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1.
Metallic crystalline/amorphous core–shell nanoparticles consisting of a crystalline Pd core (c‐Pd) surrounded by an amorphous Fe25Sc75 shell (a‐FeSc) are prepared by inert‐gas condensation. A phase transformation of the c‐Pd by a solid‐state diffusion process resulting in an amorphous core (a‐PdSc) surrounded by an amorphous FeSc shell is observed if the core–shell structure is irradiated at ambient temperature with 300 keV electrons. The amorphization process seems to involve the diffusion of irradiation‐induced defects and is presumably driven by the large negative heat of mixing of Pd and Sc, as well as by the excess enthalpy of the interfaces between the c‐Pd regions and the surrounding a‐FeSc. The structural transformation reported here opens a new way to producing metallic amorphous core–shell nanoparticles of different chemical compositions and probably novel properties.  相似文献   

2.
As one promising anode material with high theoretical capacity, metallic tin has attracted much research interest in the field of lithium‐ion batteries. Here, two types of tin/carbon (Sn@C) core–shell nanostructures with inner buffering voids are fabricated from SnO2 hollow nanospheres via a facile chemical vapor deposition (CVD) method. The crystallinity and surface topography of SnO2 hollow nanospheres are found to affect the morphology of resultant Sn@C materials. Sn@C yolk–shell nanospheres and core–sheath nanowires are obtained from the as‐prepared SnO2 and high‐temperature annealed SnO2 nanospheres, respectively. The unique Sn@C nanostructures can mitigate the agglomeration/pulverization of Sn nanoparticles and electrical disconnection from the current collector caused by the large volume change during the lithium alloying/dealloying process. Both Sn@C yolk–shell and core–sheath nanostructures show stable cycling performance up to 500 cycles with specific capacities of ca. 430 and 520 mA h g?1, respectively.  相似文献   

3.
Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L3‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.  相似文献   

4.
Irradiation effect of low-energy ion beam has been investigated on nanocoating developed with silica, titania and silica–titania core–shell nanoparticles embedded in an organic binder for nanopaint application. In this work, we have taken polyurethane as a model organic binder. Silica nanoparticles have been prepared through sol–gel synthesis with a particle size of 85?nm. Titania and core–shell nanoparticles have been prepared through both sol–gel and peptization process. Particle sizes obtained were 107?nm for titania and 240?nm for core–shell nanoparticles prepared through sol–gel process and 75?nm for TiO2 and 144?nm for core–shell nanoparticles prepared through peptization process. The coating formulations were developed with the above nanoparticles individually and nanoparticle concentration was varied from 1 to 6?wt% and the best performance in terms of hydrophobicity was obtained with 4?wt % of the nanoparticles in polyurethane coating formulation. All the coating formulations prepared were applied on a glass substrate and dried at 100°C. The dry film thickness obtained was around 100?µm in each case. These films dried on glass substrate were irradiated by nitrogen and argon ion beam with energy of 26?keV at fluences of 1014 to 1016?ions/cm2. The anti-algal property of the irradiated samples was improved and hydrophobicity was reduced.  相似文献   

5.
A scalable synthesis of magnetic core–shell nanocomposite particles, acting as a novel class of magnetic resonance (MR) contrast agents, has been developed. Each nanocomposite particle consists of a biocompatible chitosan shell and a poly(methyl methacrylate) (PMMA) core where multiple aggregated γ‐Fe2O3 nanoparticles are confined within the hydrophobic core. Properties of the nanocomposite particles including their chemical structure, particle size, size distribution, and morphology, as well as crystallinity of the magnetic nanoparticles and magnetic properties were systematically characterized. Their potential application as an MR contrast agent has been evaluated. Results show that the nanocomposite particles have good stability in biological media and very low cytotoxicity in both L929 mouse fibroblasts (normal cells) and HeLa cells (cervical cancer cells). They also exhibited excellent MR imaging performance with a T2 relaxivity of up to 364 mMFe?1 s?1. An in vivo MR test performed on a naked mouse bearing breast tumor indicates that the nanocomposite particles can localize in both normal liver and tumor tissues. These results suggest that the magnetic core–shell nanocomposite particles are an efficient, inexpensive and safe T2‐weighted MR contrast agent for both liver and tumor MR imaging in cancer therapy.  相似文献   

6.
Large‐scale and tunable synthesis of FeCo/graphitic carbon (FeCo/GC) core–shell nanoparticles as a promising material for multipurpose biomedical applications is reported. The high‐quality graphitic structure of the carbon shells is demonstrated through high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), and Raman spectroscopy. A saturation magnetization of 80.2 emu g?1 is reached for the pure FeCo/GC core–shell nanoparticles. A decrease in the saturation magnetization of the samples is observed with an increase in their carbon content with different carbon morphologies evolved in the process. It is also shown how hybrid nanostructures, including mixtures of the FeCo/GC nanoparticles and multi‐walled carbon nanotubes (MWNTs) or carbon nanorods (CNRs), can be obtained only by manipulation of the carbon‐bearing gas flow rate.  相似文献   

7.
Spinel ferrites hold great promise as attractive electrode materials for high‐performance supercapacitors owing to their multiple valence states and abundant choice of metal cation. However, the main bottleneck for most of the currently reported spinel ferrite‐based electrodes is relatively low specific capacitance. Herein, a new kind of lithium ferrites (Li0.5Fe2.5O4, LFO)@polydopamine (PDA) (denoted as LFO@PDA) core–shell nanoparticles with extraordinary capacitive performance as negative electrodes for aqueous asymmetric supercapacitors (ASCs) are reported first. Taking advantage of increased active sites, improved conductivity, enhanced hydrophilicity, and good strain accommodation in terms of the interesting core–shell architecture and PDA shell, the as‐obtained LFO@PDA electrode reaches a remarkable capacitance of 276.4 F g−1 and prominent durability (no any capacitance loss after 15 000 cycles). Moreover, a robust aqueous 1.8 V‐ASC device with a preferable energy density of 33.9 Wh kg−1 is also achieved based on the LFO@PDA electrode as negative electrode.  相似文献   

8.
Individual Au@PNIPAM/Ag composite has been designed and fabricated as surface‐enhanced Raman scattering (SERS) substrate in this paper. Because of the high porosity of the polymer shell and the driving force of the Au core to Ag+(H2O)n (n = 1–4) in aqueous solution, chemical reactions can be carried out while aggregation is completely avoided. Also, this makes the formation of vast and monodisperse Ag nanoparticles within PNIPAM and increases the colloidal stability. The Au cores with different sizes and the vast Ag nanoparticles then form core–satellite structures that can generate plasmon resonance. Moreover, this kind of individual Au@PNIPAM/Ag composite can be seen directly through Raman optical microscope, and uncertain effects on SERS signals resulting from variability of the configurations are minimized because these individual composite particles are relatively uniform. Importantly, the gaps between the Au and Ag nanoparticles can decrease because the PNIPAM shrinks from swollen to collapse state, so the substrate can also be used for inspecting pesticide residues accurately and rapidly. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

9.
A fluorescent nanoprobe is reported for rapid detection of nitrites (NO2?) in plant cells. The probe is fabricated by linking neutral reds (NR) to the surface of upconversion fluorescent core/shell nanocrystalline with the bridging of polyethylene glycol (PEG) molecules. The fluorescence of upconversion nanoparticles (UCNPs) is stored by NR through fluorescence resonance energy transfer (FRET) under 980 nm excitation that can be released by further linking to NO2?. It is observed that the intensity rate of green to red emission of NR‐modified UCNPs changes linearly with increasing the amount of NO2?. So that concentration of NO2? can be accordingly addressed. Worth mentioning is that, comparing with bare core upconversion nanoparticles (NPs), core/shell UCNPs can greatly reduce the surface quenching of the fluorescence induced by solvents instead of NR and thus leading to the enhancement of signal‐to‐noise ratios. Moreover, excitation of core/shell UCNPs requires only a much lower power (0.06 W cm?2) than bare cores which is beneficial to reducing the decomposition of NR to stabilize the FRET processes. Under the optimum conditions, the detection limit of nitrite in plant cells was 0.1 µg mL?1.  相似文献   

10.
The challenges of nanoparticles, such as size‐dependent toxicity, nonbiocompatibility, or inability to undergo functionalization for drug conjugation, limit their biomedical application in more than one domain. Oval‐shaped iron@gold core–shell (oFe@Au) magnetic nanoparticles are engineered and their applications in magnetic resonance imaging (MRI), optical coherence tomography (OCT), and controlled drug release, are explored via photo stimulation‐generated hyperthermia. The oFe@Au nanoparticles have a size of 42.57 ± 5.99 nm and consist of 10.76 and 89.24 atomic % of Fe and Au, respectively. Upon photo‐stimulation for 10 and 15 minutes, the levels of cancer cell death induced by methotrexate‐conjugated oFe@Au nanoparticles are sixfold and fourfold higher, respectively, than oFe@Au nanoparticles alone. MRI and OCT confirm the application of these nanoparticles as a contrast agent. Finally, results of in vivo experiments reveal that the temperature is elevated by 13.2 °C, when oFe@Au nanoparticles are irradiated with a 167 mW cm?2 808 nm laser, which results in a significant reduction in tumor volume and scab formation after 7 days, followed by complete disappearance after 14 days. The ability of these nanoparticles to generate heat upon photo‐stimulation also opens new doors for studying hyperthermia‐mediated controlled drug release for cancer therapy. Applications include biomedical engineering, cancer therapy, and theranostics fields.  相似文献   

11.
CaMoO4:Nd (core), CaMoO4:Nd@CaMoO4 and CaMoO4:Nd@CaMoO4@SiO2 core–shell nanoparticles were synthesized using polyol method under urea hydrolysis. X-ray diffraction and thermogravimetric analysis were employed to examine the structural and thermal properties of the as-prepared core and core–shell nanoparticles. Optical properties of core and core–shell nanoparticles were observed to investigate the influence of surface coating on the spectra of as-prepared nanomaterials in terms of ultraviolet/visible (UV-Vis) absorbance, FTIR, Raman and emission spectra. The optical band gap energy calculated from the UV-Vis absorption spectrum for CaMoO4:Nd, CaMoO4:Nd@CaMoO4 and CaMoO4:Nd@CaMoO4@SiO2 nanoparticles was 3.09, 2.06 and 1.26 eV, respectively. The photoluminescence spectra of the samples showed broad charge transfer emission band of [MoO4]2? along with sharp transitions of neodymium ion in the visible and near infrared regions, respectively.  相似文献   

12.
Fe3O4@ZnO binary nanoparticles were synthesized by a simple two-step chemical method and characterized using various analytical instruments. TEM result proved the binary nanoparticles have core/shell structures and average particle size is 60 nm. Photocatalytic investigation of Fe3O4@ZnO core/shell nanoparticles was carried out using rhodamine B (RhB) solution under UV light. Fe3O4@ZnO core/shell nanoparticles showed enhanced photocatalytic performance in comparison with the as prepared ZnO nanoparticles. The enhanced photocatalytic activity for Fe3O4@ZnO might be resulting from the higher concentration of surface oxygen vacancies and the suppressing effect of the Fe3+ ions on the recombination of photoinduced electron–hole pairs. Magnetization saturation value (5.96 emu/g) of Fe3O4@ZnO core/shell nanoparticles is high enough to be magnetically removed by applying a magnetic field. The core/shell photocatalyst can be easily separated by using a commercial magnet and almost no decrease in photocatalytic efficiency was observed even after recycling six times.  相似文献   

13.
Cleavage of disulfide bonds is a common method used in linking peptides to proteins in biochemical reactions. The structures, internal rotor potentials, bond energies, and thermochemical properties (ΔfH°, S°, and Cp(T)) of the S–S bridge molecules CH3SSOH and CH3SS(=O)H and the radicals CH3SS?=O and C?H2SSOH that correspond to H‐atom loss are determined by computational chemistry. Structure and thermochemical parameters (S° and Cp(T)) are determined using density functional Becke, three‐parameter, Lee–Yang–Parr (B3LYP)/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p). The enthalpies of formation for stable species are calculated using the total energies at B3LYP/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p), and the higher level composite CBS–QB3 levels with work reactions that are close to isodesmic in most cases. The enthalpies of formation for CH3SSOH, CH3SS(=O)H are ?38.3 and ?16.6 kcal mol?1, respectively, where the difference is in enthalpy RSO–H versus RS(=O)–H bonding. The C–H bond energy of CH3SSOH is 99.2 kcal mol?1, and the O–H bond energy is weaker at 76.9 kcal mol?1. Cleavage of the weak O–H bond in CH3SSOH results in an electron rearrangement upon loss of the CH3SSO–H hydrogen atom; the radical rearranges to form the more stable CH3SS· = O radical structure. Cleavage of the C–H bond in CH3SS(=O)H results in an unstable [CH2SS(=O)H]* intermediate, which decomposes exothermically to lower energy CH2 = S + HSO. The CH3SS(=O)–H bond energy is quite weak at 54.8 kcal mol?1 with the H–C bond estimated at between 91 and 98 kcal mol?1. Disulfide bond energies for CH3S–SOH and CH3S–S(=O)H are low: 67.1 and 39.2 kcal mol?1. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

14.
CaMoO4:Pr(core), CaMoO4:Pr@CaMoO4 (core/shell) and CaMoO4:Pr@CaMoO4@SiO2 (core/shell/shell) nanoparticles were synthesized using polyol method. X-ray diffraction (XRD), thermogravimatric analysis (TGA), UV–vis absorption, optical band gap energy analysis, Fourier transform infrared (FTIR), FT-Raman and photoluminescence (PL) spectroscopy were employed to investigate the structural and optical properties of the synthesized core and core/shell nanoparticles. The results of the XRD indicate that the obtained core, core/shell and core/shell/shell nanoparticles crystallized well at ~150 °C in ethylene glycol (EG) under urea hydrolysis. The growth of the CaMoO4 and SiO2 shell (~12 nm) around the CaMoO4:Pr core nanoparticles resulted in an increase of the average size of the nanopaticles as well as in a broadening of their size distribution. These nanoparticles can be well-dispersed in distilled water to form clear colloidal solutions. The photoluminescence spectra of core, core/shell and core/shell/shell nanoparticles show the characteristic charge transfer emission band of MoO4 2? (533 nm) and Pr3+ 4f2?→?4f2, with multiple strong 3H4?→?3P2, 1D2?→?3H4 and 3P0?→?3?F2 transitions located at ~490, 605 and 652 nm, respectively. The emission intensity of the CaMoO4:Pr@CaMoO4 core/shell and CaMoO4:Pr@CaMoO4@SiO2 core/shell/shell nanoparticles increased ~4.5 and 1.7 times,respectively, with respect to those of CaMoO4:Pr core nanoparticles. This indicates that a significant amount of nonradiative centers existing on the surface of CaMoO4:Pr@CaMoO4 core/shell nanoparticles can be eliminated by the shielding effect of CaMoO4 shells.  相似文献   

15.
Laser ablation in liquids (LAL) has emerged as a versatile approach for the synthesis of alloy particles and oxide nanomaterials. However, complex chemical reactions often take place during synthesis due to inevitable atomization and ionization of the target materials and decomposition/hydrolysis of solvent/solution molecules, making it difficult to understand the particle formation mechanisms. In this paper, a possible route for the formation of FeMn alloy nanoparticles as well as MnOx nanoparticles, ‐sheets, and ‐fibers by LAL is presented. The observed structural, compositional, and morphological variations are clarified by transmission electron microscopy (TEM). The studies suggest that a reaction between Mn atoms and Fe ions followed by surface oxidation result in nonstoichiometric synthesis of Fe‐rich FeMn@FeMn2O4 core–shell alloy particles. Interestingly, a phase transformation from Mn3O4 to Mn2O3 and finally to Ramsdellite γ‐MnO2 is accompanied by a morphology change from nanosheets to nanofibers in gradually increasing oxidizing environments. High‐resolution TEM images reveal that the particle‐attachment mechanism dominates the growth of different manganese oxides.  相似文献   

16.
In the present report, bare CdO and CdO/MnO2 core/shell nanostructures of various cores and different shell sizes were synthesized using co‐precipitation method. The phase, size, shape and structural details of the bare CdO and CdO/MnO2 nanostructures were investigated by X‐ray diffraction, transmission electron microscopy (TEM), and Raman spectroscopy measurements. TEM micrographs confirm the formation of core/shell nanostructures. The presence of CdO (core) and MnO2 (shell) crystal phases was determined by analyzing the Raman data of bare CdO and CdO/MnO2 core/shell nanostructures. The Raman spectra of bare CdO nanostructures contain one broad intense convoluted envelop of three bands in the spectral range of 200–500 cm−1 and a weaker band located at ~940 cm−1. The intensity of these two Raman bands is decreased with the increase of shell size and disappeared completely for the shell size 5.3 ± 1 nm. Further, two new Raman bands appeared at ~451 and ~665 cm−1 for the shell size 1.3 ± 0.1 nm. These two Raman bands are assigned to the deformation of Mn–O–Mn and Mn–O stretching modes of MnO2. The intensity of these two Raman bands is enhanced with the increase of shell size and attains a maximum value for the shell size 5.3 ± 1 nm. The disappearance of characteristics Raman bands of CdO phase and the appearance of characteristics Raman bands corresponding to MnO2 phase for nanostructures of shell size 5.3 ± 1 nm authenticate the presence of CdO as core and MnO2 as shell in the core/shell nanostructures. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

17.
Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm−1 for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm−1 to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

18.
Conversion of CO2 gas to CO fuels is one of the most promising solutions for the increasing threat of global warming and energy crisis. The efficient catalyst Ni–Au dumbbell converting CO2 into CO at elevated temperatures has high CO product selectivity; however, the accompanied atomic diffusion and subsequent surface reconstruction affect the catalytic efficiency of chemical reaction. Atomic scale characterization of structural evolution of the catalyst, which is essential to correlate the functional mechanism to active catalyst surfaces, is yet to be studied. Here, in situ transmission electron microscopy experiments and atomistic simulations are performed to characterize the structural evolution of Ni–Au dumbbell nanoparticles under two different external stimuli. In the condition of high temperature and vacuum, the Ni–Au nanostructure reveals a clear shape reconstruction from the initial dumbbell to core–shell‐like, which is induced by capillary force to minimize free surface energy of the system. The shape transformation involves two stages of processes, initial fast Au diffusion followed by slow source‐controlled diffusion. At ambient temperature, the combination of CO2 and electron flux surprisingly induces analogous structural transformation of Ni–Au nanostructure, where the associated chemical reaction and CO absorption stimulate the Au migration on Ni surface. Such surface reconstruction can be widely present in catalytic reactions in different environmental conditions, and the results herein demonstrate the detailed processes of Ni–Au structure evolution, which provide important insights for understanding the catalyst performance.  相似文献   

19.
Interaction of bacteria with citrate‐reduced silver nanoparticles (AgNPs) of size 25 nm ± 8.5 nm is studied using Raman spectroscopy in conjunction with plasmon resonance imaging of single bacterial cells. Distribution of isolated nanoparticles (NPs) inside Escherichia coli (ATCC 25922; E. coli) is observed by hyperspectral imaging (HSI) as a function of incubation time. Time‐dependent degradation of bacterial DNA upon incubation of AgNPs with E. coli is proven by Raman spectroscopic studies. While attachment of NPs is evident in HSI, molecular changes are evident from the surface‐enhanced Raman spectra of adsorbed DNA and its fragments. Distinct enhancement of DNA features is observed upon interaction of AgNPs and the number of such distinct features increases with incubation time, reaches a maximum, and decreases afterwards. This systematic interaction of DNA with the NPs system and its gradual chemical evolution is proven by investigating isolated plasmid DNA. A comparative Raman study with silver ions has shown that DNA features are observable only when bacteria are incubated with AgNPs. Energetics of interaction examined with microcalorimetry suggests the exothermicity of ?1.547 × 1010 cal mol?1 for the NP–bacteria system. Specific interaction of AgNPs with exocyclic nitrogen present in the bases, adenine, guanine, and cytosine, leads to the changes in DNA.  相似文献   

20.
Core–shell bimetallic Au@Ni nanoparticles, with gold cores and thin nickel shells with overall size less than 10 nm, are synthesized and stabilized in pure cubic (fcc) and hexagonal (hcp) phase. Due to their unique crystal, electronic, and geometric structure, they show interesting magnetic and chemical properties. The Au@Nifcc is magnetic, whereas Au@Nihcp is non‐magnetic. Both the bimetallic nanostructures are stable to surface oxidation until 150 °C and show excellent catalytic activity for p‐nitrophenol reduction reaction.  相似文献   

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