Nanosized Pd assembled on superparamagnetic core–shell microspheres:Synthesis,characterization and recyclable catalytic properties for the Heck reaction

A series of magnetically recyclable Pd/Fe3O4@g-Al2O3 catalysts were synthesized using the superparamagnetic Fe3O4@g-Al2O3core–shell microspheres as the supporter and nano-Pd particles assembled on g-Al2O3 shell as the active catalytic component.The structure of the catalysts was characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),N2adsorption–desorption and vibrating sample magnetometer(VSM).The catalytic activity and the recyclability properties of the catalysts for the Heck coupling reaction with aryl bromides and the olefins were investigated.The results show that the microspheres of the magnetic Pd/Fe3O4@g-Al2O3 catalysts were about 400 nm and the nano-Pd particles assembled on g-Al2O3 shell were about 3–4 nm in size.The saturation magnetization(MS) of the magnetic catalysts was sufficiently high to allow magnetic separations.In the Heck coupling reactions,the magnetic Pd/Fe3O4@g-Al2O3 catalysts exhibited good catalytic activity and recyclability.With Pd/Fe3O4@g-Al2O3(0.021 mol%) catalyst,the bromobenzene conversion and product yield reached about 96.8% and 91.2%,respectively,at 120 8C and in 14 h.After being recycled for six times,the conversion of bromobenzene and the recovery of the catalyst were about80% and 90%,respectively.The nano-Pd particles were kept well dispersed in the used Pd/Fe3O4@g-Al2O3 catalysts.     

Surface Modifications of Halloysite Nanotubes with Superparamagnetic Fe3O4 Nanoparticles and Carbonaceous Layers for Efficient Adsorption of Dyes in Water Treatment

Surface modification of halloysite nanotube(HNT) with in situ grown Fe₃O₄ nanoparticles and carbonaceous layers introduced by a hydrothermal carbonization process of glucose has been achieved. Structure and morphology investigations demonstrate that iron oxide nanoparticles are uniformly anchored on the halloysite and prevent the aggregations of halloysite and carbon, forming a protective layer that stabilizes and improves the property of HNT/Fe₃O₄/C nanocomposite. Magnetism characterization proves the superparamagnetic behavior of HNT/Fe₃O₄/C hybrid at room temperature, which makes it easily separated from dye solution under an external magnetic field. Exploration of adsorption ability demonstrates that the maximum adsorption capacity of the as-prepared HNT/Fe₃O₄/C nanocomposite for methylene blue(MB) is about twice and 1.5 times those of HNT/Fe₃O₄ and HNT according to Langmuir equation, respectively. The adsorption behavior investigations indicate that HNT/Fe₃O₄/C hybrid has a heterogeneous structure and shows a non-ideal monolayer adsorption that fits the Redlich-Peterson isotherm, and the adsorption process follows a pseudo-second-order kinetic model. Therefore, the as-prepared HNT/Fe₃O₄/C hybrid is a fast, separatable and superparamagnetic adsorbent with a good adsorption ability, demonstrating great potential in the application of water treatment.     

Metal-organic framework derived magnetic nanoporous carbon as an adsorbent for the magnetic solid-phase extraction of chlorophenols from mushroom sample

In this work, a metal-organic framework derived nanoporous carbon(MOF-5-C) was fabricated and modified with Fe_3O_4 magnetic nanoparticles. The resulting magnetic MOF-5-derived porous carbon(Fe_3O_4@MOF-5-C) was then used for the magnetic solid-phase extraction of chlorophenols(CPs) from mushroom samples prior to high performance liquid chromatography–ultraviolet detection. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N_2 adsorption were used to characterize the adsorbent. After experimental optimization, the amount of the adsorbent was chosen as 8.0 mg, extraction time as 10 min, sample volume as 50 m L, desorption solvent as 0.4 m L(0.2 mL×2)of alkaline methanol, and sample p H as 6. Under the above optimized conditions, good linearity for the analytes was obtained in the range of 0.8–100.0 ng g~(-1)with the correlation coefficients between0.9923 and 0.9963. The limits of detection(S/N = 3) were in the range of 0.25–0.30 ng g~(-1), and the relative standard deviations were below 6.8%. The result showed that the Fe3O4@MOF-5-C has an excellent adsorption capacity for the analytes.     

尺寸可控的单分散四氧化三铁微球的省时制备

Monodisperse Fe₃O₄ microspheres with tunable diameters and high magnetic saturation were synthesized by a solvothermal reduction method. It was found that the morphology and structure of the Fe₃O₄ microspheres could be tuned by simply altering the amount of the reactants such as ferric chloride, sodium acetate, water, and the reaction time. The Fe₃O₄ microspheres obtained via this method possessed high purity, crystallinity, and a nearly spherical shape. Furthermore, they were monodispersed and no aggregation was found. Such monodisperse Fe₃O₄ microspheres had tunable diameters of 400-700 nm and the fabrication time was only 2-4 h. The products showed high magnetic saturation values, and their yields were typically more than 94%.     

表面分子印迹磁性纳米粒子的制备及其血红蛋白传感应用

以Fe₃O₄磁性纳米粒子为载体、多巴胺（DA）为功能单体、血红蛋白（Hb）为模板分子,用氯铂酸氧化DA生成聚多巴胺（PDA）,同时氯铂酸还原为铂纳米粒子（PtNPs）,与Hb一起负载于Fe₃O₄纳米粒子表面,洗脱Hb后合成了表面分子印迹磁性纳米粒子（印迹Fe₃O₄/PDA-PtNPs）. 将印迹Fe₃O₄/PDA-PtNPs修饰于磁性玻碳基底表面,制得印迹Fe₃O₄/PDA-PtNPs修饰电极. 实验结果表明,印迹Fe₃O₄/PDA-PtNPs具有良好的水溶性,粒径分布均匀,生成的PtNPs具有良好的导电性和刚性. 用印迹Fe₃O₄/PDA-PtNPs构建的传感器对Hb具有良好的识别性,在0.14 ~ 2.7 μg·mL^-1 Hb浓度范围与交流阻抗变化值呈良好的线性关系,检出限（S/N=3）为0.05 μg·mL^-1.     

Effective Removal of Tetracycline by Using Biochar Supported Fe3O4 as a UV-Fenton Catalyst

Novel Fe3O4-decorate hierarchical porous carbon skeleton derived from maize straw(Fe3O4@MSC)was synthesized by a facile co-precipitation process and a calcination process,which was developed as a UV assisted heterogeneous Fenton-like catalyst.The as-synthesized catalysts were characterized via X-ray powder diffraction(XRD), scanning electron microscope(SEM),transmission electron microscope(TEM),Brunauer-Emmet-Teller(BET)and vibrating sample magnetometer(VSM)at room temperature.The morphology and structure analysis revealed that the as-prepared Fe3O4@MSC retained the original pore morphology of the maize straw material.The non-uniform poly- hedral Fe3O4 grew on the whole surface of the MSC,which reduced the aggragation of Fe3O4 and provided more active sites to strengthen the UV-assisted Fenton-like reaction.As a result,the tetracycline(TC)degradation efficiency after 40 min reaction and total organic carbon(TOC)removal efficiency after 2 h reaction of Fe3O4@MSC catalyzing UV-Fenton system reached 99.2%and 72.1%,respectively,which were more substantial than those of Fe3O4@MSC/H2O2(31.5%and 2%),UV/H2O2 system(68%and 23.4%)and UV/Fe3O4/H2O2(80% and 37.5%).The electron spin resonance(ESR)results showed that the ·OH played an important role in the catalytic reaction.A possible degradation pathway of TC was proposed on the basis of the identified intermediates.Overall,the UV assisted heterogeneous Fenton-like process in Fe3O4@MSC improved the cycle of Fe^3+/Fe^2+ and activated the interfacial catalytic site,which eventually realized the enhancement of degradation and mineralization to tetracycline.     

The fabrication of hollow magnetite microspheres with a nearly 100% morphological yield and their applications in lithium ion batteries

Hollow Fe_3O_4(H-Fe_3O_4) microspheres were fabricated through a facile one-step solvothermal synthesis,which was performed in an ethylene glycol(EG)–diethylene glycol(DEG) mixed solvent using polyethylene glycol(PEG) as the stabilizer. The addition of DEG increased the viscosity of the system,which caused the Fe_3O_4 primary crystal to aggregate slower and the morphological yield to approach nearly 100%. The as-prepared hollow Fe_3O_4 microspheres show promise for application in lithium ion battery anodes and showed a reversible specific capacity of 453.3 mAh g~(-1) after 50 cycles at 100 mA g~(-1).     

Aluminum-type superparamagnetic adsorbents: Synthesis and application on fluoride removal

Two effective types of superparamagnetic nano-scale adsorbents of bayerite/SiO₂/Fe₃O₄ have been synthesized via three sequential steps: chemical precipitation of Fe₃O₄, coating of SiO₂ on Fe₃O₄ using acidifying method, and further coating of bayerite (Al(OH)₃) on SiO₂/Fe₃O₄ adopting sol–gel (MASG) or homogeneous precipitation (MAHP) methods. The characteristics of MASG and MAHP were identified using the transmission electron microscopy (TEM) micrograph, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), X-ray powder diffractometer (XRD), and superconducing quantum interference device (SQUID). Removal of fluoride from aqueous solution was examined to evaluate the adsorptive capacity of MASG, MAHP, and commercial activated alumina (CA), and the effects of enclosure of Fe₃O₄ with SiO₂ for SiO₂/Fe₃O₄, MASG, and MAHP particles. Among the adsorbents tested under the same experimental condition, MASG is the most effective adsorbent, of which the adsorption capacities are 38 g/kg (based on adsorbent mass of adsorption in terms of equilibrium constant q_L of Langmuir isotherm), and can compete with CA even at a high pH value. The innovative superparamagnetic adsorbents synthesized in this study possess physicochemical stability at pH range of 6–8 and great potential in the adsorption processes due to not only their high adsorption capacity but also the conveniently magnetic separation which can overcome the difficulty in solid–liquid separation for nano-particles in solutions.     

磁性纳米颗粒Fe3O4的醇改性制备机理及应用

利用化学沉淀法, 以乙二醇(EG)、 聚乙二醇(PEG)和甘露醇(D-M)分别为表面改性剂制备了改性的Fe₃O₄颗粒(分别命名为E-Fe₃O₄, P-Fe₃O₄和D-Fe₃O₄). 实验结果显示, 醇类分子能成功地修饰在Fe₃O₄颗粒表面, 但 未改变其形貌、 大小、 晶相和磁性．采用傅里叶变换红外光谱、 离子选择性电极法、 Zeta电位和接触角等 手段研究其改性机理, 发现P-Fe₃O₄和D-Fe₃O₄样品表面醇修饰与水分子介导的氢键有关, E-Fe₃O₄则通过表面羟基直接与乙二醇形成了更稳定的氢键, 即使经热处理(120 ℃)乙二醇分子仍被固定在Fe₃O₄表面. 表面带有疏水基团的E-Fe₃O₄具有适中的亲水性(接触角32.92°)和水中分散性(粒径200~300 nm). 带负电荷的E-Fe₃O₄被应用于水中阳离子染料结晶紫(CV)的吸附和磁性分离, 对CV吸附量为19.33 mg/g, 是未改性前(8.41 mg/g)的2.3倍, 通过外加异丙醇可以促进CV脱附．     

Preparation and Properties of Magnetic-fluorescent Microporous Polymer Microspheres

Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe₃O₄ nanoparticles and CdSe/ZnS quantum dots(QDs) into hyper-crosslinked microporous polymer microspheres(HCMPs) via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have micropores, and their specific surface area is as high as 703.4 m²/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe₃O₄, and the saturation magnetization reaches 38.6 A·m²/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.     

Fe3O4/HA复合吸附剂对Ni(Ⅱ)的吸附性能研究

采用碱溶酸析法提取腐植酸(HA),通过CaCl₂对其改性后与Fe₃O₄进行复合,制备出不同配比的Fe₃O₄/HA复合吸附剂。利用SEM、BET、FT-IR、XRD分析方法对HA、钙改性HA、Fe₃O₄/HA复合吸附剂进行了表征,考察了物料配比及吸附时间、pH值、温度、投加量和初始浓度对Ni(Ⅱ)吸附率的影响。结果表明:质量复合比mHA:mFe₃O₄:mCaCl₂为3∶2∶2的Fe₃O₄/HA复合吸附剂(HA2)对Ni(Ⅱ)吸附效果最佳。当加入0.8 g吸附剂,Ni(Ⅱ)初始浓度为0.1 g·L^-1,吸附5 h,pH=5,温度40℃,吸附剂对Ni(Ⅱ)的吸附率为92.57%。复合吸附剂在4次吸附脱附后,对Ni(Ⅱ)的吸附率仍达到52%。吸附过程符合准二级动力学方程和Freundlich吸附等温式。在20℃~40℃条件下,热力学参数ΔG<0、ΔS=37.57 J/(mol·K)、ΔH=11.07 kJ·mol^-1,表明该吸附是自发、熵增、吸热的过程。     

Fe/Al-SiO_2复合金属氧化物用于燃煤烟气中汞的脱除

采用不同方法制备了Fe/Al-SiO_2复合金属氧化物以模拟赤泥成分,模拟烟气条件下考察其脱汞性能。结果表明,采用溶胶-凝胶法得到的复合金属氧化物在300-450℃具有优异的脱汞性能,其中,在350℃、3 h内平均脱汞率可达到94.8%。Fe_2O_3为Hg~0的氧化提供了晶格氧和化学吸附氧;SiO_2形成的硅溶胶则有利于活性组分Fe_2O_3的分散,增强了Hg~0与活性位的接触。基本模拟烟气中存在微量HCl和NO时,Hg~0脱除率接近100%;当烟气中存在0.2 mL/min、0.4 mL/min的SO_2时,吸附剂的平均脱汞率分别降至90.7%、53.4%,这主要是由于SO_2与Fe_2O_3反应生成Fe_2(SO_4)_3,导致了Fe_2O_3的失活并抑制汞的脱除。     

用于生物柴油清洁生产的磁性固体催化剂CaO/MgO/Fe_3O_4

制备了具有磁性和催化活性的双功能催化剂CaO/MgO/Fe3O4,用于催化花生油酯交换制备生物柴油的清洁生产过程。对CaO/MgO/Fe3O4进行了XRD、TEM、FT-IR和磁性等表征分析,探讨了CaO/MgO/Fe3O4催化剂的重复利用性能。结果表明,用Mg(Ac)2溶液等体积浸渍磁性基质Fe3O4,在N2气氛中600℃焙烧2 h,可得到具有磁性的载体5%MgO/Fe3O4;再用Ca(Ac)2溶液等体积浸渍MgO/Fe3O4,并在N2气氛中700℃煅烧,得到具有磁性且催化活性较高的催化剂10%CaO/MgO/Fe3O4。该催化剂具有核壳结构,磁核平均直径约为35 nm。在催化剂用量10%,醇油摩尔比12∶1,反应温度65℃,反应2 h的条件下酯交换转化率可达90%以上。在磁场的吸引下该催化剂能快速与反应体系分离,催化剂回收率达90%。但CaO/MgO/Fe3O4重复利用性能较差,其原因是在搅拌反应过程中催化活性组分逐渐从催化剂上脱落所致。     

理想与还原Fe2O3[001]表面上汞吸附协同催化CO分解作用

煤化学链燃烧必然释放汞,汞与载氧体表面相互作用,影响表界面的氧化还原反应。本文采用密度泛函理论计算,研究汞（Hg⁰）在理想表面（Fe₂O₃[001]）和一系列被还原表面（Fe₂O_2.75、Fe₂O_2.5、Fe₂O_2.25、Fe₂O_1.625、Fe₂O_0.875、Fe₂O_0.375和Fe）的吸附,以及Hg⁰对Fe₂O_1.625、Fe₂O_0.875、Fe₂O_0.375和Fe等表面催化CO分解反应的协同作用机理。Hg⁰物理吸附在理想Fe₂O₃[001]表面。随着Fe₂O₃[001]表面不断被还原,Hg⁰发生化学吸附。Hg⁰吸附降低了CO与Fe₂O₃、Fe₂O_2.75、Fe₂O_2.5和Fe₂O_2.25等表面之间的相互作用,抑制O传递氧化CO为CO₂的反应;载氧体进一步还原过程中,Hg⁰吸附促进了CO与Fe₂O_1.625、Fe₂O_0.875、Fe₂O_0.375及Fe等表面之间的相互作用,进而促进了表面对CO的催化分解反应,加速了载氧体表面的积碳,降低了化学链燃烧效率。因此,合理控制载氧体的还原程度既可以减弱Hg⁰的吸附,也可以抑制积碳的形成,这对化学链燃烧的操作优化至关重要。     

磁性纳米复合物的制备及对铜离子(Ⅱ)的传感检测

采用化学共沉淀法合成硅包覆的磁性纳米粒子Fe_3O_4@SiO_2,进一步通过六亚甲基二异氰酸酯将吡哆酰肼分子(Pyh)接枝到Fe_3O_4@SiO_2表面,制得功能化的磁性纳米复合物(Fe_3O_4@SiO_2-Pyh)。通过傅里叶变换红外光谱、透射电子显微镜、X射线衍射等技术手段对其结构、形貌和磁性能进行了表征。Fe_3O_4@SiO_2-Pyh粒子具有规则的核壳结构,粒径分布在50~55 nm,壳层厚度约为15 nm。Fe_3O_4@SiO_2-Pyh结构中含有酰腙类活性基团—CO—NH—N=CH—,能与Cu~(2+)形成稳定的配合物,在此基础上采用紫外可见吸收光谱特性建立了测定Cu~(2+)的分析方法,线性范围为3.4×10~(-7)~4.5×10~(-6)mol/L,检出限为1.03×10~(-7)mol/L。此外,利用Fe_3O_4@SiO_2-Pyh良好的磁响应,通过外部磁场能够有效地除去水中过量的铜离子,在环境领域具有潜在的应用价值。     

磁芯负载离子液体凝胶微球的制备、表征及在固定化细胞技术中的应用

选取具有良好生物相容性的壳聚糖(CS)包覆四氧化三铁纳米粒子(Fe₃O₄/CS)作为磁响应材料, 制备了磁芯负载1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF₆)凝胶微球; 对Fe₃O₄/CS及磁芯负载离子液体凝胶微球的组成、 结构、 微观形貌和磁性能进行了表征; 将其应用于固定化细胞技术, 在产紫青霉细胞全细胞生物催化甘草酸(GL)合成单葡萄糖醛酸基甘草次酸(GAMG)体系中, 实现了对全细胞生物催化剂和离子液体的快速回收和重复利用. 实验结果表明, 壳聚糖成功包裹Fe₃O₄纳米粒子; Fe₃O₄/CS均匀分布在凝胶微球内部, 并显示出良好的磁性能; 与凝胶微球固定化细胞催化体系相比, 磁芯负载[BMIM]PF₆凝胶微球固定化细胞催化体系中GAMG的产率提高了13.8%; 重复利用实验结果表明, 磁芯负载[BMIM]PF₆凝胶微球固定化产紫青霉细胞在外加磁场的作用下, 易于快速回收, 并且循环再利用9次后相对活性仍保留59.2%.     

煤化学链燃烧Fe2O3载氧体的反应性研究

利用流化床反应器并以水蒸气作为气化-流化介质,研究了温度、反应时间、循环数对Fe₂O₃载氧体反应性的影响。实验表明,载氧体与煤气化产物的反应性随温度升高而增强,且温度越高,反应受化学反应控制时间越短。当温度高于900℃时,煤中碳转化为CO₂的比率大于90%,载氧体体现了很好的反应性,但反应温度低于850℃时,比率小于75%。反应温度900℃时,CO₂干基浓度随循环数而逐渐降低,CO、CH₄浓度增加,且CH₄浓度值大于CO。利用XRD、SEM分析了固体反应产物成分与微观形态结构。分析表明,Fe₂O₃的还原产物为Fe₃O₄,载氧体颗粒随循环数增加而逐渐烧结。     

磁性可回收氟化石墨烯破乳材料的制备及乳液分离性能

以氟化石墨烯(FG)为原料, 首先制备了水合肼还原的具有一定亲水性的氟化石墨烯(HFG), 然后采用溶剂热法制备了可磁性分离的四氧化三铁负载的氟化石墨烯复合破乳材料(HFG-Fe₃O₄). 分别利用透射电子显微镜(TEM)、 扫描电子显微镜(SEM)、 傅里叶变换红外光谱仪(FTIR)、 X射线粉末衍射仪(XRD)和X射线光电子能谱仪(XPS)对HFG-Fe₃O₄的形貌、 结构和化学性质进行了表征. 最后研究了HFG-Fe₃O₄对含油废水的破乳性能, 探讨了影响其破乳性能的主要因素, 并对其破乳机理进行了分析. 结果表明: HFG-Fe₃O₄是一种表面负载有Fe₃O₄纳米颗粒的二维片状材料, 在最佳剂量为600 mg/L时对酸性和中性含油废水具有良好的破乳效果. 在酸性和中性条件下, 主要是利用HFG-Fe₃O₄与含油废水之间的静电吸引力以及HFG-Fe₃O₄与沥青质之间的π-π相互作用实现油-水分离. 但是, 在碱性条件下, HFG-Fe₃O₄与油滴之间的静电斥力将急剧增大, 最终导致破乳效率降低. 此外, 将磁性回收的HFG-Fe₃O₄循环利用4次后其乳液分离效率并没有明显下降, 表现出优异的循环稳定性.     

Mo/Fe3O4(111)表面对燃煤烟气汞吸附的密度泛函研究

利用CASTEP软件包采用密度泛函理论计算研究了过渡金属Mo掺杂Fe_3O_4(111)Fe_(tet)表面对Hg~0、HgCl和HgCl_2的吸附特征,分析了Mo掺杂前后Fe_3O_4(111)Fe_(tet)表面上不同汞物种的吸附形态。结果表明,Mo掺杂Fe_3O_4(111)Fe_(tet)表面对HgCl和HgCl_2为化学吸附,而对Hg~0的吸附为物理吸附;与纯净表面相比,HgCl在Mo原子掺杂表面上的吸附能提高了40%-66%。HgCl_2在纯净Fe_3O_4(111)Fe_(tet)表面形成"M"形结构;而掺杂Mo原子后,由于Cl原子与Mo原子之间更强的相互作用,使得HgCl_2发生了完全解离,两个Cl原子分别与Mo原子和Fe原子成键吸附在表面,Hg脱附。相关研究结果可为脱除燃煤烟气中的汞提供一定的理论指导。     

High-efficient Isolation of Plant Viral RNA via TMAOH-modified Fe3O4 Magnetic Nanoparticles

Magnetic nanoparticles show great potential in RNA enrichment and separation for rapid detection of viral infection.Fundamental studies on the interaction between RNA and nanoparticles with uniform size and surface property are necessary for designing better adsorbent and optimizing the conditions.In this study,monodispersed superparamagnetic magnetite（Fe3O4） nanoparticles were synthesized by thermal decomposition and modified with tetramethylammonium hydroxide[N（CH3）4OH,TMAOH] that become highly dispersible and stable in water.High-efficiency plant viral RNA adsorption onto TMAOH/Fe3O4 nanoparticles in the extracted solution of plant leaves was demonstrated.The changes of surface charge of TMAOH on the Fe3O4 nanoparticles with pH contribute to the RNA adsorption and elution.Separating viral RNA with magnetic nanoparticles could be a simple,quick andhighly efficient method.