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1.
Designing and developing active, robust, and noble‐metal‐free catalysts with superior stability for electrocatalytic water splitting is of critical importance but remains a grand challenge. Here, a facile strategy is provided to synthesize a series of Co‐based self‐supported electrode materials by combining electrospinning and chemical vapor deposition (CVD) technologies. The Co, Co3O4, Co9S8 nanoparticles (NPs) are formed in situ simultaneously with the formation of carbon nanofibers (CNFs) during the CVD process, respectively. The Co‐based NPs are uniformly distributed through the CNFs and they can be directly used as the electrode materials for hydrogen evolution reaction (HER) in acid and oxygen evolution reaction (OER) in alkaline. The Co9S8/CNFs membrane exhibits the best HER activity with overpotential of 165 mV at j = 10 mA cm?2 and Tafel slope of 83 mV dec?1 and OER activity with overpotential of 230 mV at j = 10 mA cm?2 and Tafel slope of 72 mV dec?1. The onion‐like graphitic layers formed around the NPs not only improve the electrical conductivity of the electrode but also prevent the separation of the NPs from the carbon matrix as well as the aggregation.  相似文献   

2.
Various C‐doped metal oxide nanoparticles (NPs) are prepared from metal nitrates in poly‐(methyl vinyl ether‐co‐maleic anhydride) (PVM/MA) nanoreactors. The loading of metal nitrates in the nanoreactors is realized via a process of solution‐enhanced dispersion by supercritical CO2. When the temperature exceeds the thermal decomposition temperature of the nitrates, the nitrates‐loaded nanoreactors transform into C‐doped metal oxide NPs. ZnO, NiO, and Co3O4 NPs as representative of the doped oxides are successfully fabricated. A precise control over the doping concentration and doping site in the lattice is achieved by changing the mass ratio between PVM/MA and metal nitrate. The controllable carbon doping avoids undesirable aggregation of carbon species and metal oxide NPs, endows the NPs with broad and strong absorption bands in the visible light region, and creates channels for separation of photo‐generated electrons and holes. In this regard, the resultant C‐doped metal oxide NPs exhibit excellent photocatalytic, photo‐induced antibacterial, and photothermal performances.  相似文献   

3.
FeNi alloy nanoparticles (NPs) supported by reduced graphene oxide (RGO) (FeNi/RGO nanocomposites) were successfully synthesized through in‐situ reduction. Large amounts of sphere‐like FeNi NPs are uniformly deposited on the RGO nanosheets. The magnetic hysteresis measurement reveals the ferromagnetic behavior of the nanocomposites at room temperature. According to the electromagnetic (EM) characteristics, the FeNi/RGO nanocomposites show outstanding EM absorption properties in the 2–18 GHz range, as evidenced by the wide effective absorption bandwidth (up to 3.3 GHz, with reflection loss RL < –10 dB) and a minimal RL (–32 dB) at 12.4 GHz with a thickness of 1.5 mm. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   

4.
A facile synthesis of porous graphitic carbon nanofibers (CNFs) with encapsulated Co nanoparticles (denote as Co@CNFs) via electrospinning and subsequent annealing is reported. The in situ generated Co nanoparticles (NPs) promote the CNF graphitization under a low temperature of 700 °C, which simultaneously results in the porous structure of the Co@CNFs with a large surface area (416 m2 g?1). Furthermore, urchin‐like CoSe2 nanorods are epitaxially grown from the Co@CNFs via a facile hydrothermal selenation, in which the embedded Co NPs serve as directing seeds and sacrificial Co‐source, and CoSe2 nanorods are rooted into the CNFs (denote as CoSe2@CNFs). When used as anode materials for lithium ion batteries, the CoSe2@CNFs demonstrate superior lithium storage properties, delivering a high reversible capacity of 1405 mA h g?1 after 300 cycles at a current density of 200 mA g?1. The enhanced lithium storage performance can be attributed to the novel hybrid structure, namely, the porous and graphitic CNFs can not only facilitate the charge/ion transfer but also buffer the volume changes of the electrode during lithiation/delithiation processes. More importantly, a general strategy is provided to graphitize amorphous carbon materials via the use of in situ generated transition metal nanoparticles as catalyst.  相似文献   

5.
In recent years, graphene‐incorporated micro‐/nanocomposites represent one of the hottest developing directions for the composite materials. However, a large number of active nanoparticles (NPs) are still in the unprotected state in most constructed graphene‐containing designs, which will seriously impair the effects of the graphene additives. Here, a fully protected Fe3O4‐based micro‐/nanocomposite (G/Fe3O4@C) is rationally developed by carbon‐boxing the common graphene/Fe3O4 microparticulates (G/Fe3O4). The processes and results of full protection are tracked in detail and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and nitrogen absorption–desorption isotherms, as well as scanning and transition electron microscopy. When used as the anode for lithium‐ion batteries, the fully protected G/Fe3O4@C exhibits the best lithium‐storage properties in terms of the highest rate capabilities and the longest cycle life compared to the common G/Fe3O4 composites and commercial Fe3O4 products. These much improved properties are mainly attributed to its novel structural features including complete protection of active Fe3O4 nanoparticles by the surface carbon box, a robust conductive network composed of nitrogen‐doped graphene nanosheets, ultra‐small Fe3O4 NPs of 4–5 nm, abundant mesopores to accommodate the volume variation during cycling, and micrometer‐sized secondary particles.  相似文献   

6.
Core–shell structured nanocomposites, a type of talented functional materials with unique microstructure and properties, have shown great promise as photocatalysts for various applications, including photocatalytic degradation of pollutants, water splitting for hydrogen production, and selective organic transformations. The synthesis and utilization of efficient core–shell nanoarchitectured photocatalysts for selective organic synthesis are at the center of our research efforts and the focus of this minireview. Specifically, semiconductor‐based core–shell nanocomposites, including metal–semiconductor, semiconductor–semiconductor, semiconductor–shell (graphene and SiO2) as photocatalysts/cocatalysts for selective oxidation of alcohols, reduction of nitro organics and carbon dioxide for synthesis of fine chemicals, and redox‐combined selective synthesis of pipecolinic acid are summarized. It is hoped that this minireview can make a contribution to catalyzing the development of smart core–shell nanostructures in the field of photocatalytic selective organic transformations for solar energy conversion.  相似文献   

7.
Synthesis of nanoparticles in high‐boiling alcohols (so‐called polyol synthesis) and surface functionalization of nanoparticles with polyethylene glycol (so‐called PEGylation) in combination with certain heating are often accompanied with an intense fluorescence in the blue to green spectral range. Based on the polyol synthesis of Zn3(PO4)2 nanoparticles and a critical consideration of the relevant experimental conditions—including the presence of nanoparticles, the role of dissolved metal salts (ZnCl2, MgCl2, KCl), the type of the polyol (DEG, GLY, PEG400), the temperature and time of heating (150–230 °C, 1–6 h)—we can correlate the observed fluorescence to the formation of carbon dots (C‐dots) stemming from thermal decomposition (i.e., dehydration and carbonization) of the polyol. Thus, the thermal decomposition of polyols results in C‐dots with a diameter of 3–5 nm at narrow size distribution. The formation of C‐dots is confirmed by transmission electron microscopy (TEM), high‐resolution TEM (HRTEM), X‐ray powder diffraction (XRD), Fourier‐transform infrared spectroscopy (FT‐IR), and fluorescence spectra.  相似文献   

8.
《Ultrasonics sonochemistry》2014,21(5):1849-1857
Novel material PtSe2–graphene/TiO2 nanocomposites were successfully synthesized through a facile ultrasonic assisted method. The prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) with an energy dispersive X-ray (EDX),transmission electron microscopy (TEM), Raman spectroscopic analysis, UV–vis absorbance spectra and UV–vis diffuse reflectance spectra (DRS) analysis were obtained. The catalytic behavior was investigated through the decomposition of rhodamine B (Rh.B) as a standard dye. Enhanced photocatalytic activities were observed by increasing the weight% of graphene in the PtSe2–graphene/TiO2 nanocomposites. We observed that the coupling of TiO2 with PtSe2–graphene alter the optical properties by observing a precise band gap in the visible range.  相似文献   

9.
Structure engineering is an effective strategy to enhance the performance of electrocatalysts for the formic acid oxidation reaction. However, it remains a challenge to prepare a highly active electrocatalyst based on a distinct understanding of its structure‐dependent performance. The design and synthesis of ultrathin‐carbon‐layer‐protected PtCu nanoparticles (NPs) encapsulated in a N‐doped carbon capsule (PtCu@NCC) is reported. This system is fabricated by using Zn‐based metal–organic frameworks as the carbon support source and metal‐containing tannic acid as the protecting shell template. It displays 9.8‐ and 9.6‐fold enhancements in mass activity and specific activity compared to commercial Pt/C. Moreover, a constructed direct formic acid fuel cell using PtCu@NCC as the anodic electrocatalyst delivers a maximum power density of 121 mW cm?2. Significantly, PtCu@NCC exhibits superior structural stability and catalytic durability in both half‐cell and full‐cell tests. A mechanism study reveals that the enhanced activity is partially attributed to facilitated electro‐oxidation kinetics of formic acid in the unique structure of PtCu@NCC, while the excellent durability stems from the “protecting effect” of the in‐situ‐formed ultrathin carbon layer on the surface of the PtCu NPs. This work opens a new avenue for the development of high‐performance electrocatalysts for fuel‐cell applications by offering essential insights into the structure–performance relationship of the materials.  相似文献   

10.
Nanocomposites based on iron and nickel particles encapsulated into carbon (Fe@C and Ni@C), with an average size of the metal core in the range from 5 to 20 nm and a carbon shell thickness of approximately 2 nm, have been prepared by the gas-phase synthesis method in a mixture of argon and butane. It has been found using X-ray diffraction, transmission electron microscopy, and Mössbauer spectroscopy that iron nanocomposites prepared in butane, apart from the carbon shell, contain the following phases: iron carbide (cementite), α-Fe, and γ-Fe. The phase composition of the Fe@C nanocomposite correlates with the magnetization of approximately 100 emu/g at room temperature. The replacement of butane by methane as a carbon source leads to another state of nanoparticles: no carbon coating is formed, and upon subsequent contact with air, the Fe3O4 oxide shell is formed on the surface of nanoparticles. Nickel-based nanocomposites prepared in butane, apart from pure nickel in the metal core, contain the supersaturated metastable solid solution Ni(C) and carbon coating. The Ni(C) solid solution can decompose both during the synthesis and upon the subsequent annealing. The completeness and degree of decomposition depend on the synthesis regime and the size of nickel nanoparticles: the smaller is the size of nanoparticles, the higher is the degree of decomposition into pure nickel and carbon. The magnetization of the Ni@C nanocomposites is determined by several contributions, for example, the contribution of the magnetic solid solution Ni(C) and the contribution of the nonmagnetic carbon coating; moreover, some contribution to the magnetization can be caused by the superparamagnetic behavior of nanoparticles.  相似文献   

11.
Natural gas (NG), as a renewable and clean energy gas, is considered to be one of the most attractive energy carriers owing to its high calorific value, low price, and less pollution. Efficiently capturing CO2 from NG is a very important issue since CO2 reduces energy density of natural gas and corrodes equipment in the presence of water. In this study, the authors use holey graphene‐like carbon derived from covalent organic polymers (COP) impregnated with nonprecious metals, i.e., COP graphene, as highly efficient separation materials. The dual‐site Langmuir–Freundlich adsorption model based ideal absorbed solution theory is applied to explore the adsorption selectivity. The experimental results along with first principles calculations show Mn‐impregnated COP graphene exhibits greater CO2/CH4 selectivity than Fe and Co impregnated materials. Particularly, the selectivity of C–COP–P–Mn reaches 11.4 at 298 K and 12 bars, which are much higher than those in many reported conventional porous materials and can be compared to the highest separation performance under similar condition. Importantly, all the three COP graphene show remarkably high regenerability (R > 77%), which are much better than many reported promising zeolites, active carbon, and metal organic frameworks. Accordingly, COP graphene are promising cyclic adsorbents with high selectivity for separation and purification of CO2 from natural gas.  相似文献   

12.
Graphene has excellent mechanical, electrical and thermal properties. Recently, graphene-metal composites have been proposed as a means to combine the properties of metals with those of graphene, leading to mechanically, electrically and thermally functional materials. The understanding of metal-graphene nanocomposites is of critical importance in developing next-generation electrical, thermal and energy devices, but we currently lack a fundamental understanding of how their geometry and composition control their thermal properties. Here we report a series of atomistic simulations, aimed at assessing the geometry and temperature effects of the thermal interface conductance for copper- and nickel-graphene nanocomposites. We find that copper-graphene and nickel-graphene nanocomposites have similar thermal interface conductances, but that both cases show a strong performance dependence on the number of graphene layers between metal phases. Single-graphene-layer nanocomposites have the highest thermal interface conductance, approaching ~500 MW m(-2) K(-1). The thermal interface conductance reduces to half this value in metal-bilayer graphene nanocomposites, and for more than three layers of graphene the thermal interface conductances further reduces to ~100 MW m(-2) K(-1) and becomes independent with respect to the number of layers of graphene. This dependence is attributed to the relatively stronger bonding between the metal and graphene layer, and relatively weaker bonding between graphene layers. Our results suggest that designs combining metal with single graphene layers provide the best thermal properties.  相似文献   

13.
Biocompatible single‐component theranostic nanoagents instinctly affording multiple imaging modalities with satisfying therapeutic functions are highly desirable for anticancer treatments. Although cobalt‐based phosphides are well‐recognized as competent electrocatalysts, their potentials for biomedical applications remain unexplored. In this work, cobalt phosphide nanoparticles (CoP NPs) are developed to be a powerful theranostic agent for multimodal imaging and anticancer photothermal therapy. The uniform CoP NPs in a size of ≈21 nm are synthesized via a facile thermal decomposition method, followed by surface modification. The resultant CoP NPs exhibit excellent compatibility and stability in water as well as various physiological solutions. Supported by the good biocompatibility, strong near‐infrared absorption, and high photothermal conversion property, significant photothermal effect of the NPs is demonstrated, realizing efficient hyperthermia ablation on cancer cells. Importantly, the CoP NPs have shown considerable capabilities on high‐contrast in vitro and in vivo triple‐modal imaging, including infrared thermal (IRT), photoacoustic (PA), and T2‐weighted magnetic resonance (MR) imaging. This work has unraveled the promising potentials of CoP‐based nanoagent for precise diagnosis and efficient therapy.  相似文献   

14.
Graphene-reinforced polymer nanocomposites are under intense investigation in recent years. In this work, graphene nanosheets have been prepared using chemical reduction method of graphene oxide. Graphene-reinforced epoxy nanocomposites show an enhancement in mechanical and thermal properties at 0.05 wt.% of graphene in epoxy matrix. Modification of graphene with polyvinylpyrrolidone (PVP) shows the significant enhancement in mechanical and thermal properties of epoxy nanocomposites. PVP-modified graphene nanosheets reduces the gap of enthalpic and entropic penalties and facilitates improved dispersion of graphene in epoxy matrix. In addition, enhanced dispersion of PVP-modified graphene in epoxy matrix results in better load transfer across graphene–epoxy interface. Glass transition temperature (Tg) of PVP-modified graphene epoxy nanocomposites increases as compared to pure epoxy because there exist an interaction between epoxy and PVP. Fractography study reveals the localized ductile fracture.  相似文献   

15.
The mechanism of charge transfer through nanomaterials such as graphene remains unclear, and the amount of charge that can be transferred from/to graphene without damaging its structural integrity is unknown. In this communication, we show that metallic nanoparticles can be decorated onto graphene surfaces as a result of charge transfer from the supporting substrate to an adjoining solution containing metal ions. Au or Pt nanoparticles were formed with relatively high yield on graphene‐coated substrates that can reduce these metal ions, such as Ge, Si, GaAs, Al, and Cu. However, metal ions were not reduced on graphene surfaces coated onto non‐reducing substrates such as SiO2 or ZnO. These results confirm that graphene can be doped by exploiting charge transfer from the underlying substrate; thus graphene is not only transparent with respect to visible light, but also with respect to the charge transfer. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)  相似文献   

16.
Elastomer nanocomposites were prepared by mixing carbon nanofiber (CNF) decorated with metal nanoparticles (CNF–Fe2O3) with latex. The Fe2O3 metal nanoparticles were decorated on the CNF by electrostatic attraction via a green and facile solution-based method. The presence of the metal nanoparticles on the surface of the CNF improved their dispersion and electric contact resistance in the elastomer matrix. Interestingly, the CNF–Fe2O3/elastomer composite exhibited improvements in both tensile strength and elongation (carbon black/elastomer), by as much as 9.7 and 28.9%, respectively, compared to an elastomer control without filler. Also, the CNF–Fe2O3/elastomer exhibited superior thermal and electrical conductivity compared with the control. In an applied magnetic field the elastomer nanocomposites showed a significant transition from dominant diamagnetism to ferromagnetism due to synergies between the Fe2O3 nanoparticles and the CNF. The elastomer nanocomposites prepared with CNF–Fe2O3 will open significant new opportunities for preparing advanced elastomer nanocomposites for future engineering applications.  相似文献   

17.

Catalytic graphitization of kraft lignin to nano-materials was investigated over four transitional metal catalysts (Ni, Cu, Fe, and Mo) through a thermal treatment process under an argon flow at 1000 °C. The catalytic thermal process was examined using thermal gravimetric analysis (TGA) and temperature-programmed decomposition (TPD) experiments. The crystal structure and morphology of the thermal-treated metal-lignin samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. Catalytic graphitization of kraft lignin to nano-materials was investigated over four transitional metal catalysts (Ni, Cu, Fe, and Mo) through a catalytic thermal treatment process. It was observed that multi-layer graphene-encapsulated metal nanoparticles were the main products, beside along with some graphene sheets/flakes. The particle sizes and graphene shell layers were significantly affected by the promoted metals. BET surface areas of samples obtained from different metal precursors were in the range of 88–115 m2/g within the order of Ni-?>?Fe-?>?Mo-?>?Cu-. Thermal gravimetric analysis (TGA) and temperature-programmed decomposition (TPD) experimental results showed that adding transitional metals could promote the decomposition and carbonization of kraft lignin. The catalytic activity increased with an order of Mo?Cu?<?Ni?Fe. XRD results show that face-centered cubic (fcc) Cu crystals is formed in the thermal-treated Cu-lignin sample, fcc nickel phase for the Ni-lignin sample, β-Mo2C hexagonal phase for the Mo-lignin sample and α-Fe, γ-iron, and cementite(Fe3C) for the Fe-lignin sample. Average particle sizes of these crystal phases calculated using the Scherrer formula are 52.4 nm, 56.2 nm, 21.0 nm, 23.3 nm, 11.3 nm, and 32.8 nm for Ni, Cu, β-Mo2C, α-Fe, γ-iron, and Fe3C, respectively. Raman results prove that the graphitization activity of these four metals is in the order of Cu?<?Mo?<?Ni?<?Fe. Metal properties such as catalytic activity, carbon solubility, and tendency of metal carbide formation were related to the graphene-based structure formation during catalytic graphitization of kraft lignin process.

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18.
Fabrication of nanoclusters on a substrate is of great interest in studies of model catalysts. The key factors that govern the growth and distribution of metal on graphene have been studied by scanning tunneling microscopy (STM) based on different behaviors of five transition metals, namely Pt, Rh, Pd, Co, and Au supported on the template of a graphene moiré pattern formed on Ru(0001). Our experimental findings show that Pt and Rh form finely dispersed small clusters located at fcc sites on graphene while Pd and Co form large clusters at similar coverages. These results, coupled with previous findings that Ir forms the best finely dispersed clusters, suggest that both metal–carbon (M–C) bond strength and metal cohesive energies play significant roles in the cluster formation process and that the M–C bond strength is the most important factor that affects the morphology of clusters at the initial stages of growth. Furthermore, experimental results show Au behaves differently and forms a single-layer film on graphene, indicating other factors such as the effect of substrate metals and lattice match should also be considered. In addition, the effect of annealing Rh on graphene has been studied and its high thermal stability is rationalized in terms of a strong interaction between Rh and graphene as well as sintering via Ostwald ripening.  相似文献   

19.
《Current Applied Physics》2020,20(4):510-518
This paper is devoted to studying the thermal and mechanical properties of aminated graphene (AG)/epoxy nanocomposites connected by covalent bond using molecular dynamics (MD) simulation. The effects of crosslinking degree, mass fraction and functionalized graphene (FG) type on AG/epoxy nanocomposites are considered. The elasticity modulus (E), the glass transition temperature (Tg), the coefficient of thermal expansion (CTE) and the interfacial energy (Eint) are also investigated. The MD simulation results indicate that, when the mass fraction of AG is between 1.2% and 3.1% and crosslinking degree reaches about 70%, the E, Tg, Eint and CTE of AG/epoxy nanocomposites are significantly improved compared with those of pure epoxy and graphene/epoxy nanocomposites. The reason is that AG not only possesses some excellent thermodynamic properties of graphene, but also has the function of curing agent to crosslink with epoxy monomer to form the carbon-nitrogen (C–N) covalent bond. A better interfacial interaction between nanoparticles and epoxy is essential in enhancing the thermal and mechanical properties of nanocomposite materials, which will provide a microscopic theoretical basis for the study of epoxy nanocomposites.  相似文献   

20.
The method of chemical deposition of metal salts from water–salt solutions with the subsequent thermal decomposition of salt to metal or metal oxide has been developed for thermoexfoliated graphite (TEG). The type of graphite support and character of metal salt thermal decomposition was shown to influence essentially the dispersity and morphology of metal particles being formed on graphite surface. Preliminary treatment of the initial dispersed graphite by H2SO4 leads to the formation of oxygen-containing groups on its surface, which are the exchange centres fixing the metal cations in graphite–metal (or graphite–metal oxide) composites. Thermal exfoliation of graphite, which is accompanied by the refinement of graphite structure, occurs as a result of oxidized graphite heat treatment. High porosity, defectiveness and chemical activity of TEG surface favour the effective impregnation of TEG by aqueous salt solution. Thermal treatment of the salt-impregnated graphite leads to formation of Co particles on graphite surface. These particles are 70–150 nm in size for TEG–Co at a relatively high metal content (up to 30 wt%) and 200 nm in size for oxidized dispersed graphite–Co at Co content ∼10 wt%.  相似文献   

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