A solvothermal post‐treatment method was developed to synthesize Fe3O4@mesosilica core–shell nanospheres (CSNs) with a well‐preserved morphology, mesoporous structure, and tunable large pore diameters (2.5–17.6 nm) for the first time. N,N‐Dimethylhexadecylamine (DMHA), which was generated in situ during the heat‐treatment process, was mainly responsible for this pore‐size enlargement, as characterized by NMR spectroscopy. This pore‐size expansion can be strengthened with the aid of hexamethyldisilazane (HMDS), whilst the nature of the surface of the Fe3O4@mesosilica CSNs can be easily modified with trimethylsilyl groups during the pore‐size‐expansion process. The hydrophobicity of the Fe3O4@mesosilica CSNs increased for the enlarged mesopores and the adsorption capacity of these CSNs for benzene (up to 1.5 g g?1) is the highest ever reported for Fe3O4@mesosilica CSNs. The resultant Fe3O4@mesosilica CSNs (pore size: 10 nm) showed a 3.6‐times higher adsorption capacity of lysozyme than those without the pore expansion (pore size: 2.5 nm), thus making them a good candidate for loading large molecules. 相似文献
Mixed‐metal sulfide Zn1?xMnxS nanorod‐assembled hierarchical hollow spheres were synthesized by a template‐free solvothermal process based on Ostwald ripening. In the reaction system, glycerol plays a key role in the formation of ZnxMn1?xS hierarchical hollow structures by a quasi‐microemulsion‐template mechanism. When applied as capacitor electrode material, the hierarchical Zn1?xMnxS hollow spheres show excellent electrochemical performance. Specifically, Zn0.25Mn0.75S hollow spheres can deliver a high specific capacitance of 664 F g?1 at a current rate of 1 A g?1, which is almost five times of that of MnS under the same conditions and higher than those of previously reported single Mn‐based compounds. 相似文献
In this work, hybrid porous Co3O4–CeO2 hollow polyhedrons have been successfully obtained via a simple cation‐exchange route followed by heat treatment. In the synthesis process, ZIF‐67 polyhedron frameworks are firstly prepared, which not only serve as a host for the exchanged Ce3+ ions but also act as the template for the synthesis of hybrid porous Co3O4–CeO2 hollow polyhedrons. When utilized as electrode materials for supercapacitors, the hybrid porous Co3O4–CeO2 hollow polyhedrons delivered a large specific capacitance of 1288.3 F g?1 at 2.5 A g?1 and a remarkable long lifespan cycling stability (<3.3 % loss after 6000 cycles). Furthermore, an asymmetric supercapacitor (ASC) device based on hybrid porous Co3O4–CeO2 hollow polyhedrons was assembled. The ASC device possesses an energy density of 54.9 W h kg?1, which can be retained to 44.2 W h kg?1 even at a power density of 5100 W kg?1, indicating its promising application in electrochemical energy storage. More importantly, we believe that the present route is a simple and versatile strategy for the preparation of other hybrid metal oxides with desired structures, chemical compositions and applications. 相似文献
Little hollow! Monodisperse ZnS hollow nanospheres (see figure) of about 200 nm in size have been fabricated on a large scale by a hydrothermal method and they show good photocatalytic activity in the decolorization of an aqueous solution of rhodamine B under UV irradiation.
Mesoporous silica synthesized from the cocondensation of tetraethoxysilane and silylated carbon dots containing an amide group has been adopted as the carrier for the in situ growth of TiO2 through an impregnation–hydrothermal crystallization process. Benefitting from initial complexation between the titania precursor and carbon dot, highly dispersed anatase TiO2 nanoparticles can be formed inside the mesoporous channel. The hybrid material possesses an ordered hexagonal mesostructure with p6mm symmetry, a high specific surface area (446.27 m2 g?1), large pore volume (0.57 cm3 g?1), uniform pore size (5.11 nm), and a wide absorption band between λ=300 and 550 nm. TiO2 nanocrystals are anchored to the carbon dot through Ti?O?N and Ti?O?C bonds, as revealed by X‐ray photoelectron spectroscopy. Moreover, the nitrogen doping of TiO2 is also verified by the formation of the Ti?N bond. This composite shows excellent adsorption capabilities for 2,4‐dichlorophenol and acid orange 7, with an electron‐deficient aromatic ring, through electron donor–acceptor interactions between the carbon dot and organic compounds instead of the hydrophobic effect, as analyzed by the contact angle analysis. The composite can be photocatalytically recycled through visible‐light irradiation after adsorption. The narrowed band gap, as a result of nitrogen doping, and the photosensitization effect of carbon dots are revealed to be coresponsible for the visible‐light activity of TiO2. The adsorption capacity does not suffer any clear losses after being recycled three times. 相似文献
A hierarchical macro‐/mesoporous Ce0.49Zr0.37Bi0.14O1.93 solid‐solution network has been synthesized on a large scale by means of a simple and general polymerization–carbonization–oxidation synthetic route. The as‐prepared product has been characterized by SEM, XRD, TEM, BET surface area measurement, UV/Vis diffuse‐reflectance spectroscopy, energy‐dispersive X‐ray spectroscopy (EDS), and photoelectrochemistry measurements. The photocatalytic activity of the product has been demonstrated through the photocatalytic degradation of methyl orange. Structural characterization has indicated that the hierarchical macro‐/mesoporous solid‐solution network not only contains numerous macropores, but also possesses an interior mesoporous structure. The mesopore size and BET surface area of the network have been measured as 2–25 nm and 140.5 m2 g?1, respectively. The hierarchical macro‐/mesoporous solid‐solution network with open and accessible pores was found to be well‐preserved after calcination at 800 °C, indicating especially high thermal stability. Due to its high specific surface area, the synergistic effect of the coupling of macropores and mesopores, and its high crystallinity, the Ce0.49Zr0.37Bi0.14O1.93 solid‐solution material shows a strong structure‐induced enhancement of visible‐light harvest and exhibits significantly improved visible‐light photocatalytic activity in the photodegradation of methyl orange compared with those of its other forms, such as mesoporous hollow spheres and bulk particles. 相似文献
Ordered mesoporous thin films of composites of rutile TiO2 nanocrystals with amorphous Ta2O5 are fabricated by evaporation‐induced self‐assembly followed by subsequent heat treatment beyond 780 °C. Incorporation of selected amounts of Ta2O5 (20 mol %) in the mesoporous TiO2 film, together with the unique mesoporous structure itself, increased the onset of crystallization temperature which is high enough to ensure the crystallization of amorphous titania to rutile. The ordered mesoporous structure benefits from a block‐copolymer template, which stabilizes the mesostructure of the amorphous mixed oxides before crystallization. The surface and in‐depth composition analysis by X‐ray photoelectron spectroscopy suggests a homogeneous intermixing of the two oxides in the thin film. A detailed X‐ray absorption fine structure measurement on the composite film containing 20 mol % Ta2O5 and heated to 800 °C confirms the amorphous nature of the Ta2O5 phase. Photocatalytic activity evaluation suggests that the rutile nanocrystals in the synthesized ordered mesoporous thin film possess good ability to assist the photodegradation of rhodamine B in water under illumination by UV light. 相似文献
A facile and efficient strategy for the synthesis of hierarchical yolk–shell microspheres with magnetic Fe3O4 cores and dielectric TiO2 shells has been developed. Various Fe3O4@TiO2 yolk–shell microspheres with different core sizes, interstitial void volumes, and shell thicknesses have been successfully synthesized by controlling the synthetic parameters. Moreover, the microwave absorption properties of these yolk–shell microspheres, such as the complex permittivity and permeability, were investigated. The electromagnetic data demonstrate that the as‐synthesized Fe3O4@TiO2 yolk–shell microspheres exhibit significantly enhanced microwave absorption properties compared with pure Fe3O4 and our previously reported Fe3O4@TiO2 core–shell microspheres, which may result from the unique yolk–shell structure with a large surface area and high porosity, as well as synergistic effects between the functional Fe3O4 cores and TiO2 shells. 相似文献
Rare‐earth borates are good candidates for optical applications. To date, however, the high‐pressure/high‐temperature technique has produced a large number of novel borates with optical properties that have rarely been investigated due to the severe problem of substantial defects. We targeted the high‐pressure polymorph of β‐GdB3O6 and synthesized three solid solutions of β‐Gd0.75−x Bi0.25Tbx B3O6 (0≤x ≤0.75), β‐Gd0.75−y Bi0.25Euy B3O6 (0≤y ≤0.75), and β‐Gd0.50−z Bi0.25Tb0.25Euz B3O6 (0≤z ≤0.05) by using typical solid‐state reactions at 820 °C. Here, the function of Bi3+ is to stabilize the high‐pressure phase by lowering the synthetic temperature and being the sensitizer to promote the green and red emissions of Tb3+ and Eu3+. The multiple energy transfer paths were investigated by using lifetime decay experiments and photoluminescent spectra, and both efficiency and mechanism were determined. Eventually, color‐tunable and white emissions were achieved by rational doping of Bi3+, Tb3+, and Eu3+ into β‐GdB3O6, that is, the CIE chromaticity coordinate for β‐Gd0.44Bi0.25Tb0.30Eu0.01B3O6 is (0.318, 0.365) with a correlated color temperature of 6101 K. 相似文献
Upon introducing Ca2+ dopants into the grain lattices by substituting Gd3+ ions, irregular Yb/Er:NaGdF4 nanocrystals prepared through a simple solvothermal route convert into highly uniform nanorods. Meanwhile, their upconversion luminescence intensifies by about 200 times, probably due to a modification of the crystal structure of NaGdF4 and an improvement in the crystallinity of the nanophase. 相似文献
Layered nickel silicate nanoflowers (NSFs) with a hierarchical nanostructure have been successfully fabricated by a template‐free solvothermal method. The as‐prepared nanoflowers were composed of many interconnected edge‐curving lamellae with a thickness of about 15 nm and had a high specific surface area (279 m2 g?1) and large pore volume (0.67 cm3 g?1). The highly dispersed small silver nanoparticles (AgNPs) were immobilized on the surface of NSFs through the in situ reduction of Ag+ by Sn2+. The AgNP/NSF nanocomposites showed a high performance in the catalytic reduction of 4‐nitrophenol. In particular, there was no visible decrease in the catalytic activity of the reused catalysts even after being recycled four times. The as‐prepared AgNP/NSF nanocomposites might be an excellent catalyst owing to their availability, formability, chemical and thermal stability, and high specific surface area. 相似文献
New heteroatom polyoxovanadates (POVs) were synthesized by applying a water‐soluble high‐nuclearity cluster as new synthon. The [V15Sb6O42]6? cluster shell exhibiting D3 symmetry was in situ transformed into completely different cluster shells, namely, the α‐[V14Sb8O42]4? isomer with D2d and the β‐[V14Sb8O42]4? isomer with D2h symmetry. The solvothermal reaction of {Ni(en)3}3[V15Sb6O42(H2O)x] ? 15 H2O (x=0 or 1; en=ethylenediamine) in water led to the crystallization of [{Ni(en)2}2V14Sb8O42] ? 5.5 H2O containing the β‐isomer. The addition of [Ni(phen)3](ClO4)2 ? 0.5 H2O (phen=1,10‐phenanthroline) to the reaction slurry gave the new compound {Ni(phen)3}2[V14Sb8O42] ? phen ? 12 H2O with the α‐isomer. Both transformation reactions are complex due the change of symmetry, the chemical composition, and rearrangement of the VO5 square pyramids and Sb2O5 handle‐like moieties. 相似文献
A facile and robust route for the pre‐synthesized Fe3O4 nanoparticles (NPs) exclusively assembled on both sides of reduced graphene oxide (RGO) sheets with tunable density forming two‐dimensional NPs composite membranes is developed in solution. The assembly is driven by electrostatic attraction, and the nanocomposite sheets display considerable mechanical robustness, such as it can sustain supersonic and solvothermal treatments without NPs falling off, also, can freely float in solution and curl into a tube. The obtained two‐dimensional composite grain membranes exhibit superparamagnetic behavior at room temperature but responds astutely to an external magnetic field. In addition, these magnetic composite membranes show an enhanced absorption capability for microwaves. The grain sheets are attractive for biomedical, sensors, environmental applications and electric‐magnetic devices benefited from large surfaces, high magnetization moment, and superparamagnetic properties. The effective integration of oxide nanocrystals on RGO sheets provides a new way to design semiconductor–carbon nanocomposites for nanodevices or catalytic applications.相似文献
Mesoporous Co3O4 nanosheets (Co3O4‐NS) and nitrogen‐doped reduced graphene oxide (N‐rGO) are synthesized by a facile hydrothermal approach, and the N‐rGO/Co3O4‐NS composite is formulated through an infiltration procedure. Eventually, the obtained composites are subjected to various characterization techniques, such as XRD, Raman spectroscopy, surface area analysis, X‐ray photoelectron spectroscopy (XPS), and TEM. The lithium‐storage properties of N‐rGO/Co3O4‐NS composites are evaluated in a half‐cell assembly to ascertain their suitability as a negative electrode for lithium‐ion battery applications. The 2D/2D nanostructured mesoporous N‐rGO/Co3O4‐NS composite delivered a reversible capacity of about 1305 and 1501 mAh g?1 at a current density of 80 mA g?1 for the 1st and 50th cycles, respectively. Furthermore, excellent cyclability, rate capability, and capacity retention characteristics are noted for the N‐rGO/Co3O4‐NS composite. This improved performance is mainly related to the existence of mesoporosity and a sheet‐like 2D hierarchical morphology, which translates into extra space for lithium storage and a reduced electron pathway. Also, the presence of N‐rGO and carbon shells in Co3O4‐NS should not be excluded from such exceptional performance, which serves as a reliable conductive channel for electrons and act as synergistically to accommodate volume expansion upon redox reactions. Ex‐situ TEM, impedance spectroscopy, and XPS, are also conducted to corroborate the significance of the 2D morphology towards sustained lithium storage. 相似文献
Flowerlike noble‐metal‐free γ‐Fe2O3@NiO core–shell hierarchical nanostructures have been fabricated and examined as a catalyst in the photocatalytic oxidation of water with [Ru(bpy)3](ClO4)2 as a photosensitizer and Na2S2O8 as a sacrificial electron acceptor. An apparent TOF of 0.29 μmols?1 m?2 and oxygen yield of 51 % were obtained with γ‐Fe2O3@NiO. The γ‐Fe2O3@NiO core–shell hierarchical nanostructures could be easily separated from the reaction solution whilst maintaining excellent water‐oxidation activity in the fourth and fifth runs. The surface conditions of γ‐Fe2O3@NiO also remained unchanged after the photocatalytic reaction, as confirmed by X‐ray photoelectron spectroscopy (XPS). 相似文献