Preparation and lithium storage of core–shell honeycomb-like Co3O4@C microspheres

Core–shell honeycomb-like Co₃O₄@C microspheres were synthesized via a facile solvothermal method and subsequent annealing treatment under an argon atmosphere. Owing to the core–shell honeycomb-like structure, a long cycling life was achieved (a high reversible specific capacity of 318.9 mA h g⁻¹ was maintained at 5C after 1000 cycles). Benefiting from the coated carbon layers, excellent rate capability was realized (a reversible specific capacity as high as 332.6 mA h g⁻¹ was still retained at 10C). The design of core–shell honeycomb-like microspheres provides a new idea for the development of anode materials for high-performance lithium-ion batteries.

The reversible specific capacity of CSHCo₃O₄@C microspheres was as high as 332.6 mA h g⁻¹ at 10C, which was significantly higher than that of SCo₃O₄ microspheres (68.7 mA h g⁻¹).     

Chemically activated core–shell structured IF-WS2@C nanoparticles enhance sugarcane-based carbon/epoxy nanocomposites

Ternary composites have demonstrated better capability than binary composites in enhancing the mechanical properties of the modified epoxy resins and are, therefore, currently under intensive investigation. Herein, we report a novel ternary nanocomposite prepared by filling a binary BPF (bisphenol F epoxy resin)/SCPs (sugarcane-based carbon powders) matrix with C-coated inorganic fullerene-like tungsten disulfide (IF-WS₂@C) nanoparticles, and the analysis of its interface synergetic effect using XPS/FTIR. This activated nano-carbon core–shell structure filler is considered an ideal nanofiller and shows the excellent mechanical performance of the ternary composites. XRD, IR, XPS, SEM, and TEM characterizations were applied in investigating this nanocomposite. The improvement of the thermal and mechanical properties demonstrated the enhancement effects of this nanofiller. The results show that the great improvement of the bending modulus of 39.4% increased with the addition of 0.5 wt% IF-WS₂@C nanoparticles, while 34.1% enhancement of bending strength was obtained with the addition of 0.2 wt% IF-WS₂@C nanoparticles. The hardness and thermal conductivity were also boosted up to 5.2% and 33.1% with 0.5 wt% addition, respectively. The incorporation of a chemically activated coating may provide a novel means for improving graphite crystallization, which could somehow expand the potential application of IF-WS₂@C nanoparticles.

Schematic diagram and typical curing mechanism of epoxy resins and the unique interactions of the IF-WS₂@C nanoparticles introduced into the matrix.     

Facile synthesis of porous Fe3O4@C core/shell nanorod/graphene for improving microwave absorption properties

Porous Fe₃O₄@C core/shell nanorods decorated with reduced graphene oxide (RGO) were fabricated through a facile one-pot method. The microwave absorption properties of the samples can be adjusted by the weight ratio of RGO. The addition of RGO not only effectively reduces the agglomeration of Fe₃O₄@C, but also has a great effect on impedance matching and dielectric loss, resulting in enhanced microwave absorption abilities. The thickness corresponding to optimum reflection loss (R_L) decreases as the weight ratio of RGO increases. For the Fe₃O₄@C/RGO composite, a maximum R_L value of −48.6 dB can be obtained at 13.9 GHz with a thickness of 3.0 mm, and the absorption bandwidth with R_L below −10 dB is 7.1 GHz from 10.9 GHz to 18 GHz. These results demonstrate a facile method to prepare a highly efficient microwave absorption material with special microstructure.

Porous Fe₃O₄@C core/shell nanorods decorated with reduced graphene oxide were synthesized by a facile one-pot method, and exhibit high microwave absorption performance: maximum reflection loss reaches −48.6 dB.     

Preparation of biomimetic non-iridescent structural color based on polystyrene–polycaffeic acid core–shell nanospheres

Caffeic acid (CA), as a natural plant-derived polyphenol, has been widely used in surface coating technology in recent years due to its excellent properties. In this work, caffeic acid was introduced into the preparation of photonic band gap materials. By controlling the variables, a reasonable preparation method of polystyrene (PS) @polycaffeic (PCA)–Cu(ii) core–shell microspheres was achieved: 1 mmol L⁻¹ cupric chloride anhydrous (CuCl₂), 3 mmol L⁻¹ sodium perborate tetrahydrate (NaBO₃·4H₂O), 2 mmol L⁻¹ CA and 2 g L⁻¹ polystyrene (PS) were reacted at 50 °C for 10 min to prepare PS@PCA–Cu(ii) core–shell microspheres through rapid oxidative polymerization of CA coated PS of different particle diameters. The amorphous photonic crystal structure was self-assembled through thermal assisted-gravity sedimentation, resulting in structural color nanomaterials with soft and uniform color, no angle dependence, stable mechanical fastness and excellent UV resistance.

Caffeic acid (CA), as a natural plant-derived polyphenol, has been widely used in surface coating technology in recent years due to its excellent properties.     

Fabrication of a novel core–shell–shell temperature-sensitive magnetic composite with excellent performance for papain adsorption

Herein, a novel temperature-sensitive magnetic composite (Fe₃O₄@SiO₂@P(NIPAM-co-VI)/Cu²⁺) with a uniform core–shell–shell structure was successfully prepared via a layer-by-layer method. The resulting magnetic composite revealed good magnetic properties and remarkable affinity to papain with a maximum adsorption capacity of 199.17 mg g⁻¹. The adsorption equilibrium data fitted the pseudo-second-order kinetic and Freundlich models well, and the major thermodynamics parameters indicated that adsorption was an endothermic and spontaneous process. Fe₃O₄@SiO₂@P(NIPAM-co-VI)/Cu²⁺ could thermally protect papain, which is attributed to the reversible hydrophilic–hydrophobic transition of the composite at temperatures below and above the lower critical solution temperature. More importantly, the magnetic composite could be recycled at least six times without a remarkable loss in its adsorption capacity, and the process of adsorption and elution had no significant effect on the activity and structure of papain. This work could provide a novel separation method for papain without loss of its activity.

A novel core–shell–shell temperature-sensitive magnetic composite was designed. The composites showed excellent performance for papain adsorption and could thermally protect papain.     

Synthesis of core–shell N-TiO2@CuOx with enhanced visible light photocatalytic performance

In this paper, a core–shell N-TiO₂@CuO_x nanomaterial with increased visible light photocatalytic activity was successfully synthesized using a simple method. By synthesizing ammonium titanyl oxalate as a precursor, N-doped TiO₂ can be prepared, then the core–shell structure of N-TiO₂@CuO_x with a catalyst loading of Cu on its surface was prepared using a precipitation method. It was characterized in detail using XRD, TEM, BET, XPS and H₂-TPR, while its photocatalytic activity was evaluated using the probe reaction of the degradation of methyl orange. We found that the core–shell N-TiO₂@CuO_x nanomaterial can lessen the TiO₂ energy band-gap width due to the N-doping, as well as remarkably improving the photo-degradation activity due to a certain loading of Cu on the surfaces of N-TiO₂ supports. Therefore, a preparation method for a novel N, Cu co-doped TiO₂ photocatalyst with a core–shell structure and efficient photocatalytic performance has been provided.

In this paper, a core–shell N-TiO₂@CuO_x nanomaterial with increased visible light photocatalytic activity was successfully synthesized using a simple method.     

Synthesis and biological characterization of alloyed silver–platinum nanoparticles: from compact core–shell nanoparticles to hollow nanoalloys

Bimetallic nanoparticles consisting of silver and platinum were prepared by a modified seeded-growth process in water in the full composition range in steps of 10 mol%. The particles had diameters between 15–25 nm as determined by disc centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). Whereas particles with high platinum content were mostly spherical with a solid silver core/platinum shell structure, mostly hollow alloyed nanoparticles were observed with increasing silver content. The internal structure and the elemental distribution within the particles were elucidated by high-resolution transmission electron microscopy (HRTEM) in combination with energy-dispersive X-ray spectroscopy (EDX). The particles were cytotoxic for human mesenchymal stem cells (hMSC) above 50 mol% silver. This was explained by dissolution experiments where silver was only released at and above 50 mol% silver. In contrast, platinum-rich particles (less than 50 mol% silver) did not release any silver ions. This indicates that the presence of platinum inhibits the oxidative dissolution of silver.

Bimetallic nanoparticles consisting of silver and platinum were prepared by a modified seeded-growth process in water in the full composition range in steps of 10 mol%.     

Synthesis and thermal stability of ZrO2@SiO2 core–shell submicron particles

ZrO₂@SiO₂ core–shell submicron particles are promising candidates for the development of advanced optical materials. Here, submicron zirconia particles were synthesized using a modified sol–gel method and pre-calcined at 400 °C. Silica shells were grown on these particles (average size: ∼270 nm) with well-defined thicknesses (26 to 61 nm) using a seeded-growth Stöber approach. To study the thermal stability of bare ZrO₂ cores and ZrO₂@SiO₂ core–shell particles they were calcined at 450 to 1200 °C. After heat treatments, the particles were characterized by SEM, TEM, STEM, cross-sectional EDX mapping, and XRD. The non-encapsulated, bare ZrO₂ particles predominantly transitioned to the tetragonal phase after pre-calcination at 400 °C. Increasing the temperature to 600 °C transformed them to monoclinic. Finally, grain coarsening destroyed the spheroidal particle shape after heating to 800 °C. In striking contrast, SiO₂-encapsulation significantly inhibited grain growth and the t → m transition progressed considerably only after heating to 1000 °C, whereupon the particle shape, with a smooth silica shell, remained stable. Particle disintegration was observed after heating to 1200 °C. Thus, ZrO₂@SiO₂ core–shell particles are suited for high-temperature applications up to ∼1000 °C. Different mechanisms are considered to explain the markedly enhanced stability of ZrO₂@SiO₂ core–shell particles.

Silica encapsulation dramatically enhances the thermal stability of zirconia submicron particles by grain growth inhibition and tetragonal phase stabilization.     

Facile synthesis of silver nanocatalyst decorated Fe3O4@PDA core–shell nanoparticles with enhanced catalytic properties and selectivity

In this work, we have successfully prepared core–shell nanoparticles (Fe₃O₄@PDA) wrapped with Ag using a simple and green synthesis method. Without an external reducing agent, silver nanoparticles (Ag NPs) with good dispersibility were directly reduced and deposited on a polydopamine (PDA) layer. Fe₃O₄@PDA@Ag showed excellent catalytic activity and recyclability for 4-nitrophenol, and also exhibited good catalytic selectivity for organic dyes (MO and MB). This simple and green synthesis method will provide a platform for other catalytic applications.

In this work, we have successfully prepared core–shell nanoparticles (Fe₃O₄@PDA) wrapped with Ag using a simple and green synthesis method.     

Magnetic–plasmonic Ni@Au core–shell nanoparticle arrays and their SERS properties

In this paper, large-area magnetic–plasmonic Ni@Au core–shell nanoparticle arrays (NPAs) with tunable compositions were successfully fabricated by a direct laser interference ablation (DLIA) incorporated with thermal dewetting method. The magnetic properties of the Ni@Au core–shell NPAs were analyzed and the saturation magnetization (M_s) of the Ni₈₀@Au₂₀ nanoparticles was found to be higher than that of nickel-only nanoparticles with the same diameter. Using Rhodamine 6G (R6G) as a Raman reporter molecule, the surface enhanced Raman scattering (SERS) property of the Ni@Au core–shell NPAs with a grain size distribution of 48 ± 42 nm and a short-distance order of about 200 nm was examined. A SERS enhancement factor of 2.5 × 10⁶ was realized on the Ni₅₀@Au₅₀ NPA substrate, which was 9 times higher than that for Au nanoparticles with the same size distribution. This was due to the enhanced local surface plasmon resonance (LSPR) between the ferromagnetic Ni cores and the surface polariton of the Au shells of each nanoparticle. The fabrication of the Ni@Au core–shell NPAs with different compositions offers a new avenue to tailor the optical and magnetic properties of the nanostructured films for chemical and diagnostic applications.

In this paper, large-area magnetic–plasmonic Ni@Au core–shell nanoparticle arrays (NPAs) with tunable compositions were successfully fabricated by a direct laser interference ablation (DLIA) incorporated with thermal dewetting method.     

Crystal-seeds induced construction of ZnO–ZnFe2O4 micro-cubic composites as excellent anode materials for lithium ion battery

This work aims at designing a fine assembly of two different transition metal oxides with a distinct band-gap energy into a bi-component-active hetero-structure to enhance the hetero-interface interactions and synergetic functionalities of bi-components to improve electrochemical performance. Herein, a facile marriage of crystal-seeds induction and hydrothermal reactions has been utilized to fabricate ZnO–ZnFe₂O₄ micro-cubic composites. Benefiting from the synergetic effects of the bi-functional components and their unique hetero-junction structure, the ZnO–ZnFe₂O₄ micro-cubic composites exhibit a significant improvement in lithium storage performance. The reversible capacity is retained at a value of 811 mA h g⁻¹ after 200 cycles at a current density of 100 mA g⁻¹. Even at high current densities of 1 and 5 A g⁻¹, the electrodes are still able to deliver capacities of 584 and 430 mA h g⁻¹ after 200 cycles, respectively.

This work aims at designing a fine assembly of two different transition metal oxides with a distinct band-gap energy into a bi-component-active hetero-structure to improve electrochemical performance.     

Synthesis of magnetic core–shell Fe3O4@PDA@Cu-MOFs composites for enrichment of microcystin-LR by MALDI-TOF MS analysis

Microcystin-LR (MC-LR) is a toxin released from cyanobacteria in eutrophicated water. MC-LR is the most abundant and the most toxic among microcystins. In this work, core–shell structured copper-based magnetic metal–organic framework (Fe₃O₄@PDA@Cu-MOFs) composites were synthesized via a solvothermal reaction and a sol–gel method. The Fe₃O₄@PDA@Cu-MOFs composites showed ultra-high surface area, strong magnetic response and outstanding hydrophilicity. The Fe₃O₄@PDA@Cu-MOFs composites combined with matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS) were used to analyse the content of MC-LR in real water samples. Under the optimised conditions, our proposed method exhibited good linearity within a concentration range of 0.05–4 μg L⁻¹ and good detection even at low limits (0.015 μg L⁻¹). The method was also successfully applied to analyse traces of MC-LR with quantitative recoveries for the real water samples in the range from 98.67% to 106.15%. Furthermore, it was characterized by high sensitivity, short operation time, being environmental friendly and having the ability to analyse other pollutants in the environment.

The synthetic route of the Fe₃O₄@PDA@Cu-MOFs microspheres and enrichment process of MC-LR.     

CNT–TiO2 core–shell structure: synthesis and photoelectrochemical characterization

Porous composite coatings, made of a carbon nanotube (CNT)–TiO₂ core–shell structure, were synthesized by the hybrid CVD-ALD process. The resulting TiO₂ shell features an anatase crystalline structure that covers uniformly the surface of the CNTs. These composite coatings were investigated as photoanodes for the photo-electrochemical (PEC) water splitting reaction. The CNT–TiO₂ core–shell configuration outperforms the bare TiO₂ films obtained using the same process regardless of the deposited anatase thickness. The improvement factor, exceeding 400% in photocurrent featuring a core–shell structure, was attributed to the enhancement of the interface area with the electrolyte and the electrons fast withdrawal. The estimation of the photo-electrochemically effective surface area reveals that the strong absorption properties of CNT severely limit the light penetration depth in the CNT–TiO₂ system.

CNT–TiO₂ core–shell nanostructured coatings were made using a hybrid CVD/ALD process. The evaluation of these films as photoanodes for the photoelectrochemical water splitting reaction reveals a clear benefit from the involvement of CNTs.     

Preparation of core–shell structured metal–organic framework@PANI nanocomposite and its electrorheological properties

A novel core–shell-type electrorheological (ER) composite material was fabricated via using polyaniline as an insulating layer to the outer surface of the core conductive metal–organic framework (MIL-125) with controlled size and morphology. MIL-125 was firstly synthesized by a solvothermal method, and then polyaniline was synthesized in a polar solvent and a tight coating was successfully achieved to form a MIL-125@PANI core–shell nanocomposite. This core–shell structure greatly enhances the polarization ability of dispersed particles, thereby improving their rheological properties. The morphology of pure MIL-125 and MIL-125@PANI has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Their structure was characterized by X-ray powder diffraction. Moreover, the ER activity of MIL-125-based and MIL-125@PANI-based ER fluids by dispersing the particles into silicone oil was studied using a rotational rheometer. The results show that the MIL-125@PANI composite particles have higher ER properties.

Core–shell-structured MIL-125@PANI nanocomposites were synthesized, which can exhibit smart electrorheological behavior under an external electric field.     

One-pot one-step synthesis of Au@SiO2 core–shell nanoparticles and their shell-thickness-dependent fluorescent properties

Herein, we report a one-pot one-step method for the preparation of Au@SiO₂ core–shell nanoparticles (NPs) via a facile heating treatment of an alcoholic-aqueous solution of chloroauric acid (HAuCl₄), 2-methylaminoethanol (2-MAE), cetyltrimethylammonimum bromide (CTAB), and tetraethylorthosilicate (TEOS). The size of the Au core and the thickness of the silica shell can be easily controlled by simply adjusting the volume of HAuCl₄ and TEOS, respectively, which can hardly be achieved by other approaches. The as-prepared Au@SiO₂ core–shell NPs exhibited shell-thickness-dependent fluorescent properties. The optimum fluorescence enhancement of fluorescein isothiocyanate (FITC) was found to occur at a silica shell thickness of 34 nm with an enhancement factor of 5.0. This work provides a new approach for the preparation of Au@SiO₂ core–shell NPs and promotes their potential applications in ultrasensitive analyte detection, theranostics, catalysts and thin-film solar cells.

Au@SiO₂ core–shell nanoparticles with tunable Au core size and silica shell thickness were prepared by a facile one-pot one-step method.     

Adsorption mechanism of polyethyleneimine modified magnetic core–shell Fe3O4@SiO2 nanoparticles for anionic dye removal

In this paper, polyethyleneimine modified magnetic core–shell Fe₃O₄@SiO₂ nanoparticles (Fe₃O₄@SiO₂/PEI) were innovatively synthesized and investigated using various techniques such as TEM, TGA, FT-IR, XRD, VSM and XPS. The adsorption performance based on the removal of the anionic dyes Methyl orange and Congo red from aqueous solution was studied systematically. The results showed that the adsorption rate of anionic dyes MO and CR increased rapidly then decreased gradually as the pH increased, the adsorption capacity of Fe₃O₄@SiO₂/PEI for MO was better than that for CR, and the maximum adsorption capacity for MO and CR was 231.0 mg g⁻¹ at pH 4 and 134.6 mg g⁻¹ at pH 6, respectively. The equilibrium adsorption capacities for MO and CR increased rapidly in the initial 40 min, and reached equilibrium in approximately 180 min, while the adsorption capacity for MB was relative low even negligible, demonstrating the strong adsorptive affinity of Fe₃O₄@SiO₂/PEI toward anionic compounds. Both of the adsorption processes followed the pseudo-second-order kinetics model and the Freundlich isotherm model. The mechanism of adsorption was mainly related to electrostatic attraction and the number of active sites occupied by anionic dyes. This study provides valuable guidance and is an effective method for the removal of anionic dyes from aquatic environments.

In this paper, polyethyleneimine modified magnetic core–shell Fe₃O₄@SiO₂ nanoparticles (Fe₃O₄@SiO₂/PEI) were innovatively synthesized and investigated using various techniques such as TEM, TGA, FT-IR, XRD, VSM and XPS.     

Dual-responsive degradable core–shell nanogels with tuneable aggregation behaviour

We report the synthesis of core–shell nanogels by sequential addition of thermoresponsive monomers; N-isopropylacrylamide (NIPAM) and N-isopropylmethacrylamide (NIPMAM). The aggregation behaviour of aqueous dispersions of these particles in the presence of salt can be tuned by varying the monomer ratio. The inclusion of degradable cross-linker bis(acryloyl)cystamine (BAC) allows the nanogels to degrade in the presence of reducing agent, with nanogels composed of a copolymer of the two monomers not showing the same high levels of degradation as the comparable core–shell particles. These levels of degradation were also seen with physiologically relevant reducing agent concentration at pH 7. Therefore, it is hoped that the aggregation of these nanogels will have applications in nanomedicine and beyond.

Core–shell nanogels with a poly(N-isopropylmethacrylamide) core and poly(N-isopropylacrylamide) shell display tuneable thermoresponsive behaviour and high degradability.     

Understanding metal-enhanced fluorescence and structural properties in Au@Ag core–shell nanocubes

Au@Ag core–shell structures have received particular interest due to their localized surface plasmon resonance properties and great potential as oxygen reduction reaction catalysts and building blocks for self-assembly. In this study, Au@Ag core–shell nanocubes (Au@AgNCs) were fabricated in a facile manner via stepwise Ag reduction on Au nanoparticles (AuNPs). The size of the Au@AgNCs and their optical properties can be simply modulated by changing the Ag shell thickness. Structural characterization has been carried out by TEM, SAED, and XRD. The metal-induced fluorescence properties of probe molecules near the Au@AgNCs were measured during sedimentation of the Au@AgNCs. The unique ring-like building block of Au@AgNCs has dual optical functions as a fluorescence quencher or fluorescence enhancement medium depending on the assembled regions.

The unique ring-like building block of Au@AgNCs has dual optical functions as a fluorescence quencher and fluorescence enhancement medium.     

Constructing high-performance electrode materials using core–shell ZnCo2O4@PPy nanowires for hybrid batteries and water splitting

Heterogeneity can be used as a promising method to improve the electrochemical performance of electrode materials; thus, ZnCo₂O₄@PPy samples were prepared using a facile hydrothermal route and an electrochemical deposition process. The as-prepared products possess a specific capacitance of 605 C g⁻¹ at a current density of 1 A g⁻¹. The asymmetric supercapacitor (ASC) possesses an energy density of 141.3 W h kg⁻¹ at a power density of 2700.5 W kg⁻¹ and capacity retention of 88.1% after 10 000 cycles, indicating its promising potential for energy devices. ZnCo₂O₄@PPy-50 exhibited an excellent OER performance and outstanding HER performance in alkaline media. As an advanced bifunctional electrocatalyst for overall water splitting, a voltage of 1.61 V at a current density of 50 mA cm⁻² outperforms the majority of noble-metal-free electrocatalysts.

Heterogeneity can be used as a promising method to improve the electrochemical performance of electrode materials; thus, ZnCo₂O₄@PPy samples were prepared using a facile hydrothermal route and an electrochemical deposition process.     

Magnetic core–shell Fe3O4@Cu2O and Fe3O4@Cu2O–Cu materials as catalysts for aerobic oxidation of benzylic alcohols assisted by TEMPO and N-methylimidazole

In this work, core–shell Fe₃O₄@Cu₂O and Fe₃O₄@Cu₂O–Cu nanomaterials for aerobic oxidation of benzylic alcohols are reported with 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and N-methylimidazole (NMI) as the co-catalysts. To anchor Cu₂O nanoparticles around the magnetic particles under solvothermal conditions, the magnetic material Fe₃O₄ was modified by grafting a layer of l-lysine (l-Lys) to introduce –NH₂ groups at the surface of the magnetic particles. With amine groups as the anchor, Cu(NO₃)₂ was used to co-precipitate the desired Cu₂O by using ethylene glycol as the reducing agent. Prolonging the reaction time would lead to over-reduced forms of the magnetic materials in the presence of copper, Fe₃O₄@Cu₂O–Cu. The nanomaterials and its precursors were fully characterized by a variety of spectroscopic techniques. In combination with both TEMPO and NMI, these materials showed excellent catalytic activities in aerobic oxidation of benzylic alcohols under ambient conditions. For most of the benzylic alcohols, the conversion into aldehydes was nearly quantitative with aldehydes as the sole product. The materials were recyclable and robust. Up to 7 repeat runs, its activity dropped less than 10%. The over-reduced materials, Fe₃O₄@Cu₂O–Cu, exhibited slightly better performance in durability. The magnetic properties allowed easy separation after reaction by simply applying an external magnet.

Robust core–shell magnetic materials catalyse quantitatively the aerobic oxidation of a wide range of benzylic alcohols into corresponding aldehydes at room temperature showing excellent tolerance towards the substituents on the phenyl ring.