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Herein, a stable and ultra-sensitive rutin electrochemical sensor was successfully developed. This sensor based on glassy carbon electrode (GCE) modified with C-GCS@ZIF-F/PL nanocomposite, which was made of thermally carbonized glucose (GCS) doped with flower-like ZIF (ZIF-F) and pencil lead (PL). The electrochemical response of rutin was considerably significant at C-GCS@ZIF-F/PL/GCE, demonstrating favorable conductivity and electrocatalytic properties for detection of rutin. Under optimal conditions, the linear range is 0.1-100 µM, with a low detection limit (LOD) of 0.0054 µM. It also exhibits excellent stability, reproducibility, as well as selectivity over common interfering ions such as Na+, uric acid, quercetin and riboflavin, etc. Meanwhile, the practical utility of developed sensor was evaluated in food samples including honey, orange, and buckwheat tea, achieving satisfactory recovery rates ranging from 98.2% to 101.7%. This paper introduces a novel technique for the detection of rutin in foods.
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Electric double-layer capacitors (EDLCs) with fast frequency response are regarded as small-scale alternatives to the commercial bulky aluminum electrolytic capacitors. Creating carbon-based nanoarray electrodes with precise alignment and smooth ion channels is crucial for enhancing EDLCs' performance. However, controlling the density of macropore-dominated nanoarray electrodes poses challenges in boosting the capacitance of line-filtering EDLCs. Herein, a simple technique to finely adjust the vertical-pore diameter and inter-spacing in three-dimensional nanoporous anodic aluminum oxide (3D-AAO) template is achieved, and 3D compactly arranged carbon tube (3D-CACT) nanoarrays are created as electrodes for symmetrical EDLCs using nanoporous 3D-AAO template-assisted chemical vapor deposition of carbon. The 3D-CACT electrodes demonstrate a high surface area of 253.0 m2 g-1, a D/G band intensity ratio of 0.94, and a C/O atomic ratio of 8. As a result, the high-density 3D-CT nanoarray-based sandwich-type EDLCs demonstrate a record high specific areal capacitance of 3.23 mF cm-2 at 120 Hz and exceptional fast frequency response due to the vertically aligned and highly ordered nanoarray of closely packed CT units. The 3D-CT nanoarray electrode-based EDLCs could serve as line filters in integrated circuits, aiding power system miniaturization.
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To date, the excellent mass-catalytic activities of Pt single-atoms catalysts (Pt-SACs) toward hydrogen evolution reaction (HER) are categorically confirmed; however, their high current density performance remains a challenge for practical applications. Here, a binder-free approach is exemplified to fabricate self-standing superhydrophilic-superaerphobic Pt-SACs cathodes by directly anchoring Pt-SAs via Pt-NxC4-x coordination bonds to the structurally-integrated 3D nitrogen-doped carbon tubes (N-CTs) array grid (denoted as Pt@N-CTs). The 3D Pt@N-CTs cathode with optimal Pt-SACs loading is capable of operating at a high current density of 1000 mA cm-2 with an ultralow overpotential of 157.9 mV with remarkable long-term stability over 11 days at 500 mA cm-2. The 3D super-wettable free-standing Pt@N-CTs possess interconnected vertical and lateral N-CTs with hierarchical-sized open channels, which facilitates the mass transfer. The binder-free immobilization adding to the large surface area and 3D-interconnected open channels endow Pt@N-CTs cathodes with high accessible active sites, electrical conductivity, and structural stability that maximize the utilization efficiency of Pt-SAs to achieve ampere-level current density HER at low overpotentials.
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Filter capacitors play a critical role in ensuring the quality and reliability of electrical and electronic equipment. Aluminum electrolytic capacitors are the most commonly used but are the largest filtering components, limiting device miniaturization. The high areal and volumetric capacitance of electric double-layer capacitors should make them ideal miniaturized filter capacitors, but they are hindered by their slow frequency responses. We report the development of interconnected and structurally integrated carbon tube grid-based electric double-layer capacitors with high areal capacitance and rapid frequency response. These capacitors exhibit excellent line filtering of 120-hertz voltage signal and volumetric advantages under low-voltage operations for digital circuits, portable electronics, and electrical appliances. These findings provide a sound technological basis for developing electric double-layer capacitors for miniaturizing filter and power devices.
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It is of great significance to develop a simple and effective method for constructing large-scale high-quality surface-enhanced Raman scattering (SERS) substrate. Here, an Ag nanoparticle-assembled micro-bowl array was prepared by a close-packed polystyrene (PS) sphere monolayer templated electrodeposition approach. The fabricated Ag nanoparticle-assembled micro-bowl array shows high SERS sensitivity to rhodamine 6G (R6G) under an ultra-low concentration of 1 fM, and exhibits excellent SERS spectral uniformity with a small relative standard deviation (RSD) of 7.6% and good reproducibility (a RSD â¼8.2% for the average peak intensities from different batches of SERS substrates). The fabricated micro-bowl array SERS substrate was employed to detect pesticide residue (thiram and methyl parathion) on vegetables. The limit of detections (LODs) for the two pesticides are lower than the maximum residue limits (MRLs) set by the European Union respectively, showing promising application in rapid inspection of food safety.
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Polycyclic aromatic hydrocarbons (PAHs) are one of the most widespread and dangerous group of pollutants existing in the environment. Trace detection of PAHs is essential and important. Surface-enhanced Raman scattering (SERS) is a powerful analytical tool for ultrasensitive chemical analysis. However, the direct detection of PAHs by SERS is difficult due to poor affinity of PAHs to metal surfaces. In this work, we present a SERS platform based on the Ag-nanoparticles/graphene hybrid for the direct detection of PAHs with graphene as PAHs assemblies. The target PAHs are captured by the graphene through π-π electronic stacking, and brought close to the hot spots generated by dense Ag-nanoparticles decorated on the graphene. Sensitive detection of PAHs has been realized using this SERS substrate without further surface modification. The limit of detection for the three typical PAHs including pyrene, anthracene and phenanthrene was as low as 0.73â¯ppb, 1.1â¯ppb and 0.57â¯ppb, respectively. Our results indicate that the immobilization of PAHs on graphene is a process that can be applied in the design of sensitive sensors for these aromatic pollutants. This functional SERS sensor shows a great potential application in food safety inspection and environment pollutants monitoring.
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An ordered array of hierarchically-structured core-nanosphere@space-layer@shell-nanoparticles has been fabricated for surface-enhanced Raman scattering (SERS) detection. To fabricate this hierarchically-structured chip, a long-range ordered array of Au/Ag-nanospheres is first patterned in the nano-bowls on the planar surface of ordered nanoporous anodic titanium oxide template. A ultra-thin alumina middle space-layer is then conformally coated on the Au/Ag-nanospheres, and Ag-nanoparticles are finally deposited on the surface of the alumina space-layer to form an ordered array of Au/Ag-nanosphere@Al2O3-layer@Ag-nanoparticles. Finite-difference time-domain simulation shows that SERS hot spots are created between the neighboring Ag-nanoparticles. The ordered array of hierarchical nanostructures is used as the SERS-substrate for a trial detection of methyl parathion (a pesticide) in water and a limit of detection of 1 nM is reached, indicating its promising potential in rapid monitoring of organic pollutants in aquatic environment.
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Ordered arrays of Au-nanorod-tips protruding from an anodic aluminum oxide (AAO) template are reported as reproducible and active surface-enhanced Raman scattering (SERS) substrates. The Au-nanorods were grown in the nanochannels of the AAO template by use of alternative current electrodeposition, then the template was strengthened using a polymer, and finally the template bottom side was selectively etched to expose the Au-nanorod tips. By controlling the thinning of the AAO-porewalls, the inter-nanorod-gaps were tuned to ~5 nm, forming dense and uniform nano-gap induced "hot spots" among the adjacent Au-nanorod tips. As a result, the electromagnetic field of the Au-nanorod-tip arrays was uniformly enhanced, and demonstrated high SERS sensitivity with good signal reproducibility. The Au-nanorod-tips have the potential to be used in SERS-based applications in order to rapidly detect trace pollutants in the environment.
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Hierarchical assembly of plasmonic nanostructures can induce high surface-enhanced Raman scattering (SERS) activity. However, it is a challenge to uniformly disperse the hierarchical nanostructures onto a planar substrate to achieve SERS signal reproducibility. This report presents a facile route to fabricate a hexagonally patterned flower-like silver particle array as the SERS substrate. First, hexagonally ordered silver hemisphere arrays with smooth surface are molded in the pores of an anodic aluminum oxide template. Ag-nanosheets are then electrodeposited onto the surface of individual silver hemispheres. The numerous nano-edges and nano-gaps between adjacent nanosheets render a large number of hot spots, leading to high SERS activity over a larger area of chip. The silver flower-like array is employed as the SERS substrate, which is able to detect 0.1 nM rhodamine 6 G and 1 µM 3,3',4,4'-tetrachlorobiphenyl (PCB-77, a persistent organic pollutant).
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Dielectric capacitors are promising candidates for high-performance energy storage systems due to their high power density and increasing energy density. However, the traditional approach strategies to enhance the performance of dielectric capacitors cannot simultaneously achieve large capacitance and high breakdown voltage. We demonstrate that such limitations can be overcome by using a completely new three-dimensional (3D) nanoarchitectural electrode design. First, we fabricate a unique nanoporous anodic aluminum oxide (AAO) membrane with two sets of interdigitated and isolated straight nanopores opening toward opposite planar surfaces. By depositing carbon nanotubes in both sets of pores inside the AAO membrane, the new dielectric capacitor with 3D nanoscale interdigital electrodes is simply realized. In our new capacitors, the large specific surface area of AAO can provide large capacitance, whereas uniform pore walls and hemispheric barrier layers can enhance breakdown voltage. As a result, a high energy density of 2 Wh/kg, which is close to the value of a supercapacitor, can be achieved, showing promising potential in high-density electrical energy storage for various applications.
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Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications.
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We present a surface-enhanced Raman scattering (SERS) substrate featured by large-scale homogeneously distributed Ag nanoparticles (Ag-NPs) with sub-10 nm gaps assembled on a two-layered honeycomb-like TiO(2) film. The two-layered honeycomb-like TiO(2) film was achieved by a two-step anodization of pure Ti foil, with its upper layer consisting of hexagonally arranged shallow nano-bowls of 160 nm in diameter, and the lower layer consisting of arrays of about fifty vertically aligned sub-20 nm diameter nanopores. The shallow nano-bowls in the upper layer divide the whole TiO(2) film into regularly arranged arrays of uniform hexagonal nano-cells, leading to a similar distribution pattern for the ion-sputtered Ag-NPs in each nano-cell. The lower layer with sub-20 nm diameter nanopores prevents the aggregation of the sputtered Ag-NPs, so that the Ag-NPs can get much closer with gaps in the sub-10 nm range. Therefore, large-scale high-density and quasi-ordered sub-10 nm gaps between the adjacent Ag-NPs were achieved, which ensures homogeneously distributed 'hot spots' over a large area for the SERS effect. Moreover, the honeycomb-like structure can also facilitate the capture of target analyte molecules. As expected, the SERS substrate exhibits an excellent SERS effect with high sensitivity and reproducibility. As an example, the SERS substrate was utilized to detect polychlorinated biphenyls (PCBs, a kind of persistent organic pollutants as global environmental hazard) such as 3,3',4,4'-pentachlorobiphenyl (PCB-77) with concentrations down to 10(-9) M. Therefore the large-scale Ag-NPs with sub-10 nm gaps assembled on the two-layered honeycomb-like TiO (2) film have potentials in SERS-based rapid trace detection of PCBs.
Asunto(s)
Membranas Artificiales , Nanopartículas del Metal/química , Nanopartículas del Metal/ultraestructura , Plata/química , Espectrometría Raman/métodos , Titanio/química , Luz , Ensayo de Materiales , Reproducibilidad de los Resultados , Dispersión de Radiación , Sensibilidad y EspecificidadRESUMEN
Silicon, being in the same group in the periodic table as carbon, plays a key role in modern semiconductor industry. However, unlike carbon nanotube (NT), progress remains relatively slow in silicon NT (SiNT) and SiNT-based heteroarchitectures, which would be the fundamental building blocks of various nanoscale circuits, devices, and systems. Here, we report the synthesis of linear and branched crystalline SiNTs via porous anodic aluminum oxide (AAO) self-catalyzed growth and postannealing, and the connection of crystalline SiNTs and gold nanowires (AuNWs) via a combinatorial process of electrodepositing AuNWs with predesired length and location in the channels of the AAO template and subsequent AAO self-catalyzed and postannealing growth of SiNTs in the remaining empty channels adjacent to the AuNWs. Using the approach, a large variety of two-segment AuNW/SiNT and three-segment SiNT/AuNW/SiNT heteronanostructures with both linear and branched topologies have been achieved, paving the way for the rational design and fabrication of SiNT-based nanocircuits, nanodevices, and multifunctional nanosystems in the future.