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Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.
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Over the years, nanoenergetic materials have attracted enormous research interest due to their overall better combustion characteristics compared to their micron-sized counterparts. Aluminum, boron, and their respective alloys are the most extensively studied nanoenergetic materials. The majority of the research work related to this topic is confined to the respective powders. However, for practical applications, the powders need to be consolidated into reactive structures. Processing the nanoenergetic materials with polymeric binders to prepare structured composites is a possible route for the conversion of powders to structures. Most of the binders, including the energetic ones, when mixed with nanoenergetic materials even in small quantities, adversely affects the ignitability and combustion performance of the corresponding composites. The passivating effect induced by the polymeric binder is considered unfavorable for ignitability. Fluoropolymers, with their ability to induce pre-ignition reactions with the nascent oxide shell around aluminum and boron, are recognized to sustain the ignitability of the composites. Initial research efforts have been focused on surface functionalizing approaches using fluoropolymers to activate them further for energy release, and to improve the safety and storage properties. With the combined advent of more advanced chemistry and manufacturing techniques, fluoropolymers are recently being investigated as binders to process nanoenergetic materials to reactive structures. This review focuses on the major research developments in this area that have significantly assisted in the transitioning of nanoenergetic powders to structures using fluoropolymers as binders.
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Replacing existing inert binders with energetic ones in composite explosives is a novel way to improve the explosive performance, on the proviso that energetic binders are capable of releasing chemical energy rapidly in the detonation environment. Known to be a promising candidate, the reaction mechanism of glycidyl azide polymer (GAP) at typical detonation temperatures higher than 3000 K has been theoretically studied in this work at the atomistic level. By analyzing and tracking the cleavage of characteristic chemical bonds, it was found that at the detonation temperature, GAP was able to release a large amount of energy and small molecule products at a speed comparable to commonly used explosives in the early reaction stage, which was mainly attributed to the decomposition of azide groups into N2 and the main chain breakage into small fragments. Moreover, N2 generation was found to be accelerated by H atom transfer at an earlier reaction step. The dissociation energy of the main chain was lowered with structure deformation so as to facilitate the fragmentation of the GAP chain. Based on this analytical study of reaction kinetics, GAP was found to have higher reactivity at the detonation temperature than at lower temperatures. The small molecules' yield rate is of the same order of magnitude as an explosive detonation reaction, indicating that GAP has the potential to improve the performance of composite explosives. Our study reveals the chemical decomposition mechanism of a typical energetic binder, which would aid in the future design and synthesis of energetic binders so as to achieve both sensitivity-reducing and energy-enhancing performance goals simultaneously.
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Recent progress in the currently available methods of producing black phosphorus bulk and phosphorene are presented. The effective passivation approaches toward improving the air stability of phosphorene are also discussed. Furthermore, the research efforts on the phosphorene and phosphorene-based materials for potential applications in lithium ion batteries, sodium ion batteries, and thermoelectric devices are summarized and highlighted. Finally, the outlook including challenges and opportunities in these research fields are discussed.
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We show that partial inhibition of the emerging Ag domain can be achieved by controlling the growth dynamics. With the symmetry broken by the "fresh" surface, sequentially growth gives (Au sphere)-(Ag wire)-(Ag plate) triblock nanostructures. This new understanding opens doors to sophisticated synthetic designs, broadening the horizon of our search for functional architectures.
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Ink-jet printing of thermoelectric nanomaterials is successfully used to fabricate flexible thin film TE devices for power generation and cooling.
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Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well-defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two-dimensional (2D) nanoflakes of transition-metal phosphates, including FePO4, Mn3(PO4)2, and Co3(PO4)2, with highly ordered mesoporous structures in a nonpolar solvent. The as-obtained nanoflakes with thicknesses of about 3.7â nm are constructed from a single layer of parallel-packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO4 nanoflakes were used as the cathode for a lithium-ion battery, which exhibits excellent stability and high rate capabilities.
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A facile and general method is reported to prepare ordered porous graphene-based binder-free electrodes on a large scale. This preparation process allows the easy adjustment of the selected components, weight ratio of componets, and the thickness of the electrodes. Such ordered porous electrodes demonstrate superior Li storage properties; for example, graphene-Fe3 O4 @C depicts high capacities of 1123.8 and 505 mAh g(-1) at current densities of 0.5 and 10 A g(-1) , respectively.
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Ultrathin single-crystalline V2 O5 ·0.76H2 O nanosheets with a thickness of 1.5-2.6 nm are prepared on the basis of molecular-level 'oriented attachment' through special sol-gel chemistry. The initial formation of 3-7 nm nanodiscs by confining the condensation reactions within the ab plane is critical to form nanosheets. As a proof-of-concept, these nanosheets exhibit good properties for hydrogen sensors and supercapacitors.
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3D Hierarchical echinus-like titanate spheres (HETSs), serving as the supporting material for CdS nanoparticles, are synthesized via a fast one-step hydrothermal method. The obtained 3D CdS-HETS composite materials show enhanced H2 generation under visible light irradiation.
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Compostos de Cádmio/química , Hidrogênio/química , Luz , Nanocompostos/química , Compostos de Selênio/química , Titânio/química , Fotoquímica/métodosRESUMO
Double-wall amorphous FePO4 nanotubes are prepared by an oil-phase chemical route. The inward diffusion of vacancies and outward diffusion of ions through passivation layers result in double-wall nanotubes with thin walls. Such a process can be extended to prepare hollow polydedral nanocrystals and hollow ellipsoids. The double-wall FePO4 nanotubes show interesting cathode performance in Li ion batteries.
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Fe(2)O(3) microboxes with hierarchically structured shells have been synthesized simply by annealing Prussian blue (PB) microcubes. By utilizing simultaneous oxidative decomposition of PB microcubes and crystal growth of iron oxide shells, we have demonstrated a scalable synthesis of anisotropic hollow structures with various shell architectures. When evaluated as an anode material for lithium ion batteries, the Fe(2)O(3) microboxes with a well-defined hollow structure and hierarchical shell manifested high specific capacity (~950 mA h g(-1) at 200 mA g(-1)) and excellent cycling performance.
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Fontes de Energia Elétrica , Óxido Ferroso-Férrico/síntese química , Lítio/química , Compostos Organometálicos/química , Óxido Ferroso-Férrico/química , Estrutura Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Graphene nanosheets and metal nanoparticles (NPs) have been used as nano-building-blocks for assembly into macroscale hybrid structures with promising performance in electrical devices. However, in most graphene and metal NP hybrid structures, the graphene sheets and metal NPs (e.g., AuNPs) do not enable control of the reaction process, orientation of building blocks, and organization at the nanoscale. Here, an electrophoretic layer-by-layer assembly for constructing multilayered reduced graphene oxide (RGO)/AuNP films and lateral micropatterns is presented. This assembly method allows easy control of the nano-architecture of building blocks along the normal direction of the film, including the number and thickness of RGO and AuNP layers, in addition to control of the lateral orientation of the resultant multilayered structures. Conductivity of multilayered RGO/AuNP hybrid nano-architecture shows great improvement caused by a bridging effect of the AuNPs along the out-of-plane direction between the upper and lower RGO layers. The results clearly show the potential of electrophoretic build-up in the fabrication of graphene-based alternately multilayered films and patterns. Finally, flexible supercapacitors based on multilayered RGO/AuNP hybrid films are fabricated, and excellent performance, such as high energy and power densities, are achieved.
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Eletroforese/métodos , Grafite/química , Nanopartículas/química , Eletrônica , NanotecnologiaRESUMO
Layered protonated titanates (LPTs), a class of interesting inorganic layered materials, have been widely studied because of their many unique properties and their use as precursors to many important TiO(2)-based functional materials. In this work, we have developed a facile solvothermal method to synthesize hierarchical spheres (HSs) assembled from ultrathin LPT nanosheets. These LPT hierarchical spheres possess a porous structure with a large specific surface area and high stability. Importantly, the size and morphology of the LPT hierarchical spheres are easily tunable by varying the synthesis conditions. These LPT HSs can be easily converted to anatase TiO(2) HSs without significant structural alteration. Depending on the calcination atmosphere of air or N(2), pure anatase TiO(2) HSs or carbon-supported TiO(2) HSs, respectively, can be obtained. Remarkably, both types of TiO(2) HSs manifest excellent cyclability and rate capability when evaluated as anode materials for high-power lithium-ion batteries.
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Single-crystalline TiOF(2) nanotubes were prepared by a one-step solvothermal method. The nanotubes are rectangular in shape with a length of 2-3â µm, width of 200-300â nm, and wall thickness of 40-60â nm. The formation of TiOF(2) nanotubes is directly driven by the interaction between TiF(4) and oleic acid in octadecane to form the 1D nanorods, and this is followed by a mass diffusion process to form the hollow structures. The synthesis approach can be extended to grow TiOF(2) nanoparticles and nanorods. Compared with TiO(2), which is the more commonly considered anode material in lithium-ion batteries, TiOF(2) has the advantages of a lower Li-intercalation voltage (e.g., to help increase the total voltage of the battery cell) and higher specific capacities. The TiOF(2) nanotubes showed good Li-storage properties with high specific capacities, stable cyclabilities, and good rate capabilities.
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A crystalline three-dimensional (3D) quaternary chalcohalide, Hg(7)InS(6)Cl(5) (1), has been synthesized through a solid-state reaction under medium temperature. It is the first example in the family of the Hg-IIIA-Q-X (Q = S, Se, Te; X = F, Cl, Br, I) systems. Compound 1 features a 3D network and has an optical band gap of 2.54 eV.
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Carbon monoxide (CO) is a highly toxic gas that can be commonly found in many places. However, it is not easily detected by human olfaction due to its colorless and odorless nature. Therefore, highly sensitive sensors need to be developed for this purpose. Carbon nanotubes (CNTs) have an immense potential in gas sensing. However, CNT-based gas sensors for sensing CO are seldom reported due to the lack of reactivity between CO and CNTs. In this work, O(2) plasma modified CNT was used to fabricate a CNT gas sensor. The plasma treated CNTs showed selectively towards CO, with the capability of sensing low concentrations of CO (5 ppm) at room temperature, while the pristine CNTs showed no response. UV spectra and oxygen reduction reaction provided evidence that the difference in sensing property was due to the elimination of metallic CNTs and enhancement of the oxygen reduction property.
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Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/métodos , Monóxido de Carbono/análise , Nanotubos de Carbono/química , Oxigênio/química , Gases em Plasma/química , Humanos , Nanotubos de Carbono/ultraestrutura , Análise Espectral RamanRESUMO
Intercalation and exfoliation of lithium: Few-layer-thick inorganic nanosheets (BN, NbSe(2), WSe(2), Sb(2)Se(3), and Bi(2)Te(3)) have been prepared from their layered bulk precursors by using a controllable electrochemical lithium intercalation process. The lithium intercalation conditions, such as cut-off voltage and discharge current, have been systematically studied and optimized to produce high-quality BN and NbSe(2) nanosheets.
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Synthesizing urea from nitrate and carbon dioxide through an electrocatalysis approach under ambient conditions is extraordinarily sustainable. However, this approach still lacks electrocatalysts developed with high catalytic efficiencies, which is a key challenge. Here, we report the high-efficiency electrocatalytic synthesis of urea using indium oxyhydroxide with oxygen vacancy defects, which enables selective C-N coupling toward standout electrocatalytic urea synthesis activity. Analysis by operando synchrotron radiation-Fourier transform infrared spectroscopy showcases that *CO2NH2 protonation is the potential-determining step for the overall urea formation process. As such, defect engineering is employed to lower the energy barrier for the protonation of the *CO2NH2 intermediate to accelerate urea synthesis. Consequently, the defect-engineered catalyst delivers a high Faradaic efficiency of 51.0%. In conjunction with an in-depth study on the catalytic mechanism, this design strategy may facilitate the exploration of advanced catalysts for electrochemical urea synthesis and other sustainable applications.
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A facile bottom-up synthesis approach is developed to prepare porous metal-oxide ultrathin sheets, e.g., SnO(2), Fe(2)O(3), and SnO(2)-Fe(2)O(3), with thicknesses of â¼5 nm. Graphene sheets are used as the sacrificing template. Such a process can be extended to the synthesis of multiphased porous metal-oxide thin sheets. These porous thin sheets show interesting applications as gas sensors, effective platforms for matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, and supercapacitors.