Low-Temperature and Fast Kinetics for CO2 Sorption Using Li6WO6 Nanowires.

In this paper, lithium hexaoxotungstate (Li6WO6) nanowires were synthesized via facile solid-state reaction and were tested for CO2 capture applications at both low (<100 °C) and high temperatures (>700 °C). Under dry conditions, the nanowire materials were able to capture CO2 with a weight increment of 12% in only 60 s at an operating temperature of 710 °C. By contrast, under humidified ambience, Li6WO6 nanowires capture CO2 with weight increment of 7.6% at temperatures as low as 30-40 °C within a time-scale of 1 min. It was observed that the CO2 chemisorption in Li6WO6 is favored in the oxygen ambience at higher temperatures and in the presence of water vapor at lower temperatures. Nanowire morphology favors the swift lithium supply to the surface of lithium-rich Li6WO6, thereby enhancing the reaction kinetics and lowering time scales for high capacity adsorption. Overall, high chemisorption capacities, superfast reaction kinetics, wide range of operating temperatures, and reasonably good recyclability make 1-D Li6WO6 materials highly suitable for various CO2 capture applications.

Ultrafast Carbon Dioxide Sorption Kinetics Using Lithium Silicate Nanowires.

In this paper, the Li4SiO4 nanowires (NWs) were shown to be promising for CO2 capture with ultrafast kinetics. Specifically, the nanowire powders exhibited an uptake of 0.35 g g-1 of CO2 at an ultrafast adsorption rate of 0.22 g g-1 min-1 at 650-700 °C. Lithium silicate (Li4SiO4) nanowires and nanopowders were synthesized using a "solvo-plasma" technique involving plasma oxidation of silicon precursors mixed with lithium hydroxide. The kinetic parameter values (k) extracted from sorption kinetics obtained using NW powders are 1 order of magnitude higher than those previously reported for the Li4SiO4-CO2 reaction system. The time scales for CO2 sorption using nanowires are approximately 3 min and two orders magnitude faster compared to those obtained using lithium silicate powders with spherical morphologies and aggregates. Furthermore, Li4SiO4 nanowire powders showed reversibility through sorption-desorption cycles indicating their suitability for CO2 capture applications. All of the morphologies of Li4SiO4 powders exhibited a double exponential behavior in the adsorption kinetics indicating two distinct time constants for kinetic and the mass transfer limited regimes.

Plasma Catalysis: Synergistic Effects at the Nanoscale.

Thermal-catalytic gas processing is integral to many current industrial processes. Ever-increasing demands on conversion and energy efficiencies are a strong driving force for the development of alternative approaches. Similarly, synthesis of several functional materials (such as nanowires and nanotubes) demands special processing conditions. Plasma catalysis provides such an alternative, where the catalytic process is complemented by the use of plasmas that activate the source gas. This combination is often observed to result in a synergy between plasma and catalyst. This Review introduces the current state-of-the-art in plasma catalysis, including numerous examples where plasma catalysis has demonstrated its benefits or shows future potential, including CO2 conversion, hydrocarbon reforming, synthesis of nanomaterials, ammonia production, and abatement of toxic waste gases. The underlying mechanisms governing these applications, as resulting from the interaction between the plasma and the catalyst, render the process highly complex, and little is known about the factors leading to the often-observed synergy. This Review critically examines the catalytic mechanisms relevant to each specific application.

Reduced SnO2 Porous Nanowires with a High Density of Grain Boundaries as Catalysts for Efficient Electrochemical CO2 -into-HCOOH Conversion.

Electrochemical conversion of CO2 into energy-dense liquids, such as formic acid, is desirable as a hydrogen carrier and a chemical feedstock. SnOx is one of the few catalysts that reduce CO2 into formic acid with high selectivity but at high overpotential and low current density. We show that an electrochemically reduced SnO2 porous nanowire catalyst (Sn-pNWs) with a high density of grain boundaries (GBs) exhibits an energy conversion efficiency of CO2 -into-HCOOH higher than analogous catalysts. HCOOH formation begins at lower overpotential (350 mV) and reaches a steady Faradaic efficiency of ca. 80 % at only -0.8 V vs. RHE. A comparison with commercial SnO2 nanoparticles confirms that the improved CO2 reduction performance of Sn-pNWs is due to the density of GBs within the porous structure, which introduce new catalytically active sites. Produced with a scalable plasma synthesis technology, the catalysts have potential for application in the CO2 conversion industry.

Stable and durable CH3NH3PbI3 perovskite solar cells at ambient conditions.

Degradation of metal-organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene-polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

Efficiency enhancement of cubic perovskite BaSnO3 nanostructures based dye sensitized solar cells.

Cubic perovskite BaSnO3 (BSO) is an important photoelectron transporting material due to its electronic structure that competes with TiO2 in dye-sensitized solar cells (DSCs). Separately, BSO/TiCl4 treated and BSO/scattering layer photoelectrodes have been used in DSCs that effectively increase the photoexcited charge carriers collection resulting in superior photovoltaic performance. In the present work, the different TiCl4 treatment time (1, 3 and 5 min), different scattering layer (tetragonal anatase TiO2 and hexagonal wurtzite ZnO) and different combinations thereof are successfully used on BSO nanocuboids/nanoparticle morphological structure photoelectrodes, and then we systematically inspected their performance in DSCs. Under the optimized conditions, a power conversion efficiency (PCE) of 3.88% is obtained by a BSO/TiCl4 treated photoanode. Furthermore, the BSO photoanodes made using a scattering layer such as anatase TiO2 and hexagonal ZnO i.e., BSO/anatase TiO2 and BSO/hexagonal ZnO, exhibited PCEs of 1.14% and 1.25% respectively. In the end, one of the highest PCEs (5.68%) was achieved using BSO/TiCl4 treated/TiO2 scattering layer photoanode. Another photoelectrode such as BSO/TiCl4 treated/ZnO scattering layer exhibited a PCE of 4.28% that is also higher than the BSO/TiCl4 treated/BSO scattering layer photoanodes. Electron lifetime versus current density studies illustrate the stability of the BSO photoelectrode in DSCs. From the observed results, it is realized that BSO is one of the most important future technological materials.

Informatics guided discovery of surface structure-chemistry relationships in catalytic nanoparticles.

A data driven discovery strategy based on statistical learning principles is used to discover new correlations between electronic structure and catalytic activity of metal surfaces. From the quantitative formulations derived from this informatics based model, a high throughput computational framework for predicting binding energy as a function of surface chemistry and adsorption configuration that bypasses the need for repeated electronic structure calculations has been developed.

Iron sulfide (FeS) nanotubes using sulfurization of hematite nanowires.

We report the phase transformation of hematite (α-Fe2O3) single crystal nanowires to crystalline FeS nanotubes using sulfurization with H2S gas at relatively low temperatures. Characterization indicates that phase pure hexagonal FeS nanotubes were formed. Time-series sulfurization experiments suggest epitaxial growth of FeS as a shell layer on hematite. This is the first report of hollow, crystalline FeS nanotubes with NiAs structure and also on the Kirkendall effect in solid-gas reactions with nanowires involving sulfurization.

MoO(3-x) nanowire arrays as stable and high-capacity anodes for lithium ion batteries.

In this study, vertical nanowire arrays of MoO(3-x) grown on metallic substrates with diameters of ~90 nm show high-capacity retention of ~630 mAhg(-1) for up to 20 cycles at 50 mAg(-1) current density. Particularly, they exhibit a capacity retention of ~500 mAhg(-1) in the voltage window of 0.7-0.1 V, much higher than the theoretical capacity of graphite. In addition, 10 nm Si-coated MoO(3-x) nanowire arrays have shown a capacity retention of ~780 mAhg(-1), indicating that hybrid materials are the next generation materials for lithium ion batteries.

Photoelectrochemical activity of as-grown, α-Fe2O3 nanowire array electrodes for water splitting.

Undoped hematite nanowire arrays grown using plasma oxidation of iron foils show significant photoactivity (~0.38 mA cm(-2) at 1.5 V versus reversible hydrogen electrode in 1 M KOH). In contrast, thermally oxidized nanowire arrays grown on iron exhibit no photoactivity due to the formation of a thick (>7 µm Fe(1-x)O) interfacial layer. An atmospheric plasma oxidation process required only a few minutes to synthesize hematite nanowire arrays with a 1­5 µm interfacial layer of magnetite between the nanowire arrays and the iron substrate. An amorphous oxide surface layer on hematite nanowires, if present, is shown to decrease the resulting photoactivity of as-synthesized, plasma grown nanowire arrays. The photocurrent onset potential is improved after removing the amorphous surface on the nanowires using an acid etch. A two-step method involving high temperature nucleation followed by growth at low temperature is shown to produce a highly dense and uniform coverage of nanowire arrays.

Core-shell MoO3-MoS2 nanowires for hydrogen evolution: a functional design for electrocatalytic materials.

We synthesize vertically oriented core-shell nanowires with substoichiometric MoO(3) cores of ∼20-50 nm and conformal MoS(2) shells of ∼2-5 nm. The core-shell architecture, produced by low-temperature sulfidization, is designed to utilize the best properties of each component material while mitigating their deficiencies. The substoichiometric MoO(3) core provides a high aspect ratio foundation and enables facile charge transport, while the conformal MoS(2) shell provides excellent catalytic activity and protection against corrosion in strong acids.

Stable and Flexible Sulfide Composite Electrolyte for High-Performance Solid-State Lithium Batteries.

Sulfide-based lithium (Li)-ion conductors represent one of the most popular solid electrolytes (SEs) for solid-state Li metal batteries (SSLMBs) with high safety. However, the commercial application of sulfide SEs is significantly limited by their chemical instability in air and electrochemical instability with electrode materials (metallic Li anode and oxide cathodes). To address these difficulties, here, we design and successfully demonstrate a novel sulfide-incorporated composite electrolyte (SCE) through the combination of inorganic sulfide Li argyrodite (Li7PS6) with poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) polymer. In this composite structure, Li7PS6 is embedded in PVDF-HFP polymer matrix, making the SCE flexible and air-stable and achieve great chemical and electrochemical stability. Meanwhile, the presence of sulfide facilitates Li-ion transport in SCE, leading to a superior room-temperature ionic conductivity of 1.1 × 10-4 S cm-1. Using the SCE with enhanced stability while maintaining high conductivity, Li||Li symmetric cells achieved stable cycling up to 1000 h at 0.2 mA cm-2. In addition, LiFePO4 (LFP)||SCE||Li cells can deliver an impressive specific capacity of 160 mAh g-1 over 150 cycles. These features indicate that Li7PS6/PVDF-HFP SCE is a promising candidate to contribute to the practical development of SSLMBs.

Rapid and Economic Synthesis of a Li7PS6 Solid Electrolyte from a Liquid Approach.

Solid electrolytes are the key to realize future solid-state batteries that show the advantages of high energy density and intrinsic safety. However, most solid electrolytes require long time and energy-consuming synthesis conditions of either extended ball milling or high-temperature solid-state reactions, impeding practical applications of solid electrolytes for large-scale systems. Here, we report a new and rapid liquid-based synthetic method for preparing a high-purity Li7PS6 solid electrolyte through the stoichemical reaction of Li3PS4 and Li2S. This method relies on facile and low-cost solution-based soft chemistry to complete chemical reaction in extensively short time (2 h). The prepared Li7PS6 solid electrolyte shows a high phase purity, an impressive ionic conductivity (0.11 mS cm-1), and a reasonable electrochemical stability with a metallic lithium anode. Our results highlight the use of an economic and nontoxic solvent to quickly synthesize a Li7PS6 solid electrolyte, which would promote the development of solid-state batteries for next-generation energy storage systems.

A new nanowire-based lithium hexaoxotungstate anode for lithium-ion batteries.

This study reports one dimensional lithium hexaoxotungstate (Li6WO6), with a diameter in the range of 200-500 nm, as a novel anode material for lithium-ion batteries. The electrochemical performance of lithium hexaoxotungstate was investigated and a discharge capacity of 705 mA h g-1 was achieved after 50 cycles, along with an excellent rate capability. The 1D morphology of the material is believed to provide excellent transport properties, resulting in a high rate capability. The remarkable electrochemical performance of the Li6WO6 nanowires indicates that this new class of anode holds a lot of promise for future deployment in energy storage devices.

Zinc Oxide Nanowires Exposure Induces a Distinct Inflammatory Response via CCL11-Mediated Eosinophil Recruitment.

High aspect ratio zinc oxide nanowires (ZnONWs) have become one of the most important products in nanotechnology. The wide range applications of ZnONWs have heightened the need for evaluating the risks and biological consequences to these particles. In this study, we investigated inflammatory pathways activated by ZnONWs in cultured cells as well as the consequences of systemic exposure in mouse models. Confocal microscopy showed rapid phagocytic uptake of FITC-ZnONWs by macrophages. Exposure of macrophages or lung epithelial cells to ZnONWs induced the production of CCL2 and CCL11. Moreover, ZnONWs exposure induced both IL-6 and TNF-α production only in macrophages but not in LKR13 cells. Intratracheal instillation of ZnONWs in C57BL/6 mice induced a significant increase in the total numbers of immune cells in the broncho alveolar lavage fluid (BALFs) 2 days after instillation. Macrophages and eosinophils were the predominant cellular infiltrates of ZnONWs exposed mouse lungs. Similar cellular infiltrates were also observed in a mouse air-pouch model. Pro-inflammatory cytokines IL-6 and TNF-α as well as chemokines CCL11, and CCL2 were increased both in BALFs and air-pouch lavage fluids. These results suggest that exposure to ZnONWs may induce distinct inflammatory responses through phagocytic uptake and formation of soluble Zn2+ ions.

Electrochemical pinning of the Fermi level: mediation of photoluminescence from gallium nitride and zinc oxide.

Charge transfer between diamond and an electrochemical redox couple in an adsorbed water film has recently been shown to pin the Fermi level in hydrogen-terminated diamond. Here we show that this effect is a more general phenomenon and influences the properties of other semiconductors when the band lineup between the ambient and electronic states in the semiconductor is appropriate. We find that the luminescent intensities from GaN and ZnO change in different, but predictable, ways when exposed to HCl and NH3 vapors in humid air. The effect is reversible and has been observed on single crystals, nanowires, flakes, and powders. These observations are explained by electron exchange between the oxygen electrochemical redox couple in an adsorbed water film and electronic states in the semiconductor. This effect can take place in parallel with other processes such as defect formation, chemisorption, and surface reconstruction and may play an important, but previously unrecognized, role when electronic and optical measurements are made in air.

Mesoporous TiO2 coating on carbon-sulfur cathode for high capacity Li-sulfur battery.

In this paper, a meso-porous TiO2 (titania) coating is shown to effectively protect a carbon-sulfur composite cathode from polysulfide dissolution. The cathode consisted of a sulfur impregnated carbon support coated with a few microns thick mesoporous titania layer. The carbon-sulfur cathode is made using activated carbon powder (ACP) derived from biomass. The mesoporous titania coated carbon-sulfur cathodes exhibit a retention capacity after 100 cycles at C/3 rate (433 mA g -1) and stabilized at a capacity around 980 mA h g-1. The electrochemical impedance spectroscopy (EIS) of the sulfur cathodes suggests that the charge transfer resistance at the anode, (R act) is stable for the titania coated sulfur electrode in comparison to a continuous increase in R act for the uncoated electrode implying mitigation of polysulfide shuttling for the protected cathode. Stability in the cyclic voltammetry (CV) data for the first 5 cycles further confirms the polysulfide containment in the titania coated cathode while the uncoated sulfur electrode shows significant irreversibility in the CV with considerable shifting of the voltage peak positions. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) studies confirm the adsorption of soluble polysulfides by mesoporous titania.

Large-scale, hot-filament-assisted synthesis of tungsten oxide and related transition metal oxide nanowires.

A scalable and versatile method for the large-scale synthesis of tungsten trioxide nanowires and their arrays on a variety of substrates, including amorphous quartz and fluorinated tin oxide, is reported. The synthesis involves the chemical-vapor transport of metal oxide vapor-phase species using air or oxygen flow over hot filaments onto substrates kept at a distance. The results show that the density of the nanowires can be varied from 10(6)-10(10) cm(-2) by varying the substrate temperature. The diameter of the nanowires ranges from 100-20 nm. The results also show that variations in oxygen flow and substrate temperature affect the nanowire morphology from straight to bundled to branched nanowires. A thermodynamic model is proposed to show that the condensation of WO(2) species primarily accounts for the nucleation and subsequent growth of the nanowires, which supports the hypothesis that the nucleation of nanowires occurs through condensation of suboxide WO(2) vapor-phase species. This is in contrast to the expected WO(3) vapor-phase species condensation into WO(3) solid phase for nanoparticle formation. The as-synthesized nanowires are shown to form stable dispersions compared to nanoparticles in various organic and inorganic solvents.