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At least 181 records · Page 10

Slippery liquid infused porous surface (SLIPS) condensers for high efficiency air gap membrane distillation

Abstract To address growing water scarcity, we must improve the energy efficiency of thermal desalination technologies such as air gap membrane distillation. However, promising functional materials such as slippery liquid infused porous surfaces have not yet implemented for any desalination technology. Here, we fabricate and test slippery liquid infused porous surfaces (using Krytox 16,256 lubricant and CuO nanostructures) in an air gap membrane distillation apparatus. System-level transport models, validated by experimental data, establish a framework for improving performance through enhanced condensation surfaces. Results are obtained across a range of temperatures (50–80 °C), salinities (5–105 g/kg), and module lengths. We find that small air gap thickness and efficient droplet shedding significantly improves performance. The CuO Krytox process achieves these with a conductive-self-limiting coating, high nanostructure rugosity, strong covalent and metallic bonding, high hydrophobicity, minimal droplet pinning sites, and ultra-low contact angle hysteresis. The greatest efficiency enhancement from SLIPS is derived from the improved droplet shedding, which allows for reduced gap sizes without flooding, and is further augmented by the increased permeate flux.

Yogi, Yashwant S.↗

Hot Electron-Driven Photocatalysis Using Sub-5 nm Gap Plasmonic Nanofinger Arrays

Semiconductor photocatalysis has received increasing attention because of its potential to address problems related to the energy crisis and environmental issues. However, conventional semiconductor photocatalysts, such as TiO2 and ZnO, can only be activated by ultraviolet light due to their wide band gap. To extend the light absorption into the visible range, the localized surface plasmon resonance (LSPR) effect of noble metal nanoparticles (NPs) has been widely used. Noble metal NPs can couple incident visible light energy to strong LSPR, and the nonradiative decay of LSPR generates nonthermal hot carriers that can be injected into adjacent semiconductor material to enhance its photocatalytic activity. Here we demonstrate that nanoimprint-defined gap plasmonic nanofinger arrays can function as visible light-driven plasmonic photocatalysts. The sub-5 nm gaps between pairs of collapsed nanofingers can support ultra-strong plasmon resonance and thus boost the population of hot carriers. The semiconductor material is exactly placed at the hot spots, providing an efficient pathway for hot carrier injection from plasmonic metal to catalytic materials. This nanostructure thus exhibits high plasmon-enhanced photocatalytic activity under visible light. The hot carrier injection mechanism of this platform was systematically investigated. The plasmonic enhancement factor was calculated using the finite-difference time-domain (FDTD) method and was consistent with the measured improvement of the photocatalytic activity. This platform, benefiting from the precise controllable geometry, provides a deeper understanding of the mechanism of plasmonic photocatalysis.

42 ENGINEERING↗

Hollow Au Nanosphere-Cu 2 O Core–Shell Nanostructures with Controllable Core Surface Morphology

Design of metal-semiconductor interfaces and heterostructures is of strong interest for various catalytic applications including photocatalysis. Here, a series of hollow Au nanosphere (HGN)-Cu 2 O core-shell nanostructures with varying core surface rugosities are synthesized and investigated for possible photocatalytic applications. HGN surface rugosity is tuned by pH modification during galvanic exchange, and carboxyl groups are utilized as coordination sites to deposit uniform Cu 2 O shells onto the gold surfaces. Final core-shell structures are verified by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), and X-ray diffraction (XRD). Information regarding chemical state and electronic band structure is acquired by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Ultrafast transient absorption (TA) reveals that charge separation in bumpy HGN (bHGN)-Cu 2 O may effectively provide longer-lived photoexcited carriers, offering great potential for utilization in advanced photocatalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Redox Agent-Driven Noncorrosive Formation of Nanoporous Mg Structures for Advanced Hydrogen Storage

Light metal-based nanomaterials are widely used for energy storage due to their high energy density and surface-to-volume ratio. However, their high reactivity is paradoxically both the source of advantageous properties and a hurdle to the fabrication of stable nanostructures. Here, in this study, we demonstrate the formation of nanoporous Mg via chemical redox agent-driven dealloying, which ensures minimized surface passivation and results in fine nanostructures with <50 nm of interconnected metallic ligament despite the labile chemical properties of Mg. The thin passivation layer protects the metallic ligaments from severe coarsening by suppressing surface diffusion. The hydrogen storage performance of nanoporous Mg is investigated as an exemplar for energy applications, and the hydrogen ab/desorption kinetics is substantially enhanced compared to other nano-Mg with similar dimensions. Mesoscale simulations highlight the significance of the bicontinuous structure compared to the particle-like counterpart. This work offers valuable insights into the unexplored realm of reactive metal-based nanoporous structures, highlighting their potential for sustainable energy storage and carrier media.

08 HYDROGEN↗

Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Stable operation of rechargeable lithium (Li)-based batteries at low temperatures is vital for cold-climate applications but is plagued with dendritic Li plating and unstable solid-electrolyte interphase (SEI). Here we report high-performance Li-metal batteries under low-temperature and high-rate-charging conditions. This is realized by utilizing a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of SEI and deposition morphology of Li metal anodes. A multilayer SEI containing a LiF-rich inner phase and amorphous outer layer effectively seals the Li surface in contrast to the conventional impassive SEI at low temperatures. As a result, galvanic Li corrosion and self-discharge were suppressed; stable Li deposition was realized from -60º to 45ºC; and a Li|LiCoO 2 cell with a capacity of 2.0 mAh cm -2 displayed a 200-cycle life at -15ºC with a recharge time of 45 minutes.

25 ENERGY STORAGE↗

Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing in Aerospace Applications

A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine an activation energy for the catalyst-assisted systems.

VanderWal, Randy L.↗

Effect of nanostructuring on the interaction of CO 2 with molybdenum carbide nanoparticles

Transition metal carbides are increasingly used as catalysts for the transformation of CO 2 into useful chemicals. Recently, the effect of nanostructuring of such carbides has started to gain relevance in tailoring their catalytic capabilities. Catalytic materials based on molybdenum carbide nanoparticles (MoC y ) have shown a remarkable ability to bind CO 2 at room temperature and to hydrogenate it into oxygenates or light alkanes. However, the involved chemistry is largely unknown. In the present work, a systematic computational study is presented aiming to elucidate the chemistry behind the bonding of CO 2 with a representative set of MoC y nanoparticles of increasing size, including stoichiometric and non-stoichiometric cases. Furthermore, the obtained results provide clear trends to tune the catalytic activity of these systems and to move towards more efficient CO 2 transformation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal-growth-dominated fabrication of metal-organic frameworks with orderly distributed hierarchical porosity

Constructing architectures with hierarchical porosity has been widely considered as the most efficient way to bypass the problems related to slow mass transfer and inaccessibility of internal space in MOFs. Now, a crystal-growth-dominated strategy is proposed to fabricate hierarchically porous MOFs (HP-MOFs). When the crystal growth is dominated by the monomer attachment, the aggregation of nonionic surfactant or polymer can be easily captured and released during the crystal growth process, resulting in the formation and ordering hierarchical pores along the radial direction. Furthermore, owing to the accelerated mass diffusion and more exposed active sites of this design, HP-MOFs exhibited an enhanced catalytic efficiency in styrene oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A soil-inspired dynamically responsive chemical system for microbial modulation

Interactions between the microbiota and their colonized environments mediate critical pathways from biogeochemical cycles to homeostasis in human health. Here, in this study, we report a soil-inspired chemical system that consists of nanostructured minerals, starch granules and liquid metals. Fabricated via a bottom-up synthesis, the soil-inspired chemical system can enable chemical redistribution and modulation of microbial communities. We characterize the composite, confirming its structural similarity to the soil, with three-dimensional X-ray fluorescence and ptychographic tomography and electron microscopy imaging. We also demonstrate that post-synthetic modifications formed by laser irradiation led to chemical heterogeneities from the atomic to the macroscopic level. The soil-inspired material possesses chemical, optical and mechanical responsiveness to yield write-erase functions in electrical performance. The composite can also enhance microbial culture/biofilm growth and biofuel production in vitro. Finally, we show that the soil-inspired system enriches gut bacteria diversity, rectifies tetracycline-induced gut microbiome dysbiosis and ameliorates dextran sulfate sodium-induced rodent colitis symptoms within in vivo rodent models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nucleation kinetics model for primary crystallization in Al–Y–Fe metallic glass

The high density of aluminum nanocrystals (>10 21 m -3 ) that develop during the primary crystallization in Al-based metallic glasses indicates a high nucleation rate (~10 18 m -3 s -1 ). Several studies have been advanced to account for the primary crystallization behavior, but none have been developed to completely describe the reaction kinetics. Recently, structural analysis by fluctuation electron microscopy has demonstrated the presence of the Al-like medium range order (MRO) regions as a spatial heterogeneity in as-spun Al 88 Y 7 Fe 5 metallic glass that is representative for the class of Al-based amorphous alloys that develop Al nanocrystals during primary crystallization. From the structural characterization, an MRO seeded nucleation configuration is established, whereby the Al nanocrystals are catalyzed by the MRO core to decrease the nucleation barrier. The MRO seeded nucleation model and the kinetic data from the delay time (τ) measurement provide a full accounting of the evolution of the Al nanocrystal density (N v ) during the primary crystallization under isothermal annealing treatments. Moreover, the calculated values of the steady state nucleation rates (J ss ) predicted by the nucleation model agree with the experimental results. Moreover, the model satisfies constraints on the structural, thermodynamic, and kinetic parameters, such as the critical nucleus size, the interface energy, and the volume-free energy driving force that are essential for a fully self-consistent nucleation kinetics analysis. In conclusion, the nucleation kinetics model can be applied more broadly to materials that are characterized by the presence of spatial heterogeneities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molybdenum disulfide and related materials for water treatment

Catalytic water treatment is provided using an active material driven with an optical and/or electrical excitation. The active material is MoS2, MoSe2, WS2, WSe2, MoxW1-xS2, MoxW1-xSe2, MoSySe2-y, WSySe2-y, or MoxW1-xSySe2-y; wherein 0 < x < 1 and 0 < y < 2. The active material is configured as one or more layered nanostructures having exposed layer edges. A metal catalyst is disposed on the active material. The combined structure of active material and metal catalyst is disposed in the water to be treated. The excitation is provided to the active material to generate one or more reactive oxygen species by dissociation of water, wherein the reactive oxygen species provide water treatment.

36 MATERIALS SCIENCE↗

Nanosynthesis by atmospheric arc discharges excited with pulsed-DC power: a review

Plasma technology is actively used for nanoparticle synthesis and modification. All plasma techniques share the ambition of providing high quality, nanostructured materials with full control over their crystalline state and functional properties. Pulsed-DC physical/chemical vapour deposition, high power impulse magnetron sputtering, and pulsed cathodic arc are consolidated low-temperature plasma processes for the synthesis of high-quality nanocomposite films in vacuum environment. However, atmospheric arc discharge stands out thanks to the high throughput, wide variety, and excellent quality of obtained stand-alone nanomaterials, mainly core–shell nanoparticles, transition metal dichalcogenide monolayers, and carbon-based nanostructures, like graphene and carbon nanotubes. Unique capabilities of this arc technique are due to its flexibility and wide range of plasma parameters achievable by modulation of the frequency, duty cycle, and amplitude of pulse waveform. The many possibilities offered by pulsed arc discharges applied on synthesis of low-dimensional materials are reviewed here. Periodical variations in temperature and density of the pulsing arc plasma enable nanosynthesis with a more rational use of the supplied power. Parameters such as plasma composition, consumed power, process stability, material properties, and economical aspects, are discussed. Lastly a brief outlook towards future tendencies of nanomaterial preparation is proposed. Atmospheric pulsed arcs constitute promising, clean processes providing ecological and sustainable development in the production of nanomaterials both in industry and research laboratories.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Carbon Nanotube Based Chemical Sensors for Space and Terrestrial Applications

A nanosensor technology has been developed using nanostructures, such as single walled carbon nanotubes (SWNTs), on a pair of interdigitated electrodes (IDE) processed with a silicon-based microfabrication and micromachining technique. The IDE fingers were fabricated using photolithography and thin film metallization techniques. Both in-situ growth of nanostructure materials and casting of the nanostructure dispersions were used to make chemical sensing devices. These sensors have been exposed to nitrogen dioxide, acetone, benzene, nitrotoluene, chlorine, and ammonia in the concentration range of ppm to ppb at room temperature. The electronic molecular sensing of carbon nanotubes in our sensor platform can be understood by intra- and inter-tube electron modulation in terms of charge transfer mechanisms. As a result of the charge transfer, the conductance of p-type or hole-richer SWNTs in air will change. Due to the large surface area, low surface energy barrier and high thermal and mechanical stability, nanostructured chemical sensors potentially can offer higher sensitivity, lower power consumption and better robustness than the state-of-the-art systems, which make them more attractive for defense and space applications. Combined with MEMS technology, light weight and compact size sensors can be made in wafer scale with low cost. Additionally, a wireless capability of such a sensor chip can be used for networked mobile and fixed-site detection and warning systems for military bases, facilities and battlefield areas.

Li, Jing↗

Metal-assisted etch combined with regularizing etch

In an aspect of the disclosure, a process for forming nanostructuring on a silicon-containing substrate is provided. The process comprises (a) performing metal-assisted chemical etching on the substrate, (b) performing a clean, including partial or total removal of the metal used to assist the chemical etch, and (c) performing an isotropic or substantially isotropic chemical etch subsequently to the metal-assisted chemical etch of step (a). In an alternative aspect of the disclosure, the process comprises (a) performing metal-assisted chemical etching on the substrate, (b) cleaning the substrate, including removal of some or all of the assisting metal, and (c) performing a chemical etch which results in regularized openings in the silicon substrate.

36 MATERIALS SCIENCE↗

Electronic growth of Pd(111) nanostructures on MoS 2

Quantum confinement effects can induce the formation of discrete nanostructures with well-defined preferred heights in thin metallic films. In most systems, such electronic growth modes are weak and limited to cryogenic conditions. Recently, however, we have discovered that metals grown upon van der Waals surfaces can exhibit electronic growth at, or even above, room temperature to spontaneously form well-defined and highly stable nanostructures. Here, we explore the initial stages of room temperature deposition of Pd onto MoS 2 . We found that, even for minimal thicknesses, Pd spontaneously formed discrete islands with three atomic layers. The islands maintained this preferred height for nominal coverages below three atomic layers. At higher coverages, the preferred height switched abruptly to six atomic layers. Unlike previous studies using Au or Ag, the islands did not increase laterally with coverage but rather increased in number with lateral size remaining about the same. The preferred heights in Pd/MoS 2 correlate to the Pd Fermi surface topography and are also consistent with thicknesses showing minima in the density of states at the Fermi level, which suggest that the electronic growth modes are the driving factors in these self-assembled Pd nanostructures. The Pd system shows a preference for island nucleation compared to Au and Ag which grow laterally with increasing coverage. Furthermore, this is likely related to differences in bonding at the interface as Pd is typically much more reactive than Ag or Au.

36 MATERIALS SCIENCE↗