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1.
Noble metal nanostructures are grown inside hollow mesoporous silica microspheres using “ship‐in‐a‐bottle” growth. Small Au seeds are first introduced into the interior of the hollow microspheres. Au nanorods with synthetically tunable longitudinal plasmon wavelengths and Au nanospheres are obtained through seed‐mediated growth within the microspheres. The encapsulated Au nanocrystals are further coated with Pd or Pt shells. The microsphere‐encapsulated bimetallic core/shell nanostructures can function as catalysts. They exhibit high catalytic performance and their stability is superior to that of the corresponding unencapsulated core/shell nanostructures in the catalytic oxidation of o‐phenylenediamine with hydrogen peroxide. Therefore, these hollow microsphere‐encapsulated metal nanostructures are promising as recoverable and efficient catalysts for various liquid‐phase catalytic reactions.  相似文献   

2.
The metallic nanostructures with unique properties of tunable plasmon resonance and large field enhancement have been cooperated with semiconductor to construct hetero‐nanostructures for various applications. Herein, a general and facile approach to synthesize uniform dumbbell‐like gold–sulfide core–shell hetero‐nanostructures is reported. The transformation from Au nanorods (NRs) to dumbbell‐like Au NRs and coating of metal sulfide shells (including Bi2S3, CdS, CuxS, and ZnS) are achieved in a one‐pot reaction. Due to the reshaping of Au core and the deposition of sulfide shell, the plasmon resonances of Au NRs are highly enhanced, especially the about 2 times enhancement for the visible transverse plasmon resonance compared with the initial Au NRs. Owing to the highly enhanced visible light absorption and strong local electric field, we find the photocatalytic activity of dumbbell‐like Au–Bi2S3 NRs is largely enhanced compared with pure Bi2S3 and normal Au–Bi2S3 NRs by testing the photodegradation rate of Rhodamine B (RhB). Moreover, the second‐layer sulfide can be coated and the double‐shell Au–Bi2S3–CdS hetero‐nanostructures show further improved photodegradation rate, especially about 2 times than that of Degussa P25 TiO2 (P25) ascribing to the optimum band arrangement and then the prolonged lifetime of photo‐generated carriers.  相似文献   

3.
The synthesis of anisotropic metal nanostructures is strongly desired for exploring plasmon‐enabled applications. Herein, the preparation of anisotropic Au/SiO2 and Au/SiO2/Pd nanostructures is realized through selective silica coating on Au nanobipyramids. For silica coating at the ends of Au nanobipyramids, the amount of coated silica and the overall shape of the coated nanostructures exhibit a bell‐shaped dependence on the cationic surfactant concentration. For both end and side silica coating on Au nanobipyramids, the size of the silica component can be varied by changing the silica precursor amount. Silica can also be selectively deposited on the corners or facets of Au nanocubes, suggesting the generality of this method. The blockage of the predeposited silica component on Au nanobipyramids enables further selective Pd deposition. Suzuki coupling reactions carried out with the different bimetallic nanostructures functioning as plasmonic photocatalysts indicate that the plasmonic photocatalytic activity is dependent on the site of Pd nanoparticles on Au nanobipyramids. Taken together, these results suggest that plasmonic hot spots play an important role in hot‐electron‐driven plasmonic photocatalysis. This study opens up a promising route to the construction of anisotropic bimetallic nanostructures as well as to the design of bimetallic plasmonic‐catalytic nanostructures as efficient plasmonic photocatalysts.  相似文献   

4.
Design of multicomponent yolk–shell structures is crucial for the fabrication of micro/nanoreactors for a variety of applications. This work reports the rational design and synthesis of yolk–shell‐structured submicroreactors with loaded metal nanoparticles into ZnO–microporous carbon core–shell structures. The solvothermal treatment and carbonization process of uniform zeolitic imidazolate framework‐8 (ZIF‐8)@resin polymer core–shell structures leads to the generation of yolk–shell‐structured ZnO@carbon. The synthesis conditions are optimized to track the evolution of ZIF‐8 in a confined space of resin polymer as a submicroreactor itself. It is found that nanoribbon evolution occurs via the formation of the intermediate needle‐like particles. The Pd&ZnO@carbon submicroreactor is shown to be a highly selective catalyst (selectivity >99%) for hydrogenation of phenylacetylene to phenylethylene. The excellent performance of Pd&ZnO@carbon particles is evidenced by higher conversion and selectivity than that of Pd/ZnO and Pd/C with similar Pd loading. Furthermore, Pd&ZnO@carbon submicroreactors show superior catalytic stability, and no deactivation after 25 h of reaction. The proposed strategy is promising for the design of multifunctional micro/nanoreactors or nanocontainers for construction of artificial cells.  相似文献   

5.
Mesostructured silica nanofibers synthesized in high yields with cetyltrimethylammonium bromide as the structure‐directing agent in HBr solutions are used as templates for the assembly of Au and Ag nanoparticles and the formation of thin Au shells along the fiber axis. Presynthesized spherical Au and Ag nanoparticles are adsorbed in varying amounts onto the silica nanofibers through bifunctional linking molecules. Nonspherical Au nanoparticles with sharp tips are synthesized on the nanofibers through a seed‐mediated growth approach. The number density of nonspherical Au nanoparticles is controlled by varying the amount of seeded nanofibers relative to the amount of supplied Au precursor. This seed‐mediated growth is further used to form continuous Au shells around the silica nanofibers. Both the Au‐ and Ag‐nanoparticle/silica‐nanofiber hybrid nanostructures and silica/Au core/shell fibers exhibit extinction spectra that are distinct from the spectra of Au and Ag nanoparticles in solution, indicating the presence of new surface plasmon resonance modes in the silica/Au core/shell fibers and surface plasmon coupling between closely spaced metal nanoparticles assembled on silica nanofibers. Spherical Au‐ and Ag‐nanoparticle/silica‐nanofiber hybrid nanostructures are further used as substrates for surface‐enhanced Raman spectroscopy, and the enhancement factors of the Raman signals obtained on the Ag‐nanoparticle/silica‐nanofiber hybrid nanostructures are 2 × 105 for 4‐mercaptobenzoic acid and 4‐mercaptophenol and 7 × 107 for rhodamine B isothiocyanate. These hybrid nanostructures are therefore potentially useful for ultrasensitive chemical and biological sensing by using molecular vibrational signatures.  相似文献   

6.
We report a general template strategy for rational fabrication of a new class of nanostructured materials consisting of multicore shell particles. Our approach is demonstrated by encapsulating Au or Pt nanoparticles in silica shells. Other superstructures of these hollow shells, like dimers, trimers, and tetramers can also be formed by nanoparticle‐mediated self‐assembly. We have also used the as‐prepared multicore Au–silica hollow particles to perform the first studies of Ostwald ripening in confined microspace, in which chloride was found to be an efficient mediating ligand. After treatment with aqua regia, Au–Cl complex is formed inside the shell, and is found to be very active under in situ transmission electron microscopy observations while confined in a microcell. This aspect of the work is expected to motivate further in situ studies of confined crystal growth.  相似文献   

7.
Hydrogen detection is crucial for the safety of all hydrogen‐related applications. Compared to electrical hydrogen sensors, which usually suffer from possible electric sparks, optical hydrogen sensors offer advantages of remote and contact‐free readout and therefore the avoidance of spark generation. Herein, bimetallic Au/Pd nanostructure monolayers that exhibit ultrasensitive plasmonic response to hydrogen are reported. Bimetallic Au/Pd nanostructures with continuous and discontinuous Pd shells are prepared. The plasmonic response to hydrogen is monitored by measuring the extinction spectra of the ensemble Au/Pd nanostructures deposited on glass slides. Introduction of hydrogen induces red plasmon shifts, which become larger for the nanostructures with thicker Pd shells. For the nanostructures with continuous Pd shell, the plasmon shift can reach 56 nm at the hydrogen volume concentration below the explosion limit. The plasmon resonance wavelength displays an excellent linear dependence on the hydrogen volume concentration below 1%. The detection limit in the experiments reaches 0.2%. The nanostructures with discontinuous Pd shell show smaller plasmon shifts than those with continuous Pd shell. The extinction measurements on the ensemble nanostructures supported on transparent substrates and the unprecedentedly large plasmon shifts and sensitivity make the results very promising for the development of practical optical hydrogen sensors.  相似文献   

8.
In this paper, a facile sol–gel process for producing monodisperse, spherical, and nonaggregated pigment particles with a core/shell structure is reported. Spherical silica particles (245 and 385 nm in diameter) and Cr2O3, α‐Fe2O3, ZnCo2O4, CuFeCrO4, MgFe2O4, and CoAl2O4 pigments are selected as cores and shells, respectively. The obtained core/shell‐structured pigment samples, denoted as SiO2@Cr2O3 (green), SiO2@α‐Fe2O3 (red), SiO2@MgFe2O4 (brown), SiO2@ZnCo2O4 (dark green), SiO2@CoAl2O4 (blue), and SiO2@CuFeCrO4 (black), are well characterized by using X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and UV‐vis diffuse reflection, as well as by investigating the magnetic properties. The results of XRD and high‐resolution TEM (HRTEM) demonstrate that the pigment shells crystallize well on the surface of SiO2 particles. The thickness of the pigment shell can be tuned by the number of coatings, to some extent. These pigment particles can be well dispersed in some solvents (such as glycol) to form relatively more stable suspensions than the commercial products. Apart from the color characteristics, some of pigments like SiO2@Cr2O3, SiO2@MgFe2O4, and SiO2@CuFeCrO4 also show magnetic properties with coercivities of 1098 Oe (5 K), 648 Oe (5 K), and 91 Oe (298 K), respectively.  相似文献   

9.
A yolk‐shell‐structured carbon@void@silicon (CVS) anode material in which a void space is created between the inside silicon nanoparticle and the outer carbon shell is considered as a promising candidate for Li‐ion cells. Untill now, all the previous yolk‐shell composites were fabricated through a templating method, wherein the SiO2 layer acts as a sacrificial layer and creates a void by a selective etching method using toxic hydrofluoric acid. However, this method is complex and toxic. Here, a green and facile synthesis of granadilla‐like outer carbon coating encapsulated silicon/carbon microspheres which are composed of interconnected carbon framework supported CVS nanobeads is reported. The silicon granadillas are prepared via a modified templating method in which calcium carbonate was selected as a sacrificial layer and acetylene as a carbon precursor. Therefore, the void space inside and among these CVS nanobeads can be formed by removing CaCO3 with diluted hydrochloric acid. As prepared, silicon granadillas having 30% silicon content deliver a reversible capacity of around 1100 mAh g?1 at a current density of 250 mA g?1 after 200 cycles. Besides, this composite exhibits an excellent rate performance of about 830 and 700 mAh g?1 at the current densities of 1000 and 2000 mA g?1, respectively.  相似文献   

10.
Au‐incorporation is a promising strategy to retard composition‐loss in Pt‐based catalyst. However, the unclear mechanism limits guided catalyst design and the performance optimization. Here, direct evidence is provided to validate the outward diffusion of Au atoms in Au‐core/Pt‐based‐shell structures. A Co interlayer is built between the Au‐core and PtCo‐based shell to exclude the possibility of atomic diffusion caused by interfacial alloying. In conjunction with the improved catalytic durability of the Au‐core@Pt‐based‐shell structure, it is reasonable to conclude that it is the subsurface segregated Au atoms rather than interfacial interaction that boosts the catalytic durability of Au‐core/Pt‐based‐shell structured catalysts towards oxygen reduction reaction. More importantly, by constructing Au‐core@Co‐interlayer@PtCoAu‐shell multilayer structure, the specific (1.730 mA cm?2) and mass (0.692 A mg?1Pt) activities are enhanced 7‐ and 4‐ fold relative to the commercial Pt/C. After 10 000 cycles of accelerated durability test, the mass activity loss for the multilayered catalyst is as low as 6.14% while the loss exceeds 35% for the commercial Pt/C catalyst. The improved catalytic performance of the Au@Co@PtCoAu multilayer structure can be ascribed to the finely modulated electronic structure and the compensated composition loss owing to the delicate structure and composition profile design.  相似文献   

11.
TiO2 hollow shells with well‐controlled crystallinity, phase, and porosity are desirable in many applications. In photocatalysis in particular, they can provide high active surface area, reduced diffusion resistance, and improved accessibility to reactants. Here, the results from studies of the causes for the failure of a prior etching and calcination scheme to make such shells and on a newly‐developed simple yet robust process for producing uniform mesoporous TiO2 shells with precisely controllable crystallinity and phase are reported. The key finding is that base etching of the SiO2@TiO2 core‐shell particles leads to the formation of sodium titanate species, which, if not removed, promote substantial crystal growth during calcination and destroy the structural integrity of the TiO2 shells. A simple acid treatment of the base‐etched samples may convert the sodium titanates into protonated titanates, which not only prevent the formation of the impurity phases, but also help to maintain the structural integrity of the shell and allow precise control of the TiO2 phase and crystallinity. This new development affords convenient optimization of the structure of the hollow TiO2 shells toward efficient photocatalysts, which outperform the commercial P25‐TiO2 in the photocatalytic decomposition of organic dye molecules.  相似文献   

12.
Tumor ablation by thermal energy via the irradiation of plasmonic nanoparticles is a relatively new oncology treatment. Hybrid plasmonic‐superparamagnetic nanoaggregates (50–100 nm in diameter) consisting of SiO2‐coated Fe2O3 and Au (≈30 nm) nanoparticles were fabricated using scalable flame aerosol technology. By finely tuning the Au interparticle distance using the SiO2 film thickness (or content), the plasmonic coupling of Au nanoparticles can be finely controlled bringing their optical absorption to the near‐IR that is most important for human tissue transmittance. The SiO2 shell facilitates also dispersion and prevents the reshaping or coalescence of Au particles during laser irradiation, thereby allowing their use in multiple treatments. These nanoaggregates have magnetic resonance imaging (MRI) capability as shown by measuring their r2 relaxivity while their effectiveness as photothermal agents is demonstrated by killing human breast cancer cells with a short, four minute near‐IR laser irradiation (785 nm) at low flux (4.9 W cm‐2).  相似文献   

13.
Nanoparticles of transition metals, particularly noble metals, are widely used in catalysis. However, enhancing their stability during catalytic reactions has been a challenge that has limited the full use of the benefits associated with their small size. In this Feature Article, a general “encapsulation and etching” strategy for the fabrication of nanocatalyst systems is introduced in which catalyst nanoparticles are protected within porous shells. The novelty of this approach lies in the use of chemical etching to assist the creation of mesopores in a protective oxide shell to promote efficient mass transfer to encapsulated metal nanoparticles. The etching process allows for the direct transformation of dense silica coatings into porous shells so that chemical species can reach the catalyst surface to participate in reactions while the shells act as physical barriers against aggregation of the catalyst particles. By using the surface‐protected etching process, both yolk–shell and core–satellite type nanoreactors are synthesized and their utilization in liquid‐ and gas‐phase catalysis is demonstrated. The thermal and chemical stability of the metallic cores during catalytic reactions is also investigated, and further work is carried out to enhance recyclability via the introduction of superparamagnetic components into the nanoreactor framework.  相似文献   

14.
Precise control of the topology of metal nanocrystals and appropriate modulation of the metal–semiconductor heterostructure is an important way to understand the relationship between structure and material properties for plasmon‐induced solar‐to‐chemical energy conversion. Here, a bottom‐up wet chemical approach to synthesize Au/Ni2P heterostructures via Pt‐catalyzed quasi‐epitaxial overgrowth of Ni on Au nanorods (NR) is presented. The structural motif of the Ni2P is controlled using the aspect ratio of the Au NR and the effective micelle concentration of the C16TAB capping agent. Highly ordered Au/Pt/Ni2P nanostructures are employed as the photoelectrocatalytic anode system for water splitting. Electrochemical and ultrafast absorption spectroscopy characterization indicates that the structural motif of the Ni2P (controlled by the outer‐shell deposition of Ni) helps to manipulate hot electron transfer during surface plasmon decay. With optimized Ni2P thickness, Pt‐tipped Au NR with an aspect ratio of 5.2 exhibits a geometric current density of 10 mA cm?2 with an overpotential of 140 mV. The photoanode displays unprecedented long‐term stability with continuous chronoamperometric performance of 50 h at an input potential of 1.5 V with over 30 days. This work provides definitive guidance for designing plasmonic–catalytic nanomaterials for enhanced solar‐to‐chemical energy conversion.  相似文献   

15.
The synthesis of large lattice mismatch metal‐semiconductor core–shell hetero‐nanostructures remains challenging, and thus the corresponding optical properties are seldom discussed. Here, we report the gold‐nanorod‐seeded growth of Au–CdS core–shell hetero‐nanorods by employing Ag2S as an interim layer that favors CdS shell formation through a cation‐exchange process, and the subsequent CdS growth, which can form complete core–shell structures with controllable shell thickness. Exciton–plasmon interactions observed in the Au–CdS nanorods induce shell thickness‐tailored and red‐shifted longitudinal surface plasmon resonance and quenched CdS luminescence under ultraviolet light excitation. Furthermore, the Au–CdS nanorods demonstrate an enhanced and plasmon‐governed two‐photon luminescence under near‐infrared pulsed laser excitation. The approach has potential for the preparation of other metal‐semiconductor hetero‐nanomaterials with complete core–shell structures, and these Au–CdS nanorods may open up intriguing new possibilities at the interface of optics and electronics.  相似文献   

16.
A rapid, simple, and efficient method for the preparation of highly dispersed supported Au catalysts has been developed. In the preparation, NaBH4 is used to reduce the Au precursor, lysine is employed to cap the formed Au colloids, and a short sonication time is applied to facilitate dispersion and deposition of the Au colloids onto the catalyst support, which has been mixed with the precursor beforehand. The end‐point pH value of the solution and the isoelectric points (IEPs) of the catalyst supports have an influence on the size of the Au particles and their deposition. The optimum value for the end‐point pH is 7.5–10.0, and the IEP should be 5–10. The amino acid capping agent is easily removed at the catalyst activation stage at 200 °C, and the Au particles are thermally stable against sintering, even at 500 °C for 3 h. It is also proven that the method is applicable to the preparation of supported Pt catalysts. The catalytic activity of the prepared Au catalysts for CO oxidation in the absence/presence of H2 is comparable to that of a Au catalyst prepared by the co‐precipitation (CP) method, and to that of the standard catalyst from the World Gold Council (WGC). X‐ray photoelectron spectroscopy (XPS) results show that only metallic Au exists in the catalysts before and after activation, and also after the catalysis reaction.  相似文献   

17.
A high‐energy conversion efficiency of 8.2% at 100 mW cm?2 is reported, one of the highest values for N719‐based, solid‐state, dye‐sensitized solar cells (ssDSSCs). The solar cells are based on hierarchical double‐shell nanostructures consisting of inner SnO2 hollow spheres (SHS) surrounded by outer TiO2 nanosheets (TNSs). Deposition of the TNS on the SHS outer surface is performed via solvothermal reactions in order to generate a double‐shell SHS@TNS nanostructure that provides a large surface area and suppresses recombination of photogenerated electrons. An organized mesoporous (OM)‐TiO2 film with high porosity, large pores, and good interconnectivity is also prepared via a sol‐gel process using a poly(vinyl chloride)‐g‐poly(oxyethylene methacrylate) (PVC‐g‐POEM) graft copolymer template. This film is utilized as a matrix to disperse the double‐shell nanostructures. Such nanostructures provide good pore‐filling for solid polymer electrolytes, faster electron transfer, and enhanced light scattering, as confirmed by reflectance spectroscopy, incident photon‐to‐electron conversion efficiency (IPCE), and intensity‐modulated photocurrent spectroscopy (IMPS)/intensity‐modulated photovoltage spectroscopy (IMVS).  相似文献   

18.
This study demonstrates a novel approach towards the development of advanced protein assay systems based on physically functionalized, magnetic‐core/porous‐shell CoFe2O4/SiO2 composite nanoparticles. The preparation, characterization, and measurement of the relevant properties of the protein assay system is discussed, and the system is used for the detection of cancer antigen 15‐3 (CA 15‐3, used as a model here) in clinical immunoassays. The protein assay system, based on nanometer‐sized magnetic cores and silica shells, shows good adsorption properties for the selective attachment of CA 15‐3 antibodies specific to CA 15‐3. The core/shell nanostructures exhibit good magnetic properties, which enables their integration into a quartz crystal microbalance (QCM) detection cell with the help of a permanent magnet. Under optimal conditions, the resulting immunoassay system presents a good QCM response for the detection of CA 15‐3, and allows the detection of CA 15‐3 at concentrations as low as 1.5 U mL–1 (U: units). Importantly, the proposed protein assay system can be extended to the detection of other antigens and biological compounds.  相似文献   

19.
The design of new functional materials with excellent hydrogen production activity under visible‐light irradiation has critical significance for solving the energy crisis. A well‐controlled synthesis strategy is developed to prepare an Au–Pt–CdS hetero‐nanostructure, in which each component of Au, Pt, and CdS has direct contact with the other two materials; Pt is on the tips and a CdS layer along the sides of an Au nanotriangle (NT), which exhibits excellent photocatalytic activity for hydrogen production under light irradiation (λ > 420 nm). The sequential growth and surfactant‐dependent deposition produce the three‐component Au–Pt–CdS hybrids with the Au NT acting as core while Pt and CdS serve as a co‐shell. Due to the presence of the Au NT cores, the Au–Pt–CdS nanostructures possess highly enhanced light‐harvesting and strong local‐electric‐field enhancement. Moreover, the intimate and multi‐interface contact generates multiple electron‐transfer pathways (Au to CdS, CdS to Pt and Au to Pt) which guide photoexcited electrons to the co‐catalyst Pt for an efficient hydrogen reduction reaction. By evaluating the hydrogen production rate when aqueous Na2SO3–Na2S solution is used as sacrificial agent, the Au–Pt–CdS hybrid exhibits excellent photocatalytic activity that is about 2.5 and 1.4 times larger than those of CdS/Pt and Au@CdS/Pt, respectively.  相似文献   

20.
Janus particles have proven to be original particles to sense protein-cell interactions or to organize cell on a substrate. This work presents a covalent coupling strategy to graft fibronectin on a specific side of Au/PS or Au/SiO2 1 μm Janus particles. By studying several buffers that could limit adsorption of protein on plain particles of PS, SiO2 and Au, fibronectin is covalently grafted on those particles. We demonstrate two ways of grafting proteins on one side of the Janus particles, either on the Au side functionalized with thiols or on the PS/SiO2 side activated with carboxylate groups.  相似文献   

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