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1.
The confinement of air‐protected metallic magnetic nanoparticles in the inner cavity of carbon nanotubes (CNTs) should offer an interesting perspective for biomedical applications or for controlling CNT alignment in composites. Because the direct confinement of polymer‐precoated nanoparticles in CNTs could be restricted by diffusion limitations, we developed a process based on: 1) the confinement of iron nanoparticles surface‐modified with an iron polymerization catalyst in the cavity of CNTs and 2) the polymerization of isoprene on the confined nanoparticles. The resulting material consists in CNT‐confined iron nanoparticles coated with a polyisoprene air barrier. This approach constitutes a proof of concept for the development of smart materials for use in medicine or composites.  相似文献   

2.
《先进技术聚合物》2018,29(3):1138-1149
Developing polymer catalytic membrane reactors is an aim due to its outstanding advantages. In this paper, a novel catalytic membrane containing palladium‐supported magnetic nanoparticles is introduced. Silica‐iron oxide core shell nanoparticles were first prepared and functionalized by phosphine ionic liquid functionalized poly(ethylene glycol). The modified magnetic nanoparticles were used as support for immobilization of palladium. The final palladium‐immobilized nanoparticles were used as active filler for the preparation of membrane reactor. The prepared membranes were characterized, and their activities were tested in carbon‐carbon bond formation and catalytic reduction. The catalytic membrane showed good performance in the mentioned reactions.  相似文献   

3.
Iron oxide nanoparticles as contrast agents are reported to effectively improve magnetic resonance imaging of tissues and cells. In this work, cleaved iron oxide nanoparticles (CIONPs) were generated from hydrophobic FeO nanoparticles (HIONPs) by coating their surfaces with PEG‐phospholipids, oxidizing them under water, and slowly removing the residual FeO phase in phthalate buffer. The synthesized CIONPs showed good r2 values of up to 258 s?1 mM ?1. Thus, the CIONPs can be employed as vectors for drug delivery due to their unique structure with an empty inner space, which enables their use in a wide range of applications.  相似文献   

4.
吕雅茹  翟雪静  王珊  徐虹  王锐  臧双全 《催化学报》2021,42(3):490-500,中插53-中插60
氧还原反应在一些能源转换系统如金属-空气电池中起着至关重要的作用.目前贵金属基材料(Pt/C)被认为是最有效的氧还原电催化剂,然而价格昂贵和储量有限等因素限制了它的商业化应用,因此探索高效的非贵金属氧还原电催化剂具有重要的意义.近年来,负载过渡金属铁的多孔碳催化剂由于独特的结构和优异的氧还原催化活性成为替代铂基催化剂最有潜力的候选者.该类材料的合成通常采用直接煅烧含有氮源、碳源和铁盐的混合前驱体的制备方法,但是热解时材料的多孔结构以及活性位点的均匀分布很难得到有效的控制.近年来,金属有机框架(MOFs)由于其多孔结构和组成可控等优点而经常被用作自牺牲模板来制备负载铁基纳米材料的多孔碳催化剂,并表现出优异的电催化活性.目前以MOF为前驱体制备高活性的载铁氮掺杂碳复合材料通常需要引入额外的氮源或铁源,因此选择氮含量丰富的铁基MOF材料作为单源前驱体制备载铁氮掺杂多孔碳复合材料具有重要的意义.除此之外,具有多级孔隙率的催化剂可以改善反应时的传质过程,同时有序交联的网络结构能够提供连续的电子传输.本文报道了一种简单可控的制备具有三维有序大孔结构的载铁氮掺杂多孔碳复合催化剂的合成方法,该材料表现出优异的电催化氧气还原性能和优异的催化稳定性.首先,以氮含量丰富的双氰胺和吡嗪配体所构筑的Fe-MOF作为前驱体,利用具有均一尺寸的聚苯乙烯微球作为造孔剂,合成得到了具有三维有序大孔结构的Fe-MOF前驱体,然后通过高温煅烧该单源前驱体制备得到具有三维有序大孔结构的氮掺杂多孔碳包覆铁-氮合金的复合型催化剂(3DOM Fe/Fe-NA@NC).扫描电镜和透射电镜结果表明,材料内形成了有序交联的大孔结构;氮气吸附测试表明,刻蚀之后材料的比表面积明显增加,结合分级多孔特性可以共同促进催化反应的传质过程.粉末X射线衍射结果证实了多孔碳材料中铁和铁-氮合金物种的成功合成.电化学测试结果表明,在0.1 M KOH电解液中,3DOM Fe/Fe-NA@NC-800催化剂表现出优于Pt/C的氧还原活性,其半波电位(E1/2)为0.88 V,大于商业Pt/C的半波电位(E1/2=0.85 V).同时,3DOM Fe/Fe-NA@NC-800表现出更加优异的稳定性,经过20000 s测试后,其电流保持率为94%,而Pt/C只保持了78%.关于活性位点探究的对比实验证明在所制备的复合材料中,铁物种作为高效的活性位点参与了电催化氧还原反应,与氮掺杂多孔碳之间的协同作用共同主导了3DOM Fe/Fe-NA@NC优异的氧还原活性.得益于其优异的氧还原活性,将其作为阴极活性材料组装为锌-空气电池进一步探究了其在实际应用中的可行性.本结果拓宽了高效的铁基催化剂的类型,同时也为制备封装非贵金属的多孔碳基催化剂提供了实验指导和理论依据.  相似文献   

5.
Based on the preparation of biocompatible polysaccharide-based hydrogels with stimuli-responsive properties by the copolymerization of maleilated carboxymethyl chitosan with N-isopropylacrylamide, novel magnetic hybrid hydrogels were fabricated by the in situ embedding of magnetic iron oxide nanoparticles into the porous hydrogel networks. Scanning electron microscopy (SEM) and thermogravimetric (TG) analyses showed that the size, morphology, and content of the iron oxide nanoparticles formed could be modulated by controlling the amount of maleilated carboxymethyl chitosan. As confirmed by X-ray diffractometry (XRD), equilibrium swelling ratio, and differential scanning calorimetry (DSC) measurements, the embedding process did not induce a phase change of the magnetic iron oxide nanoparticles, and the resultant hybrid hydrogels could retain the pH- and temperature-responsive characteristics of their hydrogel precursors. By investigating the partition coefficients of bovine serum albumin as a model protein, this magnetic hydrogel material was found to hold a potential application in magnetically assisted bioseparation.  相似文献   

6.
磁性有序介孔炭的制备及药物吸附行为研究   总被引:2,自引:0,他引:2  
邢伟  禚淑萍  司维江  袁勋 《化学学报》2009,67(8):761-766
采用纳米共铸法将磁性纳米粒子包埋到有序介孔炭的骨架中, 制成含有磁性纳米粒子的有序介孔炭(Fe/OMCs). 实验通过氮气吸附、扫描电镜、X射线衍射、磁性测试等手段对Fe/OMCs进行了系统的表征. 研究表明, Fe/OMCs基本保持了有序介孔结构, 磁性粒子在材料中以纳米α-Fe粒子的形式存在, 并且具有超顺磁特性. 盐酸四环素(TH)在Fe/OMCs上的吸附研究表明, Fe/OMCs的介孔表面积和介孔孔容是决定TH吸附量的关键因素. 脱附动力学研究表明, Fe/OMCs的孔尺寸是影响脱附速率的关键因素, 孔径越大, TH的脱附速率就越大.  相似文献   

7.
Carbon nanotubes‐magnetic nanoparticles, comprising ferroferric oxide nanoparticles and carbon nanotubes, were prepared through a simple one‐step synthesis method and subsequently applied to magnetic solid‐phase extraction for the determination of polyether antibiotic and s‐triazine drug residues in animal food coupled with liquid chromatography with tandem mass spectrometry. The nanocomposites were characterized by transmission electron microscopy, X‐ray diffraction, and vibrating sample magnetometry. The components within the nanocomposites endowed the material with high extraction performance and manipulative convenience. Compared with carbon nanotubes, the as‐prepared carbon nanotubes‐magnetic nanoparticles showed better extraction and separation efficiencies for polyether antibiotics and s‐triazine drugs thanks to the contribution of the iron‐containing magnetic nanoparticles. Various experimental parameters affecting the extraction efficiency had been investigated in detail. Under the optimal conditions, the good linearity ranging from 1 to 200 μg/kg for diclazuril, toltrazuril, toltrazuril sulfone, lasalocid, monensin, salinomycin, narasin, nanchangmycin, and maduramicin, low limits of detection ranging from 1 to 5 μg/kg, and satisfactory spiked recoveries (77.1–91.2%, with the inter relative standard deviation values from 4.0 to 12.2%) were shown. It was confirmed that this novel method was an efficient pretreatment and enrichment procedure and could be successfully applied for extraction and determination of polyether and s‐triazine drug residues in complex matrices.  相似文献   

8.
Injection of nanoscale zero-valent iron (NZVI) is potentially a promising technology for remediation of contaminated groundwaters. However, the efficiency of this process is significantly hindered by the rapid aggregation of the iron nanoparticles. The aim of this study was to enhance the colloidal stability of the nanoparticles through the addition of the "green" polymer guar gum. We evaluated the properties of guar gum and its influence on the surface properties, particle size, aggregation, and sedimentation of iron nanoparticles. Commercial iron nanoparticles were dispersed in guar gum solutions, and their aggregation and sedimentation behaviors were compared to those of bare iron nanoparticles and commercial nanoparticles modified with a biodegradable polymer (polyaspartate). High performance size exclusion chromatography, charge titration, and viscosity assessment showed that guar gum is a high molecular weight polymer which is nearly neutrally charged, rendering it suitable for steric stabilization of the iron nanoparticles. Electrophoretic mobility measurements demonstrated the ability of guar gum to adsorb on the nanoparticles, forming a slightly negatively charged layer. Dynamic light scattering experiments were conducted to estimate the particle size of the different nanoparticle suspensions and to determine the aggregation behavior at different ionic strengths. Guar gum effectively reduced the hydrodynamic radius of the bare nanoparticles from 500 nm to less than 200 nm and prevented aggregation of the nanoparticles even at very high salt concentrations (0.5 M NaCl and 3 mM CaCl(2)). Sedimentation profiles of the different nanoparticle suspensions confirmed the improved stability of the iron nanoparticles in the presence of guar gum. The results strongly suggest that guar gum can be used to effectively deliver stabilized zero-valent iron nanoparticles for remediation of contaminated groundwater aquifers.  相似文献   

9.
Heteroatom doped carbon dots(CDs) with distinct merits are of great attractions in various fields such as solar cells, catalysis, trace element detection and photothermal therapy. In this work, we successfully synthesized blue-fluorescence and photostability manganese-doped carbon dots(Mn-CDs) with a quantum yield up to 7.5%, which was prepared by a facile one-step hydrothermal method with sodium citrate and manganese chloride. The Mn-CDs is the high mono-dispersity, uniform spherical nanoparticles. The Mn element plays a critical role in achieving a high quantum yield in synthesis of carbon dots, which was confirmed by the structure analysis using XPS and FTIR. Spectroscopic investigations proved that the decent PLQY and luminescence properties of Mn-CDs are due to the heteroatom doped, oxidized carbon-based surface passivation. In addition, the Mn-CDs are demonstrated as promising fluorescent sensors for iron ions with a linear range of 0–500 mmol/L and a detection limit of2.1 nmol/L(turn-off), indicating their great potential as a fluorescent probe for chemical sensing.  相似文献   

10.
Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.  相似文献   

11.
采用Polyol合成法,以三嵌段共聚物PEO-PPO-PEO为表面活性剂,以1,2-十六烷二醇为还原剂,乙酰丙酮钴(Ⅱ)、乙酰丙酮铁(Ⅱ)和醋酸金为前驱体,成功合成了CoFeAu纳米粒子.傅立叶变换红外光谱(FT-IR)分析证实了共聚物PEO-PPO-PEO包裹在CoFeAu纳米颗粒表面,X射线衍射仪(XRD)测试得出该纳米粒子是面心立方晶体结构、晶格参数为0.406nm、结晶性能好.紫外可见近红外分光光度计吸收光谱仪和振动样品磁强计(VSM)测试证明了该纳米粒子兼具良好的光学和磁学特性.该多功能CoFeAu纳米粒子有望在催化材料、磁材料、光电和生物医药等方面发挥有益作用.  相似文献   

12.
以热解型Fe/N/C为代表的碳基非贵金属材料被认为是当前最具潜力替代铂的非贵金属氧还原催化剂,其综合性能的进一步突破,对于推动质子交换膜燃料电池商业化应用具有重要意义。对热解型Fe/N/C催化剂活性位结构的深入认识是实现催化剂高活性位密度和高稳定性理性设计的关键。本文总结了热解型Fe/N/C活性位的研究进展,重点介绍了非晶态铁氮配位活性中心、氮掺杂和碳缺陷三类活性位构型。由于热解型Fe/N/C是非均相的,结构非常复杂,导致在活性位认识上还存在诸多争议,本文总结阐述了活性位结构的不同观点。最后,我们展望了Fe/N/C催化剂活性位研究的未来方向。  相似文献   

13.
Dai X  Wildgoose GG  Compton RG 《The Analyst》2006,131(8):901-906
The electrocatalytic detection of the anaesthetic halothane on a multiwalled carbon nanotube modified glassy carbon electrode is reported with a low limit of detection of 4.6 microM. A thorough investigation of the underlying cause of this apparent catalytic effect is undertaken by comparing the response of various carbon electrodes including glassy carbon, basal- and edge-plane pyrolytic graphite electrodes (bppg and eppg respectively) to increasing additions of halothane. The reduction of halothane is shifted by 250-300 mV to more negative potentials at an eppg electrode than that observed at the GC-CNT electrode. Therefore the results of this investigation show that, surprisingly, the electrocatalysis is not solely due to the introduction of edge-plane-like defect sites on the carbon nanotubes as is commonly found for many other substrates showing favourable voltammetry at nanotube modified electrodes. Instead, we reveal that in this unusual case the electroactive sites for the reduction of halothane are due to the presence of copper nanoparticles occluded within the carbon nanotubes during their production, which are never completely removed by standard purification techniques such as acid washing. This is only the third known case where apparent electrocatalysis by carbon nanotube modified electrodes is due to occluded metal-related nanoparticles within the nanotube structure, rather than the active sites being the edge-plane-like defect sites on the nanotubes. Furthermore this is the first case where the active sites are nanoparticles of copper metal, rather than metal oxide nanoparticles (namely oxides of iron(II)/(III)) as was found to be the case in the previous examples.  相似文献   

14.
Computer simulations were carried out to investigate the magnetic and wave-absorbing characteristics of iron nanoparticles. The magnetic properties were found to depend on the shape, aggregation, and array of the nanoparticles. Nanoparticle systems were simulated using a molecular dynamics (MD) method, and the resulting configurations were used to compute the magnetic properties of the systems. In this work, microdot magnetic dipoles were assumed to localize on the iron atoms of nanoparticles. The dynamics of these magnetic dipoles under an external magnetic field were simulated by solving the Landau-Lifshitz-Gilbert equation numerically. The energy loss of a system under an external magnetic field was computed from the hysteresis curve and was correlated with the wave-absorbing characteristic of the system. The findings suggested that the disk-shaped iron particles had a greater hysteresis loss energy than the ball-shaped iron particles. It was also found that the aggregation of nanoparticles apparently reduced the wave-absorbing characteristic of the system. All the outcomes were in good agreement with the experimental measurements.  相似文献   

15.
In this research work, novel magnetic superabsorbent hydrogel nanocomposites (MSHNs) based on carboxymethyl cellulose were prepared via a facile “one‐pot” two step approach. Magnetic iron oxide nanoparticles were in situ synthesized and incorporated into carboxymethyl cellulose/poly(acrylic acid) polymer hydrogel. The morphology and chemical composition of MSHNs as well as the presence of magnetic iron oxide nanoparticles were evaluated by using Fourier transform infrared, scanning electron microscopy, transmission electron microscopy, X‐Ray diffraction, ultraviolet–visible spectroscopy, thermogravimetric analysis, and vibrating sample magnetometer. The effect of different reaction parameters on the swelling capacity of MSHNs was investigated. Furthermore, batch adsorption experiments of crystal violet dye onto MSHNs were studied by varying solution pH, initial dye concentration, and temperature. Evaluation of thermodynamic parameters of crystal violet adsorption confirmed that the adsorption was spontaneous and endothermic process in nature. The equilibrium study revealed that the dye adsorption behavior of MHSNs followed the Redlich‐Peterson isotherm model. Finally, the dye adsorption experiment data was well fitted by the pseudo‐second‐order kinetic model with the regression coefficient (R2) of 0.9979. Our results suggest that the MHSNs with facile preparation method, high swelling capacity, and high dye adsorption capacity may be used as promising adsorbents for fast removal of various dyes from aqueous solutions. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

16.
The synthesis and characterization of catalysts based on nanomaterials, supported on multi-walled carbon nanotubes (CNT) for ethylene glycol (EG) oxidation is investigated. Platinum (Pt) and platinum-ruthenium (Pt-Ru) nanoparticles are deposited on surface-oxidized multi-walled carbon nanotubes [Pt/CNT; Pt-Ru/CNT] by the aqueous solution reduction of the corresponding metal salts with glycerol. The electrocatalytic properties of the modified electrodes for oxidation of ethylene glycol in acidic solution have been studied by cyclic voltammetry (CV), and excellent activity is observed. This may be attributed to the small particle size of the metal nanoparticles, the efficacy of carbon nanotubes acting as good catalyst support and uniform dispersion of nanoparticles on CNT surfaces. The nature of the resulting nanoparticles decorated multiwalled carbon nanotubes are characterized by scanning electron microscopy (SEM) and transmission electron microscopic (TEM) analysis. The cyclic voltammetry response indicates that Pt-Ru/CNT catalyst displays a higher performance than Pt/CNT, which may be due to the efficiency of the nature of Ru species in Pt-Ru systems. The fabricated Pt and Pt-Ru nanoparticles decorated CNT electrodes shows better catalytic performance towards ethylene glycol oxidation than the corresponding nanoparticles decorated carbon electrodes, demonstrating that it is more promising for use in fuel cells.  相似文献   

17.
通过油酸盐前驱体高温热解法制备出大小均匀的钴掺杂四氧化三铁球形纳米粒子, 其钴/铁摩尔比可以通过调节油酸钴与油酸铁的比例进行调变. 当产物中钴/铁摩尔比从0.024增加到0.156, 所制备的氧化铁纳米粒子的饱和磁矩从39 emu·g-1逐渐减小到30 emu·g-1, 而矫顽力从0 Oe升至190 Oe. 在305℃下, 随着反应体系的热解时间由0.5 h 增加到3 h, 所制备出的氧化铁纳米粒子尺寸逐渐由7 nm增加到14 nm. 热解时间较短时, 以高价态的四氧化三铁的晶型为主, 辅之以少量的氧化亚铁; 热解时间增加至2 h, 产物的晶型为四氧化三铁和氧化亚铁的复合物; 而继续增加热解时间至3 h, 除四氧化三铁和氧化亚铁之外, 还出现少量的零价态的CoFe合金, 说明铁(钴)元素经历了由三价到二价, 最后被还原为零价的过程. 随着反应温度的升高, 产物的尺寸逐渐增大, 同时产物中氧化亚铁的含量增多.  相似文献   

18.
Hollow magnetic nanoparticles (MNPs) with tetrahedral morphology were synthesized and then covered by a shell prepared by coating with melamine–formaldehyde followed by the introduction of glucose‐derived carbon. Subsequently, Pd nanoparticles were immobilized and the core–shell nanocomposite was carbonized. The obtained magnetic catalyst was successfully applied for the hydrogenation of nitroarenes in aqueous media. To investigate the effects of the morphology of MNPs, the nature of carbon shell, and the order of incorporation of Pd nanoparticles, several control catalysts, including the MNPs with different morphologies (disc‐like and cylinder); MNPs coated with different shells (sole glucose‐derived carbon or melamine–formaldehyde carbon shell); and a nanocomposite, in which Pd was immobilized after carbonization, were prepared and examined as catalyst for the model reaction. To justify the observed different catalytic activities of the catalysts, their Pd loadings, leaching, and specific surface areas were compared. The results confirmed that tetrahedral MNPs coated with porous N‐rich carbon shell exhibited the best catalytic activity. The high catalytic activity of this catalyst was attributed to its high surface area and the interaction of N‐rich shell with Pd nanoparticles that led to the higher Pd loading and suppressed Pd leaching.  相似文献   

19.
采用一罐纳米乳液法,以聚乙二醇-聚丙二醇-聚乙二醇(PEO-PPO-PEO)三嵌段共聚物为表面活性剂,通过还原前驱体乙酰丙酮镍、乙酰丙酮铁(Ⅱ)和醋酸金,成功制备了NiFeAu纳米粒子.采用透射电镜和X射线衍射仪分析了NiFeAu纳米粒子的形貌和结构;采用傅立叶变换红外光谱仪分析了三嵌段共聚物在NiFeAu纳米颗粒表面的覆盖情况;采用紫外-可见吸收光谱仪和振动样品磁强计测试了纳米粒子的光学和磁学特性.结果表明,三嵌段共聚物成功地结合于NiFeAu纳米颗粒表面;所制备的纳米粒子粒径分布较窄、结晶性能良好,并兼具光学和磁学特性.  相似文献   

20.
Efficient hydrogen evolution reaction (HER) through effective and inexpensive electrocatalysts is a valuable approach for clean and renewable energy systems. Here, single‐shell carbon‐encapsulated iron nanoparticles (SCEINs) decorated on single‐walled carbon nanotubes (SWNTs) are introduced as a novel highly active and durable non‐noble‐metal catalyst for the HER. This catalyst exhibits catalytic properties superior to previously studied nonprecious materials and comparable to those of platinum. The SCEIN/SWNT is synthesized by a novel fast and low‐cost aerosol chemical vapor deposition method in a one‐step synthesis. In SCEINs the single carbon layer does not prevent desired access of the reactants to the vicinity of the iron nanoparticles but protects the active metallic core from oxidation. This finding opens new avenues for utilizing active transition metals such as iron in a wide range of applications.  相似文献   

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