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1.
A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 103 per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd2+ after the dissolution of the CdTe tags with HNO3. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.  相似文献   

2.
A novel approach combining layer‐by‐layer (LbL) assembly with biomimetic mineralization is proposed to prepare protamine–titiania hybrid microcapsules. More specifically, these microcapsules are fabricated by alternative deposition of positively charged protamine layers and negatively charged titania layers on the surface of CaCO3 microparticles, followed by dissolution of the CaCO3 microparticles using EDTA. During the deposition process, the protamine layer induces the hydrolysis and condensation of a titania precursor, to form the titania layer. Thereafter, the negatively charged titania layer allows a new cycle of deposition step of the protamine layer, which ensures a continuous LbL process. The morphology, structure, and chemical composition of the microcapsules are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, and X‐ray photoelectron spectroscopy. Moreover, these protamine–titania hybrid microcapsules are first employed as the carrier for the immobilization of yeast alcohol dehydrogenase (YADH), and the encapsulated YADH displays enhanced recycling stability. This approach may open a facile, general, and efficient way to prepare organic–inorganic hybrid materials with different compositions and shapes.  相似文献   

3.
Novel, 3D hierarchical Co3O4 twin‐spheres with an urchin‐like structure are produced successfully on the large scale for the first time by a solvothermal synthesis of cobalt carbonate hydroxide hydrate, Co(CO3)0.5(OH)·0.11H2O, and its subsequent calcination. The morphology of the precursor, which dominates the structure of the final product, evolves from nanorods to sheaf‐like bundles, to flower‐like structures, to dumbbell‐like particles, and eventually to twin‐spheres, accompanying a prolonged reaction time. A multistep‐splitting growth mechanism is proposed to understand the formation of the 3D hierarchical twin‐spheres of the precursor, based on the time effect on the morphologies of the precursor. The 3D hierarchical Co3O4 twin‐spheres are further used as electrode materials to fabricate supercapacitors with high specific capacitances of 781, 754, 700, 670, and 611 F g?1 at current densities of 0.5, 1, 2, 4, and 8 A g?1, respectively. The devices also show high charge‐discharge reversibility with an efficiency of 97.8% after cycling 1000 times at a current density of 4 A g?1.  相似文献   

4.
Negatively charged gold nanoparticles (AuNPs) and a polyelectrolyte (PE) have been assembled alternately on a polystyrene (PS) colloid by a layer‐by‐layer (LBL) self‐assembly technique to form three‐dimensional (Au/PAH)4/(PSS/PAH)4 multilayer‐coated PS spheres (Au/PE/PS multilayer spheres). The Au/PE/PS multilayer spheres have been used to modify a boron‐doped diamond (BDD) electrode. Cyclic voltammetry is utilized to investigate the properties of the modified electrode in a 1.0 M KCl solution that contains 5.0 × 10?3 M K3Fe(CN)6, and the result shows a dramatically decreased redox activity compared with the bare BDD electrode. The electrochemical behaviors of dopamine (DA) and ascorbic acid (AA) on the bare and modified BDD electrode are studied. The cyclic voltammetric studies indicate that the negatively charged, three‐dimensional Au/PE/PS multilayer sphere‐modified electrodes show high electrocatalytic activity and promote the oxidation of DA, whereas they inhibit the electrochemical reaction of AA, and can effectively be used to determine DA in the presence of AA with good selectivity. The detection limit of DA is 0.8 × 10?6 M in a linear range from 5 × 10?6 to 100 × 10?6 M in the presence of 1 × 10?3 M AA.  相似文献   

5.
The quality of heterojunctions at the quantum dot (QD)‐TiO2 nanotube (TNT) interface has important implications on the efficiencies of photoelectrochemical solar cells. Here, it is shown that electrophoretic deposition of pre‐synthesized thioacid‐capped CdTe QDs results in relatively poor charge transfer across the heterojunctions. This is likely due to the intermediate layer of bifunctional linkers (S‐R‐COOH) in between the QDs and TNT. On the other hand, CdTe QD‐sensitized TNT prepared by in situ deposition in aqueous medium provides direct QD‐TNT contact, and hence more favorable heterojunction for charge transfer. This is exemplified not only by the drastic improvement in photocurrent efficiencies, but also provides clear difference on the size‐dependent electron injection efficiencies from the CdTe QDs of different sizes. By extending the system further to CdSe QDs, drastic enhancement is found when carrying out the in situ deposition in an organic medium. The results are discussed in terms of the nature of deposition and the corresponding charge transport characteristics. More importantly, the work reflects the intricacy of the effects of QD size and the quality of the heterojunctions on the overall photoconversion efficiencies.  相似文献   

6.
MXene materials have attracted increasing attention in electrochemical energy‐storage applications while MXene also becomes photo‐active at the quantum dot scale, making it an alternative for solar‐energy‐conversion devices. A Janus‐structured cobalt‐nanoparticle‐coupled Ti3C2 MXene quantum dot (Co‐MQD) Schottky catalyst with tunable cobalt‐loading content serving as a photoelectrochemical water oxidation photoanode is demonstrated. The introduction of cobalt triggers concomitant surface‐plasmon effects and acts as a water oxidation center, enabling visible‐light harvesting capability and improving surface reaction kinetics. Most importantly, due to the rectifying effects of Co‐MQD Schottky junctions, photogenerated carrier separation/injection efficiency can be fundamentally facilitated. Specifically, Co‐MQD‐48 exhibits both superior photoelectrocatalysis (2.99 mA cm?2 at 1.23 V vs RHE) and charge migration performance (87.56%), which corresponds to 194% and 236% improvement compared with MQD. Furthermore, excellent photostability can be achieved with less than 6.6% loss for 10 h cycling reaction. This fills in gaps in MXene material research in photoelectrocatalysis and allows for the extension of MXene into optical‐related fields.  相似文献   

7.
Free‐standing CaCO3 materials are an important member in biological systems because of their existence in many natural organisms such as nacre, shell, and crustacean cuticle. However, toughness of those artificial mineral films is sacrificed once their inorganic content is up to 90%, thus free‐standing characteristics have seldom been achieved for CaCO3 films, let alone their real applications. Herein a fast and simple method for constructing hydrogel “bridges” for CaCO3 microparticles is presented, developing highly flexible free‐standing CaCO3 films with only 5% organic content. Such integrated films have underwater superoleophobicity and self‐cleaning function, which guarantee their repeated application in oil/water separation. Furthermore, heavy metal ions can be efficiently removed by simple filtration with the films. Because of the self‐similar structure, the films are able to resist mechanical abrasion without losing the anti‐wetting property and separation efficiency. The free‐standing CaCO3 films are put forward for the first time to practical application, demonstrating the strategy can bring a brilliant prospect to artificial biomineral materials.  相似文献   

8.
The refractive indices of naturally occurring materials are limited, and there exists an index gap between indices of air and available solid materials. With many photonics and electronics applications, there has been considerable effort in creating artificial materials with optical and dielectric properties similar to air while simultaneously being mechanically stable to bear load. Here, a class of ordered nanolattice materials consisting of periodic thin‐shell structures with near‐unity refractive index and high stiffness is demonstrated. Using a combination of 3D nanolithography and atomic layer deposition, these ordered nanostructured materials have reduced optical scattering and improved mechanical stability compared to existing randomly porous materials. Using ZnO and Al2O3 as the building materials, refractive indices from 1.3 down to 1.025 are achieved. The experimental data can be accurately described by Maxwell Garnett effective media theory, which can provide a guide for index design. The demonstrated low‐index, low‐scattering, and high‐stiffness materials can serve as high‐quality optical films in multilayer photonic structures, waveguides, resonators, and ultra‐low‐k dielectrics.  相似文献   

9.
The short‐wavelength response of cadmium sulfide/cadmium telluride (CdS/CdTe) photovoltaic (PV) modules can be improved by the application of a luminescent down‐shifting (LDS) layer to the PV module. The LDS layer contains a mixture of fluorescent organic dyes that are able to absorb short‐wavelength light of λ < 540 nm, for which the PV module exhibited low external quantum efficiency (EQE), and re‐emit it at a longer wavelength (λ > 540 nm), where the solar cell EQE is high. Ray‐tracing simulations indicate that a mixed LDS layer containing three dyes could lead to an increase in the short‐circuit current density from Jsc = 19.8 mA/cm2 to Jsc = 22.9 mA/cm2 for a CdS/CdTe PV module. This corresponds to an increase in conversion efficiency from 9.6% to 11.2%. This indicates that a relative increase in the performance of a production CdS/CdTe PV module of nearly 17% can be expected via the application of LDS layers, possibly without any making any alterations to the solar cell itself. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

10.
To fabricate a high‐efficiency polycrystalline thin‐film tandem cell, the most critical work is to make a high‐efficiency top cell ( > 15%) with high bandgap (Eg = 1·5–1·8 eV) and high transmission (T > 70%) in the near‐infrared (NIR) wavelength region. The CdTe cell is one of the candidates for the top cell, because CdTe state‐of‐the‐art single‐junction devices with efficiencies of more than 16% are available, although its bandgap (1·48 eV) is slightly lower for a top cell in a current‐matched dual‐junction device. In this paper, we focus on the development of a: (1) thin, low‐bandgap CuxTe transparent back‐contact; and (2) modified CdTe device structure, including three novel materials: cadmium stannate transparent conducting oxide (TCO), ZnSnOx buffer layer, and nanocrystalline CdS:O window layer developed at NREL, as well as the high‐quality CdTe film, to improve transmission in the NIR region while maintaining high device efficiency. We have achieved an NREL‐confirmed 13·9%‐efficient CdTe transparent solar cell with an infrared transmission of ∼50% and a CdTe/CIS polycrystalline mechanically stacked thin‐film tandem cell with an NREL‐confirmed efficiency of 15·3%. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

11.
High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs2CO3) or lithium carbonate (Li2CO3). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs2CO3 show a luminous efficiency (LE) of 35.1 cd A?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs2CO3 have a luminous efficiency of 37.7 cd A?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.  相似文献   

12.
In the study of hybrid quantum dot light‐emitting diodes (QLEDs), even for state‐of‐the‐art achievement, there still exists a long‐standing charge balance problem, i.e., sufficient electron injection versus inefficient hole injection due to the large valence band offset of quantum dots (QDs) with respect to the adjacent carrier transport layer. Here the dedicated design and synthesis of high luminescence Zn1?x CdxSe/ZnSe/ZnS QDs is reported by precisely controlled shell growth, which have matched energy level with the adjacent hole transport layer in QLEDs. As emitters, such Zn1?xCdxSe‐ based QLEDs exhibit peak external quantum efficiencies (EQE) of up to 30.9%, maximum brightness of over 334 000 cd m?2, very low efficiency roll‐off at high current density (EQE ≈25% @ current density of 150 mA cm?2), and operational lifetime extended to ≈1 800 000 h at 100 cd m?2. These extraordinary performances make this work the best among all solution‐processed QLEDs reported in literature so far by achieving simultaneously high luminescence and balanced charge injection. These major advances are attributed to the combination of an intermediate ZnSe layer with an ultrathin ZnS outer layer as the shell materials and surface modification with 2‐ethylhexane‐1‐thiol, which can dramatically improve hole injection efficiency and thus lead to more balanced charge injection.  相似文献   

13.
High‐performance graphene microwave absorption materials are highly desirable in daily life and some extreme situations. A simple technique for the direct growth of graphene as absorption fillers in wave‐transmitting matrices is of paramount importance to bring it to real‐world application. Herein, a simple chemical vapor deposition (CVD) route for the direct growth of edge‐rich graphene (ERG) with tailored structures and tunable dielectric properties in porous Si3N4 ceramics using only methyl alcohol (CH3OH) as precursor is reported. The large O/C atomic ratio of CH3OH helps to build a mild oxidizing atmosphere and leads to a unique structure featuring open graphite nanosteps and freestanding nanoplanes, endowing the ERG/Si3N4 hybrid with an appropriate balance between good impedance matching and strong loss capacity. Accordingly, the prepared materials exhibit superior electromagnetic wave absorption, far surpassing that of traditional CVD graphene and reduced graphene oxide‐based materials, achieving an effective absorption bandwidth of 4.2 GHz covering the entire X band, with a thickness of 3.75 mm and a negligibly low loading content of absorbents. The results provide new insights for developing novel microwave absorption materials with strong reflection loss and wide absorption frequency range.  相似文献   

14.
A method is presented for predicting and precisely controlling the structure of photonic crystals fabricated using sacrificial‐layer atomic layer deposition. This technique provides a reliable method for fabrication of high‐quality non‐close‐packed inverse shell opals with large static tunability and precise structural control. By using a sacrificial layer during opal infiltration, the inverse‐opal pore size can be increased with sub‐nanometer resolution and without distorting the lattice to allow for a high degree of dielectric backfilling and increased optical tunability. For a 10 % sacrificial layer, static tunability of 80 % is predicted for the inverse opal. To illustrate this technique, SiO2 opal templates were infiltrated using atomic layer deposition of ZnS, Al2O3, and TiO2. Experimentally, a static tunability of over 600 nm, or 58 %, was achieved and is well described by both a geometrical model and a numerical‐simulation algorithm. When extended to materials of higher refractive index, this method will allow the facile fabrication of 3D photonic crystals with optimized photonic bandgaps.  相似文献   

15.
Black phosphorus (BP) is an interesting two‐dimensional material with low‐cost and abundant metal‐free properties and is used as one cocatalyst for photocatalytic H2 production. However, the BP quantum dot (BPQD) is not studied. Herein, for the first time, BPQD is introduced as a hole‐migration cocatalyst of layered g‐C3N4 for visible‐light‐driven photocatalytic hydrogen generation. A high‐vacuum stirring method is developed for BPQD loading without the dissociation of BP. The layered BPQD is coupled on the layered g‐C3N4 surface to form a heterojunction structure. The 7% BPQD–C3N4 samples show similar time‐resolved photoluminescence curves as 0.5% Pt–C3N4. The optimum hydrogen rates of the modified sample (7% BPQD–C3N4) are 190, 133, 90, and 10.4 µmol h?1 under simulated sunlight, LED‐405, LED‐420, and LED‐550 nm irradiation, respectively, which are 3.5, 3.6, and 3 times larger than that of the pristine g‐C3N4. Such low‐cost layered system not only optimizes the optical, electrical, and texture properties of the hybrid materials for photocatalytic water splitting to generate hydrogen but also provides ideas for designing novel or easily oxidized candidates by incorporating different available materials with given carriers.  相似文献   

16.
Improving the capacitance of carbon materials for supercapacitors without sacrificing their rate performance, especially volumetric capacitance at high mass loadings, is a big challenge because of the limited assessable surface area and sluggish electrochemical kinetics of the pseudocapacitive reactions. Here, it is demonstrated that “self‐doping” defects in carbon materials can contribute to additional capacitance with an electrical double‐layer behavior, thus promoting a significant increase in the specific capacitance. As an exemplification, a novel defect‐enriched graphene block with a low specific surface area of 29.7 m2 g?1 and high packing density of 0.917 g cm?3 performs high gravimetric, volumetric, and areal capacitances of 235 F g?1, 215 F cm?3, and 3.95 F cm?2 (mass loading of 22 mg cm?2) at 1 A g?1, respectively, as well as outstanding rate performance. The resulting specific areal capacitance reaches an ultrahigh value of 7.91 F m?2 including a “self‐doping” defect contribution of 4.81 F m?2, which is dramatically higher than the theoretical capacitance of graphene (0.21 F m?2) and most of the reported carbon‐based materials. Therefore, the defect engineering route broadens the avenue to further improve the capacitive performance of carbon materials, especially for compact energy storage under limited surface areas.  相似文献   

17.
High activity, carbon supported Pt electrocatalysts were synthesized using a supercritical fluid method and a selective heterogeneous nucleation reaction to disperse Pt onto single walled carbon nanotube and carbon fiber supports. These nanocomposite materials were then incorporated into catalyst and gas diffusion layers consisting of polyelectrolytes, i.e., Nafion, polyaniline, and polyethyleneimine using layer‐by‐layer (LBL) assembly techniques. Due to the ultrathin nature and excellent homogeneity characteristics of LBL materials, the LBL nanocomposite catalyst layers (LNCLs) yielded much higher Pt utilizations, 3,198 mW mgPt?1, than membrane electrode assemblies produced using conventional methods (~800 mW mgPt?1). Thinner membranes (100 bilayers) can further improve the performance of the LNCLs and these layers can function as catalyzed gas diffusion layers for the anode and cathode of a polymer electrolyte membrane fuel cell.  相似文献   

18.
A series of compounds containing arylamine and 1,2‐diphenyl‐1H‐benz[d]imidazole moieties are developed as ambipolar, blue‐emitting materials with tunable blue‐emitting wavelengths, tunable ambipolar carrier‐transport properties and tunable triplet energy gaps. These compounds possess several novel properties: (1) they emit in the blue region with high quantum yields; (2) they have high morphological stability and thermal stability; (3) they are capable of ambipolar carrier transport; (4) they possess tunable triplet energy gaps, suitable as hosts for yellow‐orange to green phosphors. The electron and hole mobilities of these compounds lie in the range of 0.68–144 × 10?6 and 0.34–147 × 10?6 cm2 V?1 s?1, respectively. High‐performance, single‐layer, blue‐emitting, fluorescent organic light‐emitting diodes (OLEDs) are achieved with these ambipolar materials. High‐performance, single‐layer, phosphorescent OLEDs with yellow‐orange to green emission are also been demonstrated using these ambipolar materials, which have different triplet energy gaps as the host for yellow‐orange‐emitting to green‐emitting iridium complexes. When these ambipolar, blue‐emitting materials are lightly doped with a yellow‐orange‐emitting iridium complex, white organic light‐emitting diodes (WOLEDs) can be achieved, as well by the use of the incomplete energy transfer between the host and the dopant.  相似文献   

19.
Mosaic, single‐crystal CaCO3 thin films have been prepared on modified poly(ethylene terephthalate) (PET) templates. Surface modification of PET through the introduction of carboxylic acid groups (COOH‐PET), and the subsequent physical and chemical adsorption of poly(allylamine hydrochloride) (PAH) at pH 8 (PAH8‐PET) and pH 11 (PAH11‐PET), afford template surfaces that influenced the phase transition of an amorphous CaCO3 (ACC) films during crystallization in air. Macroscopic ACC thin films are prepared on modified PET films in the presence of poly(acrylic acid). Polycrystalline, spherulitic vaterite (CaCO3) films are observed to form on native PET and PAH11‐PET, while mosaic, single‐crystal calcitic (CaCO3) films form on COOH‐PET and PAH8‐PET templates. These results confirm that single‐crystal CaCO3 growth patterns are dependent on the surface characteristics of the PET template. We infer therefore, that the nucleation and growth of ceramic films on polymeric templates can be controlled by chemical modification of the polymeric template surface, and by the subsequent attachment of ionic polyelectrolytes.  相似文献   

20.
Planar perovskite solar cells (PSCs) based on low‐temperature‐processed (LTP) SnO2 have demonstrated excellent photovoltaic properties duo to the high electron mobility, wide bandgap, and suitable band energy alignment of LTP SnO2. However, planar PSCs or mesoporous (mp) PSCs based on high‐temperature‐processed (HTP) SnO2 show much degraded performance. Here, a new strategy with fully HTP Mg‐doped quantum dot SnO2 as blocking layer (bl) and a quite thin SnO2 nanoparticle as mp layer are developed. The performances of both planar and mp PSCs has been greatly improved. The use of Mg‐SnO2 in planar PSCs yields a high‐stabilized power conversion efficiency (PCE) of close to 17%. The champion of mp cells exhibits hysteresis free and stable performance with a high‐stabilized PCE of 19.12%. The inclusion of thin mp SnO2 in PSCs not only plays a role of an energy bridge, facilitating electrons transfer from perovskite to SnO2 bl, but also enhances the contact area of SnO2 with perovskite absorber. Impedance analysis suggests that the thin mp layer is an “active scaffold” selectively collecting electrons from perovskite and can eliminate hysteresis and effectively suppress recombination. This is an inspiring advance toward high‐performance PSCs with HTP mp SnO2.  相似文献   

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