeneous nucleation. The high-frequency impingements of 24 thin liquid sheets greatly accelerated the macro-mixing and the initial dispersion. The high-frequency reversing high-gravity fields promoted the meso-and micro-mixing. As a result, nano Fe3O4 cores were fleetly and uniformly covered by MnOOH precursor. As a continuously operated and static high-gravity reactor, the high-frequency impinging stream (HFIS) reactor is being developed to the large-scaled and low-cost production of various nanocomposites.     

Fe3O4@PGMA-Arg磁性吸附剂的制备及对亚铁离子的吸附性能

为脱除油田采出水中的Fe(Ⅱ)合成磁性吸附剂，本文以溶剂热法制得亲水性Fe₃O₄纳米颗粒，使用盐酸多巴胺（DA）进行包覆得到Fe₃O₄@PDA，再以甲基丙烯酸缩水甘油酯（GMA）在其表面聚合接枝得到Fe₃O₄@PGMA，后经精氨酸（Arg）修饰后得到功能化的Fe₃O₄@PGMA-Arg。通过红外光谱、X射线光电子能谱、X射线衍射和磁化强度对制备的纳米颗粒进行表征，结果表明Fe₃O₄@PGMA-Arg中具有伯胺、亚胺双键、羟基和羧基官能团，其中伯胺基团和亚胺双键上的N可与Fe(Ⅱ)形成配位键，羟基和羧基的O可与Fe(Ⅱ)形成配位键，从而达到吸附Fe(Ⅱ)的目的。合成产物仍保持了Fe₃O₄的反尖晶石结构，具有好的磁响应性能。通过静态吸附实验探究吸附条件对Fe₃O₄@PGMA-Arg吸附Fe(Ⅱ)的影响因素，结果表明，Fe(Ⅱ)的吸附量随着温度和初始浓度的增加而增加，适宜的pH为4。动力学和热力学研究表明，吸附Fe(Ⅱ)过程符合准二级反应动力学模型，吸附等温线符合Langmuir模型，吸附过程活化能为45.60kJ/mol，为化学吸附。Fe₃O₄@PGMA-Arg经5次再生后，对亚铁离子仍保持较高的脱除率。     

氧化铁/石墨烯原位复合物对铬酸钾吸附性能研究

采用共沉淀法制备Fe_3O_4磁性纳米颗粒以及通过原位生长法制备Fe_3O_4与氧化石墨烯的复合物,并加入十六烷基三甲基溴化铵形成共价键交联反应化合物。采用X射线衍射仪和透射电子显微镜表征样品的形貌与尺寸,并以铬酸钾为吸附对象,研究吸附温度、吸附时间和溶液p H值对Fe_3O_4吸附性能的影响。结果表明,椭圆形颗粒的Fe_3O_4尺寸约(10~15)nm,与氧化石墨烯复合后,分散性明显提高;在室温和p H=3.5条件下,以Fe_3O_4与氧化石墨烯的质量比2∶1复合物作为吸附剂对铬酸钾的吸附效果达到最佳,每克的吸附容量可达251 mg;复合物经过磁分离、反复吸附循环实验6次后,对铬酸钾的吸附率仅下降10个百分点。     

Crystallization of the molten phase in portland cement clinker

Crystallization of a liquid similar to that present in Portland cement at clinkering temperatures has been studied. Its composition (in wt %) is CaO = 54.8, Aℓ₂O₃ = 22.7, Fe₂O₃ = 16.5, SiO₂ = 6.0. Prolonged crystallization or slow cooling yields the equilibrium phases: C₃A, ferrite close to C₄AF, and C₂S. With more rapid cooling or with static crystallization at lower temperatures, metastable phases form. The most important is a hitherto-unreported cubic polymorph of C₃A having a_o 3.9 Å. It is designated “proto-C₃A’ to distinguish it from ordinary cubic C₃A.