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Conventional templating synthesis confines the growth of seeds in rigid spaces to achieve faithful morphological replication. Herein, we explore the use of spherical shape-deformable polymeric nanoshells to regulate the anisotropic growth of Ag nanoplates. The flexible shells deform adaptively to accommodate the initial overgrowth of the seeds but restrict the growth in the directions where the shells are fully stretched, eventually producing nanoplates with an unconventional circular profile. The diameter of the final Ag nanoplates can be precisely predicted by stretching and flattering the nanoshells into a plate-like capsule while retaining their original internal surface area. Furthermore, unlike conventional templates, the polymer shells eventually turn themselves into a conformal coating that binds to the surface of the full-grown Ag nanoplates and significantly enhances their stability against oxidative etching.
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Dynamic manipulation of optical properties through the reversible assembly of plasmonic nanoparticles offers great opportunities for practical applications in many fields. The previous success, however, has been limited to Au nanoparticles. Reversible assembly and plasmonic tuning of Ag nanoparticles (AgNPs) have remained a significant challenge due to difficulty in finding an appropriate surface agent that can effectively stabilize the particle surface and control their interactions. Here, we overcome the challenge by developing a limited-ligand-protection (LLP) strategy for introducing poly(acrylic acid) with precisely controlled coverage to the AgNP surface to not only sufficiently stabilize the nanoparticles but also enable effective control over the surface charge and particle interaction through pH variation. The as-synthesized AgNPs can be reversibly assembled and disassembled and accordingly display broadly tunable coupling of plasmonic properties. Compared to the Au-based system, the success in the reversible assembly of AgNPs represents a significant step toward practical applications such as colorimetric pressure sensing because they offer many advantages, including broader spectral tuning range, higher color contrast, a one-pot process, and low materials and production cost. This work also highlights LLP as a new avenue for controlling the interparticle forces, their reversible assembly, and dynamic coupling of physical properties.
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A novel ratiometric surface-enhanced Raman scattering (SERS) nanosensor has been developed to probe the activity of endonuclease under in vitro and in living cells conditions. The optimized alloyed Au/Ag nanoparticles (NPs) were synthesized as the SERS substrate, which combined the superior properties of both pure Au and pure Ag nanoparticles: they exhibit excellent plasmonic property with high chemical stability and low cytotoxicity. They were then employed for quantitative detection of endonuclease through functionalization with single-stranded DNA (ssDNA) carrying 3-[4-(phenylethynyl)benzylthio]propanoic acid (PEB) as endonuclease-responsive SERS signaling molecule and 4-thiophenylacetylene (TPA) as the internal standard SERS signaling molecule. In the presence of endonuclease, the ssDNA was cleaved, releasing PEB molecules from the particle surface and decreasing the SERS signal at 2215 cm-1 from PEB. Since the SERS signal at 1983 cm-1 from alkynyl TPA remained the same, quantitative detection of endonuclease was achieved, based on the ratiometric peak intensity of I1983/ I2215, with a detection limit as low as 0.056 unit/mL. A highly biocompatible and antijamming ratiometric SERS sensor was established by combining the alloyed Au/AgNPs with two unique alkynes molecules with Raman signals in the cellular silent region. The ratiometric sensor was successfully employed to detect intracellular endonuclease activity as well as endonuclease in living cells for the first time.
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Alcinos/química , DNA de Cadeia Simples/química , Endonucleases/análise , Ouro/química , Nanopartículas Metálicas/química , Prata/química , Análise Espectral Raman/métodos , Ligas/química , DNA de Cadeia Simples/metabolismo , Endonucleases/metabolismo , Ensaios Enzimáticos/métodos , Células HeLa , Humanos , Limite de Detecção , Nanopartículas Metálicas/ultraestrutura , Propriedades de SuperfícieRESUMO
In this Review, we aim to provide an updated summary of the research related to hollow micro- and nanostructures, covering both their synthesis and their applications. After a brief introduction to the definition and classification of the hollow micro-/nanostructures, we discuss various synthetic strategies that can be grouped into three major categories, including hard templating, soft templating, and self-templating synthesis. For both hard and soft templating strategies, we focus on how different types of templates are generated and then used for creating hollow structures. At the end of each section, the structural and morphological control over the product is discussed. For the self-templating strategy, we survey a number of unconventional synthetic methods, such as surface-protected etching, Ostwald ripening, the Kirkendall effect, and galvanic replacement. We then discuss the unique properties and niche applications of the hollow structures in diverse fields, including micro-/nanocontainers and reactors, optical properties and applications, magnetic properties, energy storage, catalysis, biomedical applications, environmental remediation, and sensors. Finally, we provide a perspective on future development in the research relevant to hollow micro-/nanostructures.
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Colloidal plasmonic metal nanoparticles have enabled surface-enhanced Raman scattering (SERS) for a variety of analytical applications. While great efforts have been made to create hotspots for amplifying Raman signals, it remains a great challenge to ensure their high density and accessibility for improved sensitivity of the analysis. Here we report a dealloying process for the fabrication of porous Au-Ag alloy nanoparticles containing abundant inherent hotspots, which were encased in ultrathin hollow silica shells so that the need of conventional organic capping ligands for stabilization is eliminated, producing colloidal plasmonic nanoparticles with clean surface and thus high accessibility of the hotspots. As a result, these novel nanostructures show excellent SERS activity with an enhancement factor of â¼1.3 × 10(7) on a single particle basis (off-resonant condition), promising high applicability in many SERS-based analytical and biomedical applications.
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Plasmonic metal nanostructures can simultaneously scatter and absorb light, with resonance wavelength and strength depending on their morphology and composition. This work demonstrates that unique dichroic effects and high-contrast colour-switching can be achieved by leveraging the resonant scattering and absorption of light by plasmonic nanostructures and the specular reflection of the resulting transmitted light. Using core/shell nanostructures comprising a metal core and a dielectric shell, we show that their spray coating on reflective substrates produces dichroic films that can display colour switching at different viewing angles. The high-contrast colour switching, high flexibility in designing multicolour patterns, and convenience for large-scale production promise their wide range of applications, including anticounterfeiting, mechanochromic sensing, colour display, and printing.
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Lithium-ion battery cathode materials suffer from bulk and interfacial degradation issues, which negatively affect their electrochemical performance. Oxide coatings can mitigate some of these problems and improve electrochemical performance. However, current coating strategies have low throughput, are expensive, and have limited applicability. In this article, we describe a low-cost and scalable strategy for applying oxide coatings on cathode materials. We report synergistic effects of these oxide coatings on the performance of aqueously processed cathodes in cells. The SiO2 coating strategy developed herein improved mechanical, chemical, and electrochemical performance of aqueously processed Ni-, Mn- and Co-based cathodes. This strategy can be used on a variety of cathodes to improve the performance of aqueously processed Li-ion cells.
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Thermal insulation materials are highly desirable for several applications ranging from building envelopes to thermal energy storage systems. A new type of low-cost insulation material called hollow silica particles (HSPs) was recently reported. The present work presents an HSP-based stand-alone composite that has very low thermal conductivity and is highly stable to moisture.
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The proper handling of end-of-life (EOL) lithium-ion batteries (LIBs) has become an urgent and challenging issue with the surging use of LIBs, in which recovering high-value cathodes not only relieves the pressure on the raw material supply chain but also minimizes environmental pollution. Beyond direct recycling of spent cathodes to their pristine states, the direct upcycling of spent cathodes to the next-generation cathodes is of great significance to maximize the value of spent materials and to sustain the fast development of LIBs. Herein, a "reciprocal ternary molten salts" (RTMS) system was developed to directly upcycle spent NMC 111 to Ni-rich NMCs by simultaneously realizing the addition of Ni and the relithiation of Li in spent NMC 111. After RTMS flux upcycling, the obtained Ni-rich NMCs exhibited an α-NaFeO2-type layered structure, restored Li content, and excellent performance, which is very similar to that of the pristine NMC 622.
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We report here that dissolution and regrowth of resorcinol formaldehyde (RF) colloidal particles can occur spontaneously when they are subjected to etching in solvents such as ethanol and tetrahydrofuran, resulting in the formation of hollow nanostructures with controllable shell thickness. The hollowing process of the RF particles is attributed to their structural inhomogeneity, which results from the successive deposition of oligomers with different chain lengths during their initial growth. As the near-surface layer of RF colloids mainly consists of long-chain oligomers while the inner part consists of short-chain oligomers, selective etching removes the latter and produces the hollow structures. By revealing the important effects of the condensation degree of RF, the etching time and temperature, and the composition of solvents, we demonstrate that the morphology and structure of the resulting RF nanostructures can be conveniently and precisely controlled. This study not only improves our understanding of the structural heterogeneity of colloidal polymer particles, but also provides a practical and universal self-templated approach for the synthesis of hollow nanostructures.
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An engaging area of research in sodium-ion batteries (SIBs) has been focusing on discovery, design, and synthesis of high-capacity cathode materials in order to boost energy density to levels close enough to that of state-of-the-art lithium-ion batteries. Of particular interest, P2-type layered oxide, Na2/3Fe1/2Mn1/2O2, has been researched as a potential cathode in SIBs based on its high theoretical capacity of 260 mA h/g and use of noncritical materials. However, the reported synthesis methods are not only complex and energy-demanding but also often yield inhomogeneous and impure materials with capacities less than 200 mA h/g under impractical test conditions. Here, we report a novel synthesis route using low-temperature eutectic reaction to produce highly homogeneous, crystalline, and impurity-free P2-NaxFe1/2Mn1/2O2 with enhanced Na-ion diffusivity and kinetics. The overall electrochemical performances of the Na-ion cells have been improved by pairing the P2-cathode with presodiated hard carbon anodes, leading to reversible capacities in the range of 180 mA h/g. This new approach is a contribution toward the simplification of synthesis and scalability of sodium-based cathodes with high crystallinity and fine-tuned morphology and the realization of a sodium-ion battery system with lower cost and improved electrochemical performance.
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The formation of a solid-electrolyte interphase (SEI) on the surface of Li4 Ti5 O12 (LTO) has become a highly controversial topic, with arguments for it and against it. However, prior studies supporting the formation of an SEI layer have typically suggested that a layer forms upon cycling of a cell, although the layer is probed after disassembling. In this study, cubic mesostructured LTO is synthesized with crystallite domain sizes between 3 and 4â nm and uniform pores with diameters ≤8â nm. The mean pore size is controlled between 4-8â nm through the use of a triblock amphipathic copolymer with a tunable hydrophobic block as template and by thermal treatment. The LTO morphology obtained is spherical and evolves upon heat treatment. These materials show excellent electrochemical performance, including high rate capability and capacity retention. The LTO material is subjected to operando small-angle neutron scattering and X-ray photoelectron spectroscopy experiments, which reveal that the highly debated SEI forms at potentials as high as 2.2â V, first as a LiF-rich layer and subsequently by the growth of a carbonaceous layer. These SEI products form first on the smaller pores before forming on the mesopores.
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We prepared an ultrathin porous silica shell-coated Au-Ag alloy nanoparticle (AuAg@p-SiO2NP) and developed it as a novel alkyne-based surface-enhanced Raman scattering (SERS) nanoprobe for the ratiometric Raman imaging of exogenous and endogenous H2O2 in live cells. The AuAg@p-SiO2NPs functionalized with 4-mercaptophenylboronic acid (MPBA) and 4-mercaptophenylacetylene (MPAE, 1986â¯cm-1) as internal standard were first incubated with dopamine (DA) to incorporate the bridging molecules through the formation of borate bond between DA and MPBA on the surface of nanoparticle. Then, the signaling alkyne molecules of 3-(4-(phenylethynyl) benzylthio) propanoic acid (PEB, 2214â¯cm-1) were conjugated to the surface of nanoparticle through the formation of amide bond between the carboxyl group on the PEB and the amino group on the DA, forming the ratiometric SERS nanoprobe. In the presence of H2O2, the alkynyl on the PEB is released from the surface of the Au-Ag alloy nanoparticle due to the boronate-to-phenol switch, decreasing the Raman signal at 2214â¯cm-1 significantly. Since the Raman signal of MPAE at 1986â¯cm-1 remains unchanged, quantitative analysis of H2O2 concentration can be achieved based on the ratiometric value of I1986/I2214. Under the optimized conditions, the plot of the ratiometric value of I1986/I2214 versus the H2O2 concentration in the range from 0.12 to 8⯵M revealed a good linear response with a detection limit of 52â¯nM based on a signal-to-noise ratio of S/Nâ¯=â¯3. The porous SiO2-coated Au-Ag alloy nanoparticle provides a novel SERS substrate with excellent biocompatibility, high stability, and effective anti-interference ability. Together with the alkynyl derivatives as internal standard, the SERS nanoprobe reported here allows the ratiometric detection of H2O2 in live cells and can be further applied to quantify many other biomolecules by using different signaling agents.
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Alcinos/química , Ligas/química , Peróxido de Hidrogênio/metabolismo , Nanopartículas Metálicas/química , Imagem Molecular/métodos , Dióxido de Silício/química , Análise Espectral Raman , Transporte Biológico , Sobrevivência Celular , Ouro/química , Células HeLa , Humanos , Espaço Intracelular/metabolismo , Modelos Moleculares , Conformação Molecular , Porosidade , Prata/químicaRESUMO
In spite of the recent advances in the development of high performing piezoelectric materials, their applications are typically limited to the direct conversion of mechanical impact energy to electrical energy, potentially risking mechanical failures. In this study, we developed piezoelectric poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) nanofibers integrated with SiO2-shelled Fe3O4 magnetic nanoparticles, to utilize magnetic energy to reliably drive the piezoelectric effect. Specifically, we show that the shape of the magnetic nanoparticles exerts a significant effect on the efficiency of the magneto-mechano-electrical energy conversion as magnetic nanorods exhibit approximately 70% enhancement in electric field generation under cyclic magnetic fields as compared to nanospheres. Under an alternating magnetic field of 200 mT, the magnetic nanorod-piezoelectric nanofiber composite generated a peak-to-peak voltage of approximately 30 mVp-p with a superior durability without any performance degradation after over 1 million cycles. This study demonstrates the potential of magnetic-field responsive, piezoelectric-based materials in energy harvesting applications from non-mechanical energy sources.
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All nanostructures share a common feature of large surface-to-volume ratio, which makes surface engineering a vital tool for exploring their new and important applications in many different areas. Particularly, inorganic nanostructures represent a class of intriguing catalysts that can find wide uses in energy conversion, energy storage, and environmental remediation. Here, a number of surface engineering strategies, including morphology control, defect incorporation, and interface manipulation for tailoring the shape, facet, defect, interfacial property, and composition of nanostructures, aiming at controlling the chemical and physical properties such as energy bandgap and surface energy toward great enhancement in catalytic performance, are discussed.
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Limited success has been achieved in preparing nanorods of silver with uniform sizes and tunable localized surface plasmon resonances. Also, the practical applications of silver nanostructures have been hindered by their poor chemical stability in a corrosive environment. Here we address these issues by converting Au@Ag core/shell nanorods into fully alloyed ones through controlled high-temperature annealing in confined spaces. Compared with their core/shell counterparts, the obtained alloy nanorods demonstrated significantly enhanced stability toward oxidative etching. We also systematically investigated their novel plasmonic properties, and revealed that the band positions of both longitudinal and transverse modes can be readily tuned by either manipulating the Ag/Au ratio or starting with gold cores of different aspect ratios. Moreover, we have achieved widely adjusted peak intensity ratios between the transverse and longitudinal bands from 0.14 to 1.22, which is impossible for nonalloyed nanorods. The alloy nanorods developed in this work are believed to find great uses in fundamental spectroscopic studies as well as many attractive plasmonic applications.
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Identification of active sites for oxygen evolution reaction (OER) plays a key role in the design and fabrication of high-performance cobalt-based electrocatalysts. Herein, we report the synthesis of two types of two-dimensional monometallic cobalt hydroxide nanoplates in aqueous solution for OER: α-Co(OH)2 with both Co2+Td and Co2+Oh sites and ß-Co(OH)2 with Co2+Oh sites. Electrochemical characterization reveals that α-Co(OH)2 is more active than ß-Co(OH)2 towards OER. The better activity can be attributed to the presence of Co2+Td sites in α-Co(OH)2, which are more active than Co2+Oh sites. Our finding clarifies the contribution of the two catalytic sites and helps future rational design of high-performance OER electrocatalysts.
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Here, this study reports a novel confined-space thermal dewetting strategy for the fabrication of Au nanocups with tunable diameter, height, and size of cup opening. The nanocup morphology is defined by the cup-shaped void space created by a yolk-shell silica template that spontaneously takes an eccentric configuration during annealing. Thermal dewetting of Au, which is sandwiched between the yolk and shell, leads to the desired nanocup morphology. With strong scattering in near infrared, the Au nanocups exhibit superior efficiency as contrast agents for spectral-domain optical coherence tomography imaging. This confined-space thermal dewetting strategy is scalable and general, and can be potentially extended to the synthesis of novel anisotropic nanostructures of various compositions that are difficult to produce by conventional wet chemical or physical methods, thus opening up opportunities for many new applications.
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Plasmonic noble metal nanocrystals with interior nanogaps have attracted great attention in surface-enhanced Raman scattering (SERS) applications due to the presence of built-in hotspots. Herein, we report a synthesis route to holey Au-Ag alloy nanoplates by controlled galvanic replacement with Ag nanoplates as the sacrificial template, a sulfite-coordinated Au(i) salt as the Au source, and polyvinylpyrrolidone (PVP) as the capping agent. PVP helps regulate the anisotropic growth of nanopores on the Ag nanoplates to afford a highly holey nanostructure, and the monovalent Au(i) salt plays a critical role in stabilizing these holey nanoplates by rapidly enriching Au in the alloy nanostructures. Numerical simulations and experimental results suggest that these holey Au-Ag alloy nanoplates possess enormous internal hotspots for high sensitivity in the SERS analysis, and high stability for excellent reliability of the analysis under many harsh conditions. We believe that this strategy is potentially applicable to the synthesis of many other types of plasmonic nanostructures with inherent nanogaps for many sensing and imaging applications.
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A novel pressure sensor has been developed by taking advantage of the orientational dependence of localized surface plasmon resonance of gold nanorods embedded in a polymer matrix. This stress-responsive material can be used to record the distribution and magnitude of pressure between two contacting surfaces by outputting optical response.