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1.
Developing microwave absorption materials with ultrawide bandwidth and low density still remains a challenge, which restricts their actual application in electromagnetic signal anticontamination and defense stealth technology. Here a series of olive‐like γ‐Fe2O3@C core–shell spindles with different shell thickness and γ‐Fe2O3@C@α‐MnO2 spindles with different volumes of dipolar‐distribution cavities were successfully prepared. Both series of absorbers exhibit excellent absorption properties. The γ‐Fe2O3@C@α‐MnO2 spindle with controllable cavity volume exhibits an effective absorption (2O3@C spindle reaches as high as ?45 dB because of the optimized electromagnetic impedance balance between polymer shell and γ‐Fe2O3 core. Intrinsic ferromagnetism of the anisotropy spindle is confirmed by electron holography. Strong coupling of magnetic flux stray lines between spindles is directly imaged. This unique morphology and facile etching technique might facilitate the study of core–shell type microwave absorbers.  相似文献   

2.
Magnetic fluid hyperthermia has been recently considered as a Renaissance of cancer treatment modality due to its remarkably low side effects and high treatment efficacy compared to conventional chemotheraphy or radiotheraphy. However, insufficient AC induction heating power at a biological safe range of AC magnetic field (Happl·fappl < 3.0–5.0 × 109 A m?1 s?1), and highly required biocompatibility of superparamagnetic nanoparticle (SPNP) hyperthermia agents are still remained as critical challenges for successful clinical hyperthermia applications. Here, newly developed highly biocompatible magnesium shallow doped γ‐Fe2O3 (Mg0.13‐γFe2O3) SPNPs with exceptionally high intrinsic loss power (ILP) in a range of 14 nH m2 kg?1, which is an ≈100 times higher than that of commercial Fe3O4 (Feridex, ILP = 0.15 nH m2 kg?1) at Happl·fappl = 1.23 × 109 A m?1 s?1 are reported. The significantly enhanced heat induction characteristics of Mg0.13‐γFe2O3 are primarily due to the dramatically enhanced out‐of‐phase magnetic susceptibility and magnetically tailored AC/DC magnetic softness resulted from the systematically controlled Mg2+ cations distribution and concentrations in octahedral site Fe vacancies of γ‐Fe2O3 instead of well‐known Fe3O4 SPNPs. In vitro and in vivo magnetic hyperthermia studies using Mg0.13‐γFe2O3 nanofluids are conducted to estimate bioavailability and biofeasibility. Mg0.13‐γFe2O3 nanofluids show promising hyperthermia effects to completely kill the tumors.  相似文献   

3.
Highly porous hosting materials with conducting (favorable to electron transfer) and magnetic (favorable to product separation) bicontinuous networks should possess great potentials for immobilization of various enzymes in the field of biocatalytic engineering, but the synthesis of such materials is still a great challenge. Herein, bifunctional graphene/γ‐Fe2O3 hybrid aerogels with quite low density (30–65 mg cm?3), large specific surface area (270–414 m2 g?1), high electrical conductivity (0.5–5 × 10?2 S m?1), and superior saturation magnetization (23–54 emu g?1) are fabricated. Single networks of either graphene aerogels or γ‐Fe2O3 aerogels are obtained by etching of the hybrid aerogels with acid solution or calcining of the hybrid aerogels in air, indicative of the double networks of the as‐synthesized graphene/γ‐Fe2O3 hybrid aerogels for the first time. The resulting bifunctional aerogels are used to immobilize β‐glucuronidase for biocatalytic transformation of glycyrrhizin into glycyrrhetinic acid monoglucuronide or glycyrrhetinic acid, with high biocatalytic activity and definite repeatability.  相似文献   

4.
In this work, the optical and mechanical properties of Fe2O3 nanoparticles (NPs)/chitosan nanocomposite films have been investigated. Nanocomposite films of different weight ratios of Fe2O3 NPs/chitosan (0, 1, 5, 10, 20 and 30 wt%) were fabricated using casting technique. The optical properties of colloidal Fe2O3 NPs and Fe2O3 NPs/chitosan nanocomposite films were recorded using UV–visible spectrophotometer. As the ratio of Fe2O3 NPs to chitosan increases from 0 to 30%, the energy band gap of Fe2O3 NPs/chitosan films decreases from 3.16 to 2.11 eV. This decrease is due to quantum confinement effect. The mechanical properties of the nanocomposite films as a function of sweeping temperature were measured using a dynamic mechanical analyzer. An enhancement in storage modulus, stiffness and glass transition temperature (Tg) has been observed as the ratio of Fe2O3 NPs/chitosan increases. Tg of Fe2O3 NPs/chitosan nanocomposite film shifts towards higher temperature side with respect to pure chitosan film from 152.1 to 166.3?°C as the ratio of Fe2O3 NPs/chitosan increases from 0 to 30 wt%. The increase in Tg is mainly attributed to the decrease in free volumes and vacancies in the nanocomposite films as the weight ratio of Fe2O3 NPs/chitosan increases.  相似文献   

5.
Although chemoselective hydrogenation of unsaturated aldehydes is the major route to highly valuable industrially demanded unsaturated alcohols, it is still challenging, as the production of saturated aldehydes is more favorable over unsaturated alcohols from the view of thermodynamics. By combining the structural features of porous nanowires (NWs) and metal‐organic frameworks (MOFs), a unique class of porous Pt‐Ni NWs in situ encapsuled by MOFs (Pt‐Ni NWs@Ni/Fex‐MOFs) is designed to enhance the unsaturated alcohols selectivity in the cinnamaldehyde (CAL) hydrogenation. A detailed catalytic study shows that the porous Pt‐Ni NWs@Ni/Fex‐MOFs exhibit volcano‐type activity and selectivity in CAL hydrogenation as a function of Fe content. The optimized porous PtNi2.20 NWs@Ni/Fe4‐MOF is highly active and selective with 99.5% CAL conversion and 83.3% cinnamyl alcohol selectivity due to the confinement effect, appropriate thickness of MOF and its optimized electronic structure, and excellent durability with negligible activity and selectivity loss after five runs.  相似文献   

6.
AuroShell nanoparticles (sealed gold nanoshell on silica) are the only inorganic materials that are approved for clinical trial for photothermal ablation of solid tumors. Based on that, porous gold nanoshell structures are thus critical for cancer multiple theranostics in the future owing to their inherent cargo‐loading ability. Nevertheless, adjusting the diverse experimental parameters of the reported procedures to obtain porous gold nanoshell structures is challenging. Herein, a series of amino‐functionalized porous metal–organic frameworks (NH2‐MOFs) nanoparticles are uncovered as superior templates for porous gold nanoshell deposition (NH2‐MOFs@Aushell) by means of a more facile and general one‐step method, which combines the enriched functionalities of NH2‐MOFs with those of porous gold nanoshells. Moreover, in order to illustrate the promising applications of this method in biomedicine, platinum nanozymes‐encapsulated NH2‐MOFs are further designed with porous gold nanoshell coating and photosensitizer chlorin e6 (Ce6)‐loaded nanoparticles with continuous O2‐evolving ability (Pt@UiO‐66‐NH2@Aushell‐Ce6). The combination of photodynamic and photothermal therapy is then carried out both in vitro and in vivo, achieving excellent synergistic therapeutic outcomes. Therefore, this work not only presents a facile strategy to fabricate functionalized porous gold nanoshell structures, but also illustrates an excellent synergistic tumor therapy strategy.  相似文献   

7.
Titanium dioxide (TiO2) has been widely investigated and used in many areas due to its high refractive index and ultraviolet light absorption, but the lack of absorption in the visible–near infrared (Vis–NIR) region limits its application. Herein, multifunctional Fe@γ‐Fe2O3@H‐TiO2 nanocomposites (NCs) with multilayer‐structure are synthesized by one‐step hydrogen reduction, which show remarkably improved magnetic and photoconversion effects as a promising generalists for photocatalysis, bioimaging, and photothermal therapy (PTT). Hydrogenation is used to turn white TiO2 in to hydrogenated TiO2 (H‐TiO2), thus improving the absorption in the Vis–NIR region. Based on the excellent solar‐driven photocatalytic activities of the H‐TiO2 shell, the Fe@γ‐Fe2O3 magnetic core is introduced to make it convenient for separating and recovering the catalytic agents. More importantly, Fe@γ‐Fe2O3@H‐TiO2 NCs show enhanced photothermal conversion efficiency due to more circuit loops for electron transitions between H‐TiO2 and γ‐Fe2O3, and the electronic structures of Fe@γ‐Fe2O3@H‐TiO2 NCs are calculated using the Vienna ab initio simulation package based on the density functional theory to account for the results. The reported core–shell NCs can serve as an NIR‐responsive photothermal agent for magnetic‐targeted photothermal therapy and as a multimodal imaging probe for cancer including infrared photothermal imaging, magnetic resonance imaging, and photoacoustic imaging.  相似文献   

8.
The challenge of bacterial infection increases the risk of mortality and morbidity in acute and chronic wound healing. Silver nanoparticles (Ag NPs) are a promising new version of conventional antibacterial nanosystem to fight against the bacterial resistance in concern of the drug discovery void. However, there are several challenges in controlling the size and colloidal stability of Ag NPs, which readily aggregate or coalesce in both solid and aqueous state. In this study, a template‐guided synthesis of ultrafine Ag NPs of around 2 nm using water‐soluble and biocompatible γ‐cyclodextrin metal‐organic frameworks (CD‐MOFs) is reported. The CD‐MOF based synthetic strategy integrates AgNO3 reduction and Ag NPs immobilization in one pot achieving dual functions of reduced particle size and enhanced stability. Meanwhile, the synthesized Ag NPs are easily dispersible in aqueous media and exhibit effective bacterial inhibition. The surface modification of cross‐linked CD‐MOF particles with GRGDS peptide boosts the hemostatic effect that further enhances wound healing in synergy with the antibacterial effect. Hence, the strategy of ultrafine Ag NPs synthesis and immobilization in CD‐MOFs together with GRGDS modification holds promising potential for the rational design of effective wound healing devices.  相似文献   

9.
Metal–organic frameworks (MOFs) have recently emerged as a type of uniformly and periodically atom‐distributed precursor and efficient self‐sacrificial template to fabricate hierarchical porous‐carbon‐related nanostructured functional materials. For the first time, a Cu‐based MOF, i.e., Cu‐NPMOF is used, whose linkers contain nitrogen and phosphorus heteroatoms, as a single precursor and template to prepare novel Cu3P nanoparticles (NPs) coated by a N,P‐codoped carbon shell that is extended to a hierarchical porous carbon matrix with identical uniform N and P doping (termed Cu3P@NPPC) as an electrocatalyst. Cu3P@NPPC demonstrates outstanding activity for both the hydrogen evolution and oxygen reduction reaction, representing the first example of a Cu3P‐based bifunctional catalyst for energy‐conversion reactions. The high performances are ascribed to the high specific surface area, the synergistic effects of the Cu3P NPs with intrinsic activity, the protection of the carbon shell, and the hierarchical porous carbon matrix doped by multiheteroatoms. This strategy of using a diverse MOF as a structural and compositional material to create a new multifunctional composite/hybrid may expand the opportunities to explore highly efficient and robust non‐noble‐metal catalysts for energy‐conversion reactions.  相似文献   

10.
Pd@CeO2/Al2O3 catalysts are of great importance for real applications, such as three‐way catalysis, CO oxidation, and methane combustion. In this article, the Pd@CeO2 core@shell nanospheres are prepared via the autoredox reaction in aqueous phase. Three kinds of methods are then employed, that is, electrostatic interaction, supramolecular self‐assembly, and physical mixing, to support the as‐prepared Pd@CeO2 nanospheres on γ‐Al2O3. A model reaction of catalytic methane‐combustion is employed here to evaluate the three Pd@CeO2/γ‐Al2O3 samples. As a result, the sample Pd@CeO2‐S‐850 prepared via supramolecular self‐assembly and calcined at 850 °C exhibits superior catalytic performance to the others, which has a far lower light‐off temperature (T50 of about 364 °C). Moreover, almost no deterioration of Pd@CeO2‐S‐850 is observed after five sequent catalytic cycles. The analysis of H2‐TPR curves concludes that there exists hydrogen spillover related to the strong metal–support interaction between Pd species and oxides. The strong metal–support interaction and the specific surface areas might be responsible for the catalytic performance of the Pd@CeO2 samples toward catalytic methane combustion.  相似文献   

11.
The hydrogen and carbon monoxide separation is an important step in the hydrogen production process. If H2 can be selectively removed from the product side during hydrogen production in membrane reactors, then it would be possible to achieve complete CO conversion in a single‐step under high temperature conditions. In the present work, the multilayer amorphous‐Si‐B‐C‐N/γ‐Al2O3/α‐Al2O3 membranes with gradient porosity have been realized and assessed with respect to the thermal stability, geometry of pore space and H2/CO permeance. The α‐Al2O3 support has a bimodal pore‐size distribution of about 0.64 and 0.045 µm being macroporous and the intermediate γ‐Al2O3 layer—deposited from boehmite colloidal dispersion—has an average pore‐size of 8 nm being mesoporous. The results obtained by the N2‐adsorption method indicate a decrease in the volume of micropores—0.35 vs. 0.75 cm3 g?1—and a smaller pore size ?6.8 vs. 7.4 Å—in membranes with the intermediate mesoporous γ‐Al2O3 layer if compared to those without. The three times Si‐B‐C‐N coated multilayer membranes show higher H2/CO permselectivities of about 10.5 and the H2 permeance of about 1.05 × 10?8 mol m?2 s?1 Pa?1. If compared to the state of the art of microporous membranes, the multilayer Si‐B‐C‐N/γ‐Al2O3/α‐Al2O3 membranes are appeared to be interesting candidates for hydrogen separation because of their tunable nature and high‐temperature and high‐pressure stability.  相似文献   

12.
Metal–organic frameworks (MOFs) are very promising self‐sacrificing templates for the large‐scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N‐doped carbon‐coated ZnO/ZnCo2O4/CuCo2O4 nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore‐forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium‐ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g?1 after 500 cycles at a current density of 0.3 mA g?1. Furthermore, the material shows large storage capacities (1009 and 667 mAh g?1), even at high current flow (3 and 10 A g?1). The remarkable high‐rate capability and outstanding long‐life cycling stability of the multidoped metal oxide benefits from the carbon‐coated integrated nanostructure with a hollow interior and the three active metal oxide components.  相似文献   

13.
Fe3O4 nanoparticles (NPs) with Ag NPs evenly distributed on the surface are fabricated by using polydopamine (PDA) as the intermediate layer. Silanization and thiol chemistry are used to firmly combine the Fe3O4@ PDA core and outer surface Ag NPs. The spherical and hybrid nanoparticles are termed Fe3O4@PDA@Ag NPs, which possess a core–shell and hierarchical structure. After surface modification with 1H,1H,2H,2H‐perfluorodecanethiol, the hybrid Fe3O4@PDA@Ag NPs become highly hydrophobic. Slight rolling of a water droplet on the as‐prepared NPs causes the formation of a “liquid marble”, which is capable of performing remote actuation on various solid surfaces, such as glass sheet, paper, plastic, textile, and ceramic, and at the liquid–air interface using a permanent magnet. Liquid marbles with self‐assembled NPs on the liquid surface have potential to act as a miniaturized reactor for manipulation of inner liquid droplet with high positioning precision. In addition, the Fe3O4@PDA@Ag NPs are multifunctional and can be applied for oil/water separation and antibacterial purpose.  相似文献   

14.
An effective colloidal process involving the hot‐injection method is developed to synthesize uniform nanoflowers consisting of 2D γ‐In2Se3 nanosheets. By exploiting the narrow direct bandgap and high absorption coefficient in the visible light range of In2Se3, a high‐quality γ‐In2Se3/Si heterojunction photodiode is fabricated. This photodiode shows a high photoresponse under light illumination, short response/recovery times, and long‐term durability. In addition, the γ‐In2Se3/Si heterojunction photodiode is self‐powered and displays a broadband spectral response ranging from UV to IR with a high responsivity and detectivity. These excellent performances make the γ‐In2Se3/Si heterojunction very interesting as highly efficient photodetectors.  相似文献   

15.
When using the bottom‐up approach with anisotropic building‐blocks, an important goal is to find simple methods to elaborate nanocomposite materials with a truly macroscopic anisotropy. Here, micrometer size colloidal mesoporous particles with a highly anisotropic rod‐like shape (aspect ratio ≈ 10) have been fabricated from silica (SiO2) and iron oxide (Fe2O3). When dispersed in a solvent, these particles can be easily oriented using a magnetic field (≈200 mT). A macroscopic orientation of the particles is achieved, with their long axis parallel to the field, due to the shape anisotropy of the magnetic component of the particles. The iron oxide nanocrystals are confined inside the porosity and they form columns in the nanochannels. Two different polymorphs of Fe2O3 iron oxide have been stabilized, the superparamagnetic γ‐phase and the rarest multiferroic ε‐phase. The phase transformation between these two polymorphs occurs around 900 °C. Because growth occurs under confinement, a preferred crystallographic orientation of iron oxide is obtained, and structural relationships between the two polymorphs are revealed. These findings open completely new possibilities for the design of macroscopically oriented mesoporous nanocomposites, using such strongly anisotropic Fe2O3/silica particles. Moreover, in the case of the ε‐phase, nanocomposites with original anisotropic magnetic properties are in view.  相似文献   

16.
Multi-walled carbon nanotubes (MWCNTs) can act not only as a support for Fe3O4 nanoparticles (NPs) but also as a coworker with synergistic effect, accordingly improving the heterogeneous Fenton-like efficiency of Fe3O4 NPs. In this study, Fe3O4 NPs were in situ anchored onto MWCNTs by a moderate co-precipitation method and the as-prepared Fe3O4/MWCNTs nanocomposites were employed as the highly efficient Fenton-like catalysts. The analyses of XRD, FTIR, Raman, FESEM, TEM and HRTEM results indicated the formation of Fe3O4 crystals in Fe3O4/MWCNTs nanocomposites prepared at different conditions and the interaction between Fe3O4 NPs and MWCNTs. Over a wide pH range, the surface of modified MWCNTs possessed negative charges. Based on these results, the possible combination mechanism between Fe3O4 NPs and MWCNTs was discussed and proposed. Moreover, the effects of preparation and catalytic conditions on the Fenton-like catalytic efficiency were investigated in order to gain further insight into the heterogeneous Fenton-like reaction catalyzed by Fe3O4/MWCNTs nanocomposites.  相似文献   

17.
A simple and quick microwave method to prepare high performance magnetite nanoparticles (Fe3O4 NPs) directly from Fe has been developed. The as-prepared Fe3O4 NPs product was fully characterized by X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The results show that the as-prepared Fe3O4 NPs are quite monodisperse with an average core size of 80 × 5 nm. The microwave synthesis technique can be easily modified to prepare Fe3O4/Ag NPs and these NPs possess good magnetic properties. The formation mechanisms of the NPs are also discussed. Our proposed synthesis procedure is quick and simple, and shows potential for large-scale production and applications for catalysis and biomedical/biological uses.  相似文献   

18.
High capacity transition‐metal oxides play significant roles as battery anodes benefiting from their tunable redox chemistry, low cost, and environmental friendliness. However, the application of these conversion‐type electrodes is hampered by inherent large volume variation and poor kinetics. Here, a binary metal oxide prototype, denoted as nonhierarchical heterostructured Fe2O3/Mn2O3 porous hollow spheres, is proposed through a one‐pot self‐assembly method. Beyond conventional heteromaterial, Fe2O3/Mn2O3 based on the interface of (104)Fe2O3 and (222)Mn2O3 exhibits the nonhierarchical configuration, where nanosized building blocks are integrated into microsized spheres, leading to the enhanced structural stability and boosted reaction kinetics. With this design, the Fe2O3/Mn2O3 anode shows a high reversible capacity of 1075 mA h g?1 at 0.5 A g?1, an outstanding rate capability of 638 mA h g?1 at 8 A g?1, and an excellent cyclability with a capacity retention of 89.3% after 600 cycles.  相似文献   

19.
Carbon micro‐/nanocages have attracted great attention owing to their wide potential applications. Herein, a self‐templated strategy is presented for the synthesis of a hydrangea‐like superstructure of open carbon cages through morphology‐controlled thermal transformation of core@shell metal–organic frameworks (MOFs). Direct pyrolysis of core@shell zinc (Zn)@cobalt (Co)‐MOFs produces well‐defined open‐wall nitrogen‐doped carbon cages. By introducing guest iron (Fe) ions into the core@shell MOF precursor, the open carbon cages are self‐assembled into a hydrangea‐like 3D superstructure interconnected by carbon nanotubes, which are grown in situ on the Fe–Co alloy nanoparticles formed during the pyrolysis of Fe‐introduced Zn@Co‐MOFs. Taking advantage of such hierarchically porous superstructures with excellent accessibility, synergetic effects between the Fe and the Co, and the presence of catalytically active sites of both metal nanoparticles and metal–Nx species, this superstructure of open carbon cages exhibits efficient bifunctional catalysis for both oxygen evolution reaction and oxygen reduction reaction, achieving a great performance in Zn–air batteries.  相似文献   

20.
A unique dendrimer‐assisted approach is reported to create Fe3O4/Au nanocomposite particles (NCPs) for targeted dual mode computed tomography/magnetic resonance (CT/MR) imaging of tumors. In this approach, preformed Fe3O4 nanoparticles (NPs) are assembled with multilayers of poly(γ‐glutamic acid) (PGA)/poly(l ‐lysine)/PGA/folic acid (FA)‐modified dendrimer‐entrapped gold nanoparticles via a layer‐by‐layer self‐assembly technique. The interlayers are crosslinked via 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide chemistry, the assembled Au core NPs are then used as seed particles for subsequent seed‐mediated growth of Au shells via iterative Au salt reduction process, and subsequent acetylation of the remaining amines of dendrimers leads to the formation of Fe3O4/Aun.Ac‐FA NCPs with a tunable molar ratio of Au/Fe3O4. It is shown that the Fe3O4/Aun.Ac‐FA NCPs at an optimized Au/Fe3O4 molar ratio of 2.02 display a relatively high R2 relaxivity (92.67 × 10?3 M?1 s?1) and good X‐ray attenuation property, and are cytocompatible and hemocompatible in the given concentration range. Importantly, with the FA‐mediated targeting, the Fe3O4/Aun.Ac‐FA NCPs are able to be specifically uptaken by cancer cells overexpressing FA receptors, and be used as an efficient nanoprobe for targeted dual mode CT/MR imaging of a xenografted tumor model. With the versatile dendrimer chemistry, the developed Fe3O4/Au NCPs may be differently functionalized, thereby providing a unique platform for diagnosis and therapy of different biological systems.  相似文献   

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