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At least 1,081 records · Page 60

Spectral characteristics of nanoamorphous phosphors obtained by evaporation of Sr{sub 2}Gd{sub 8}(SiO{sub 4}){sub 6}O{sub 2}: Eu polycrystals

Amorphous nanophosphors have been obtained for the first time by pulsed electron beam evaporation of targets from bulk polycrystalline phosphors of the composition Sr{sub 2}Gd{sub 8}(SiO{sub 4}){sub 6}O{sub 2}: Eu with oxyapatite structure. The processes of crystallization of amorphous nanopowder were studied using differential scanning calorimetry and termogravimetry (40−1400 °C). It was found that the Raman spectra of the samples are modified when the particles decrease from bulk to nanodimensional state. The spectral and luminescent characteristics of the phosphors in polycrystalline and nanoamorphous states have been examined. It was established that Eu{sup 3+} forms two types of optical centers. Unlike bulk phosphors, in the nanophosphors no Eu{sup 2+} ions are formed. The ratio of red to orange luminescence intensity for nanophosphors was found to increase as compared with bulk phosphors. This effect is due to disordering of nanoparticles. A resonant transfer of excitation energy from Gd{sup 3+} to Eu{sup 3+} ions was found in bulk and nanophosphors. Upon transition from polycrystalline to nanoamorphous state and laser excitation of phosphors, the luminescence intensity of Eu{sup 3+} ions increases approximately 10 times. This effect is explained in the framework of the configuration coordinates model. - Graphical abstract: Schematic configurational-coordinate diagram for Eu{sup 3+} ion in polycrystalline Sr{sub 2}Gd{sub 6.4}Eu{sub 1.6}Si{sub 6}O{sub 26−δ} and nanoamorphous phosphor. - Highlights: • Nanoamorphous phosphor is obtained by electron-beam evaporation of bulk silicate. • In nanoamorphous samples Raman spectra are modified intensity. • Nanofosfor luminescence by 10 times more intensively, than bulk phosphorus. • There is a transfer of energy of excitation from Gd{sup 3+} to Eu{sup 3+} in bulk- and nanophosphor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile synthesis of B-type carbonated nanoapatite with tailored microstructure

Nanolime and a phosphate-based chelating agent were used to synthesize B-type carbonated apatite. Developed Rietveld refinement strategies allowed one to determine process yield, product crystallinity as well as structural (unit cell) and microstructural (size, strain) parameters. The effect of synthesis temperature (20–60 °C) as well as Ca/P ratio (1.5–2.5) and solid content (10–30 wt%) of the starting batch on these properties were investigated. FTIR, TEM and gas adsorption data provided supporting evidence. The process yield was 42–60 wt% and found to be governed by the Ca/P ratio. The purified products had high specific surface area (107–186 m{sup 2}/g) and crystallinity (76–97%). The unit cell parameters, correlated to the degree of structural carbonate, were sensitive to the Ca/P ratio. Instead, temperature governed the microstructural parameters. Less strained and larger crystals were obtained at higher temperatures. Long-term aging up to 6 months at 20 °C compensated for higher crystal growth kinetics at higher temperature. - Graphical abstract: Controlled synthesis of carbonated apatite at moderate temperatures using nanolime and sodiumhexametaphosphate as starting reagent. - Highlights: • Chemical synthesis of nano-sized apatite with tailored microstructure was performed. • Colloidal Ca(OH){sub 2} and a phosphorus-based chelating agents were used as reagents. • The method is simple and reproducible which facilitate industrial process scale-up. • Rietveld refinement strategies for product characterization were developed. • Rietveld analyses provided yield, microstructural and structure information.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance

Graphical abstract: Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance. - Highlights: • Three-dimensional Ni{sub 2}P has been prepared using foam nickel as a template. • The microstructures interconnected and formed sponge-like porous networks. • Three-dimensional Ni{sub 2}P shows superior hydrodesulfurization activity. - Abstract: Three-dimensional microstructured nickel phosphide (Ni{sub 2}P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni{sub 2}P samples, as interconnected networks, maintained the original mesh structure of foamed nickel. The crystal structure and morphology of the as-synthesized Ni{sub 2}P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the three-dimensionally structured Ni{sub 2}P was postulated and discussed in detail. To investigate its catalytic properties, SiO{sub 2} supported three-dimensional Ni{sub 2}P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni{sub 2}P/SiO{sub 2}.

36 MATERIALS SCIENCE↗

Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

Nanostructured TiO{sub 2} and mixed oxides of Ti and Fe, Hf, In, Mn or Zr -were prepared by homogeneous hydrolysis of aqueous solution of metal sulphates with urea. The oxides were characterised by X-ray powder diffraction (XRD), scanning electron microscopy, particle size distribution, surface area and porosity. The oxide materials consists of a few nanometre primary crystals (mainly anatase) arranged in a few micrometre regular spherical agglomerates with specific surface area 133–511 m{sup 2} g{sup −1}. The FTIR diffuse spectroscopy was used for monitoring chemical degradation of trimethylphosphate (TMP) as a surrogate for organo-phosphorus pesticides under ambient and higher temperatures. Undoped TiO{sub 2} and Ti,Mn-mixed oxide were most active in cleavage (hydrolysis) of CH{sub 3}O from TMP at room temperature and 100 °C. Cleavage of CH{sub 3}O in the other studied mixed oxides was not complete until temperature exceeds the boiling point of TMP.

36 MATERIALS SCIENCE↗

Phase-control synthesis and catalytic property of magnetic Ni@NixPy core-shell microstructures

Highlights: • Ni@Ni{sub x}P{sub y} core-shell microstructures are synthesized by a low-temperature phosphidation route. • The initial Ni/NaH{sub 2}PO{sub 2} molar ratio can strongly affect the phase of the final product. • Ni@Ni{sub x}P{sub y} microstructures present good catalytic activity for the reduction of 4-nitrophenol. • The catalytic property of Ni@Ni{sub x}P{sub y} microstructures presents markedly phase-dependent features. - Abstract: Magnetic Ni@Ni{sub x}P{sub y} core-shell microstructures were successfully synthesized by a simple low-temperature phosphidation route, employing Ni nanospheres as the initial nickel source, NaH{sub 2}PO{sub 2}·H{sub 2}O as the phosphorus ion source. The phosphidation reaction was carried out in N{sub 2} atmosphere at 300 °C for 2 h. Experiments showed that the initial Ni/NaH{sub 2}PO{sub 2} molar ratio could strongly affect the phase of the final product. When the Ni/NaH{sub 2}PO{sub 2} molar ratio of 1:2.77 was used, hexagonal Ni{sub 2}P phase was obtained; while the Ni/NaH{sub 2}PO{sub 2} molar ratio was 1:5.54, hexagonal Ni{sub 5}P{sub 4} phase was produced. It was found that the magnetic properties of the products gradually decreased with the conversion from Ni nanospheres, to Ni@Ni{sub 2}P and to Ni@Ni{sub 5}P{sub 4}. Moreover, initial Ni nanospheres, Ni@Ni{sub 2}P and Ni@Ni{sub 5}P{sub 4} core-shell microstructures presented outstanding catalytic activities for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in excess NaBH{sub 4} solution. Ni@Ni{sub 5}P{sub 4} core-shell microstructures owned the best catalytic activity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Climate-eutrophication-anoxia interactions in Late Glacial Soppensee, Switzerland: Forcings, non-linear responses and recovery

Combined effects of climate warming and anthropogenic nutrient loadings lead to lake eutrophication and anoxia globally. Because of chemical feedbacks, lakes under multiple stressors often respond in non-linear ways. However, it remains unclear whether climate change alone can lead to non-linear lake responses in the absence of anthropogenic nutrient disturbances. Here, we investigate the interactions between climate variability, nutrient cycling and trophic state changes, mixing regimes, anoxia and related chemical feedback in a small kettle-hole lake in Switzerland during Late Glacial times (15.2–12.6 cal ka BP), a period known for high-amplitude climate change in pre-anthropogenic times. After its formation during Heinrich Stadial 1 (>15 cal ka BP), Soppensee was oligotrophic and well-mixed. Soppensee became eutrophic and developed anoxia at 14.25 cal ka BP. Phosphorus (P) was released from sediments through the reductive dissolution of Fe-oxyhydroxides, fuelling eutrophication. Eutrophication lagged the Bølling warming (14.65 cal ka BP) by 400 years, suggesting that rising temperatures were not the trigger for eutrophication. Instead, eutrophication responded non-linearly to forest closure (threshold at 76 % arboreal pollen AP), which shielded Soppensee from wind mixing, enhancing lake stratification, anoxia and P release, intensifying eutrophication. These conditions ended during the 200-years cold period of the Aegelsee Oscillation (GI-1d, ca. 14.0 cal ka BP) when the landscape regionally opened (AP<76 %); the lake became well-mixed, oxygenated and P was efficiently sequestered. Throughout the Allerød (13.9–12.8 cal ka BP), enhanced Fe input prompted diagenetic vivianite formation, sequestering P in sediments, naturally remediating lake eutrophication despite closed forests, warm temperatures, lake stratification and anoxia.

Environmental sciences↗

Spatiotemporal patterns of livestock manure nutrient production in the conterminous United States from 1930 to 2012

Manure nitrogen (N) and phosphorus (P) from livestock husbandry are important components of terrestrial biogeochemical cycling. Assessment of the impacts of livestock manure on terrestrial biogeochemistry requires a compilation and analysis of spatial and temporal patterns of manure nutrients. In this study, we reconstructed county-level manure nutrient data of the conterminous United States (U.S.) in 4- to 5-year increments from 1930 to 2012. Manure N and P were 5.89 +/- 0.64 Tg N yr.(-1) (Mean +/- Standard Deviation) and 1.73 +/- 0.29 Tg P yr.(-1) (1 Tg=10(12) g), and increased by 46% and 92% from 1930 to 2012, respectively. Prior to 1970, manure provided more N to the U.S. lands than chemical fertilizer use. Since 1970, however, increasing chemical N fertilizer use has exceeded manure N production. Manure was the primary P source in the U.S. during 1930-1969 and 1987-2012, but was lower than P fertilizer use in 1974, 1978, and 1982. High-nutrient-production regions shifted towards eastern and western areas of the U.S. Decreasing small farms and increasing Concentrated Animal Feeding Operations (CAFOs) induced concentrated spatial patterns in manure nutrient loads. Counties with cattle or poultry as the primary manure nutrient contributors expanded significantly from 1930 to 2012, whereas regions with sheep and hog as the primary contributors decreased. We identified regions facing environmental threats associated with livestock farming. Effective management of manure should consider the impacts of CAFOs inmanure production, and changes in livestock population structure. The long-term county-level manure nutrient dataset provides improved spatial and temporal information on manure nutrients in the U.S. This dataset is expected to help advance research on nutrient cycling, ammonia volatilization, greenhouse gas (GHG) emissions from livestock husbandry, recovery and reuse of manure nutrients, and impacts of livestock feeding on human health in the context of global change.

Livestock↗

Windrow co-composting of natural casings waste with sheep manure and dead leaves

Highlights: • Waste management opportunities in small and medium companies were highlighted. • Pilot scale program for windrow co-composting of natural casings was investigated. • Compost preparation, characterization and application phases were discussed. • Natural casings co-composting has proved more viable and cost effective solution. - Abstract: After studying the waste management opportunities in small and medium companies of natural casings, composting has proved more viable and cost effective solution for the valorization of these types of waste, but its feasibility depends on the final product value. This paper investigated a pilot scale program for the windrow co-composting of natural casings waste with sheep manure and dead leaves incorporation. Processing, characterization and application of the final compost were described and the final compost was analyzed for pathogens, metals, nutrients, maturity, and agronomic parameters. The results showed that all test result levels were below the limits specified in the EPA regulations published in Title 40, Section 503, of the Code of Federal Regulations (40 CFR 503). Moreover, the agronomic value tests which include nutrients, organic matter, pH, electrical conductivity, etc. showed that the compost had high organic-matter content and low salt content, all of which indicate good compost characteristics. The ratio of nitrogen (N), phosphorus (P), and potassium (K), or NPK ratio, was measured at 1.6–0.9–0.7. Reported units are consistent with those found on fertilizer formulations.

60 APPLIED LIFE SCIENCES↗

Recovery of essential nutrients from municipal solid waste – Impact of waste management infrastructure and governance aspects

Every year 120–140 million tonnes of bio-waste are generated in Europe, most of which is landfilled, incinerated or stabilized and used as covering material in landfill operation. None of these practices enables the recovery of essential nutrients such as phosphorus (P) and nitrogen (N), which are in great demand for agricultural production. Recovery of these nutrients is a matter of international concern considering the non-renewable nature of P sources and the energy intensive production process required for the synthesis of N fertilizers. The objective of this research is to understand the relation between the municipal solid waste management (MSWM) system, both its the physical components and governance aspects, and the recovery of nutrients in Vitoria-Gasteiz (Basque Country) as a benchmark for European medium-size cities. The analysis shows that the existing physical infrastructure and facilities for bio-waste have high potential for nutrient recovery, 49% for N and 83% for P contained in bio-waste. However, governance aspects of the MSWM system such as legislation and user inclusivity play an important role and decrease the actual nutrient recovery to 3.4% and 7.4% for N and P respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Environmental assessment of alternative treatment schemes for energy and nutrient recovery from livestock manure

Highlights: • Energy and nutrient recovery from manure was environmentally evaluated. • Direct digestate application is not always feasible. • AD+centrifugation+N-removal was the most environmentally favourable scenario. • N-removal through HRAS+PNA considerably improved the environmental performance. • UF membrane+acidification were needed to improve struvite quantity and quality. - Abstract: The application of livestock manure on agricultural land is being restricted due to its significant content of phosphorus (P) and nitrogen (N), leading to eutrophication. At the same time, the growing demand for N and P mineral fertilizers is increasing their production costs and causing the depletion of natural phosphate rock deposits. In the present work, seven technologically feasible treatment schemes for energy (biogas) and nutrient recovery (e.g., struvite precipitation) and/or removal (e.g., partial nitritation/anammox) were evaluated from an environmental perspective. In general, while approaches based solely on energy recovery and use of digestate as fertilizer are commonly limited by community regulations, strategies pursuing the generation of high-quality struvite are not environmentally sound alternatives. In contrast, schemes that include further solid/liquid separation of the digestate improved the environmental profile, and their combination with an additional N-removal stage would lead to the most environmental-friendly framework. However, the preferred scenario was identified to be highly dependent on the particular conditions of each site, integrating environmental, social and economic criteria.

09 BIOMASS FUELS↗

Nanostructured Black Phosphorus/Ketjenblack–Multiwalled Carbon Nanotubes Composite as High Performance Anode Material for Sodium-Ion Batteries

Sodium-ion batteries are promising alternatives to lithium-ion batteries for large-scale applications. However, the low capacity and poor rate capability of existing anodes for sodium-ion batteries are bottlenecks for future developments. Here, we report a high performance nanostructured anode material for sodium-ion batteries that is fabricated by high energy ball milling to form black phosphorus/Ketjenblack–multiwalled carbon nanotubes (BPC) composite. With this strategy, the BPC composite with a high phosphorus content (70 wt %) could deliver a very high initial Coulombic efficiency (>90%) and high specific capacity with excellent cyclability at high rate of charge/discharge (~1700 mAh g–1 after 100 cycles at 1.3 A g–1 based on the mass of P). In situ electrochemical impedance spectroscopy, synchrotron high energy X-ray diffraction, ex situ small/wide-angle X-ray scattering, high resolution transmission electronic microscopy, and nuclear magnetic resonance were further used to unravel its superior sodium storage performance. The scientific findings gained in this work are expected to serve as a guide for future design on high performance anode material for sodium-ion batteries.

25 ENERGY STORAGE↗

Thick Layered Semiconductor Devices with Water Top-Gates: High On–Off Ratio Field-Effect Transistors and Aqueous Sensors

Layered semiconductors show promise as channel materials for field-effect transistors (FETs). Usually, such devices incorporate solid back or top gate dielectrics. Here, we explore deionized (DI) water as a solution top-gate for field-effect switching of layered semiconductors including SnS 2 , MoS 2 , and black phosphorus. The DI water gate is easily fabricated, can sustain rapid bias changes, and its efficient coupling to layered materials provides high on–off current ratios, near-ideal subthreshold swing, and enhanced short-channel behavior even for FETs with thick, bulk-like channels, where such control is difficult to realize with conventional back gating. Screening by the high-k solution gate eliminates hysteresis due to surface and interface trap states and substantially enhances the field-effect mobility. The onset of water electrolysis sets the ultimate limit to DI water gating at large negative gate bias. Measurements in this regime show promise for aqueous sensing, demonstrated here by the amperometric detection of glucose in aqueous solution. In conclusion, DI water gating of layered semiconductors can be harnessed in research on novel materials and devices, and it may with further development find broad applications in microelectronics and sensing.

36 MATERIALS SCIENCE↗

Mechanical Properties of 2D LiInP 2 Se 6 : Implication for Semiconductor Applications

Metal phosphorus trichalcogenides (MPTCs) are emerging 2D semiconductor materials with unique functional properties that set them apart from other 2D systems. Despite the importance of their mechanical properties for improving the semiconductor device’s durability and performance, as well as for utilizing strain effects to customize material properties and create new functionality, our current understanding of MPTCs’ mechanical behavior is lacking and lags behind our knowledge of their other properties. Here, we use LiInP 2 Se 6 as a model example of MPTCs and report the first experimental measurements of the elastic and plastic (fracture) properties along both in-plane and out-of-plane directions by atomic force microscopy and nanoindentation. Being a 2D material that is entirely inorganic, LiInP 2 Se 6 surprisingly exhibits mechanical properties that resemble those of hybrid organic–inorganic materials rather than pure inorganic 2D materials. It has a soft crystal structure with low elastic moduli, a low difference in in-plane vs out-of-plane mechanical properties, and a combination of elastic and plastic characteristics of hybrid organic–inorganic materials. Furthermore, our work provides the mechanical information critically needed to mitigate and/or harness the strain effects in LiInP 2 Se 6 -based semiconductor devices and sheds light on the mechanical behaviors of MPTCs with indispensable insights.

2D semiconductor↗

Electron-Beam Induced Emergence of Mesoscopic Ordering in Layered MnPS 3

Ordered mesoscale structures in 2D materials induced by small misorientations have allowed for a wide variety of electronic, ferroelectric, and quantum phenomena to be explored. Until now, the only mechanism to induce this periodic ordering was via mechanical rotations between the layers, with the periodicity of the resulting moiré pattern being directly related to twist angle. Here we report a fundamentally distinct mechanism for emergence of mesoscopic periodic patterns in multilayer sulfur-containing metal phosphorus trichalcogenide, MnPS3, induced by the electron beam. The formation under the beam of periodic hexagonal patterns with several characteristic length scales, nucleation and transitions between the phases, and local dynamics are demonstrated. The associated mechanisms are attributed to the relative contraction of the layers caused by beam-induced sulfur vacancy formation with subsequent ordering and lattice parameter change. As a result, the plasmonic response of the system is locally altered, suggesting an element of control over plasmon resonances by electron beam patterning. To conclude, we pose that harnessing this phenomenon provides both insight into fundamental physics of quantum materials and enables device applications by enabling controlled periodic potentials on the atomic scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal Structures of Phosphite Dehydrogenase Provide Insights into Nicotinamide Cofactor Regeneration

The enzyme phosphite dehydrogenase (PTDH) catalyzes the NAD{sup +}-dependent conversion of phosphite to phosphate and represents the first biological catalyst that has been shown to conduct the enzymatic oxidation of phosphorus. Despite investigation for more than a decade into both the mechanism of its unusual reaction and its utility in cofactor regeneration, there has been a lack of any structural data for PTDH. Here we present the cocrystal structure of an engineered thermostable variant of PTDH bound to NAD{sup +} (1.7 {angstrom} resolution), as well as four other cocrystal structures of thermostable PTDH and its variants with different ligands (all between 1.85 and 2.3 {angstrom} resolution). These structures provide a molecular framework for understanding prior mutational analysis and point to additional residues, located in the active site, that may contribute to the enzymatic activity of this highly unusual catalyst.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts

Ru2P/SiO2 and RuP/SiO2 catalysts were prepared by the temperature-programmed reduction (TPR) of uncalcined precursors containing hypophosphite ion (H2PO2-) as the phosphorus source. The Ru2P/SiO2 and RuP/SiO2 catalysts had small average particle sizes (~4 nm) and high CO chemisorption capacities (90-110 umol/g). The Ru phosphide catalysts exhibited similar or higher furan (C4H4O) hydrodeoxygenation (HDO) activities than did a Ru/SiO2 catalyst, and the phosphide catalysts favored C4 hydrocarbon products while the Ru metal catalyst produced primarily C3 hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphate Bonding on Non-crystalline Al/Fe-hydroxide Co-Precipitates

Poorly crystalline minerals have high sorption capacities for environmentally important chemical species, but molecular-level mechanisms of sorption on complex mineral assemblages remain largely unknown. We determined the distribution of orthophosphate (PO{sub 4}) bonding between Al and Fe in relation to structural properties of Al/Fe-hydroxide coprecipitates. Phosphate was sorbed at concentrations between 0.042 and 0.162 mol P mol{sup -1} Al+Fe on coprecipitates containing 0, 20, 50, 75, or 100 mol % of metal as Al. Phosphorus XANES analyses showed preferential bonding of PO{sub 4} for Al on coprecipitates with 20 and 50 mol % Al, and no preference for either metal at 75 mol % Al, consistent with X-ray photoelectron spectroscopy (XPS) analyses of near-surface metal distributions. Structural ordering and the Fe-hydroxide domain size in coprecipitates decreased with increasing Al proportion, as shown by X-ray diffraction (XRD) and Fe EXAFS analyses. Structural interactions in coprecipitates imparted unique PO{sub 4} sorption properties compared with isolated Al- or Fe-hydroxide.

54 ENVIRONMENTAL SCIENCES↗

Separating and Stabilizing Phosphate from High-Level Radioactive Waste: Process Development and Spectroscopic Monitoring

Removing phosphate from alkaline high-level waste sludges at the Department of Energy's Hanford Site in Washington State is necessary to increase the waste loading in the borosilicate glass waste form that will be used to immobilize the highly radioactive fraction of these wastes. We are developing a process which first leaches phosphate from the high-level waste solids with aqueous sodium hydroxide, and then isolates the phosphate by precipitation with calcium oxide. Tests with actual tank waste confirmed that this process is an effective method of phosphate removal from the sludge and offers an additional option for managing the phosphorus in the Hanford tank waste solids. The presence of vibrationally active species, such as nitrate and phosphate ions, in the tank waste processing streams makes the phosphate removal process an ideal candidate for monitoring by Raman or infrared spectroscopic means. As a proof-of-principle demonstration, Raman and Fourier transform infrared (FTIR) spectra were acquired for all phases during a test of the process with actual tank waste. Quantitative determination of phosphate, nitrate, and sulfate in the liquid phases was achieved by Raman spectroscopy, demonstrating the applicability of Raman spectroscopy for the monitoring of these species in the tank waste process streams.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗