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At least 631 records · Page 35

Enhancement under UV–visible and visible light of the ZnO photocatalytic activity for the antibiotic removal from aqueous media using Ce-doped Lu3Al5O12 nanoparticles

We report the first synthesis of Ce-doped Lu{sub 3}Al{sub 5}O{sub 12} Nanoparticles/ZnO Nanostructure (LuAG:Ce/ZnO NS) via a rapid hydrolysis/condensation of Zn(OAc){sub 2} on the surface of LuAG:Ce NPs. The structural, morphological and optical properties of LuAG:Ce/ZnO NS have been fully investigated using X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM), Energy Dispersive X-ray Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR), diffuse reflectance UV–visible spectroscopy and N2 adsorption/desorption measurements. Results showed that ZnO Nanocrystals (ZnO NCs) of about 10 nm diameter are homogeneously grown on the surface of 100 nm LuAG:Ce NPs in a core/shell-like structure. The photocatalytic activity of the as-prepared nanostructure has been evaluated throught the photodegradation of sulfathiazole (STZ), a molecule widely used as antibiotic, under UV–vis and visible light irradiation. Results showed that STZ undergoes much higher photodegradation in the presence of LuAG:Ce/ZnO NS compared to the pure ZnO NCs under both UV–vis and visible light. This enhanced photocatalytic capability was found to result from higher specific surface area and visible light absorption in LuAG:Ce/ZnO NS, which allowed for more surface active sites and enhanced hydroxyl radicals (·OH) production from the nanostructured photocatalyst. The recyclability of LuAG:Ce/ZnO NS was also demonstrated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Electrochemical Residence Time Distribution as a Diagnostic Tool for Redox Flow Batteries

The fluid dynamic and electrochemical performance of redox flow batteries (RFBs) stems from the relationship between the flow field and the porous electrode, whose interplay determines how active species move and react during device operation. While characterization techniques, such as residence time distribution, offer insights into species mobility within a reactive volume for a traditional chemical reactor, electrochemical reactors also enable simultaneous measurement of the redox reactions, unlocking another dimension of analysis. Herein, we demonstrate how potentiodynamic measurements, using injections of electrolyte examined through moment analysis, can provide electrode-specific performance scaling relationships across a matrix of carbon paper and cloth electrodes with flow through and interdigitated flow fields. We further combine experimental campaigns with multiphysics simulations to demonstrate how electrode surface area can be estimated with this technique, which we then validate with activated and unactivated commercial carbon cloth electrodes. These studies reveal the multiscale observations that potentiodynamic measurements afford, augmenting existing electrochemical techniques for holistic electrochemical reactor diagnostics.

Electrochemistry↗

Altimetry data and the elastic stress tensor of subduction zones

The maximum shear stress (mss) field due to mass anomalies is estimated in the Apennines, the Kermadec-Tonga Trench, and the Rio Grande Rift areas and the results for each area are compared to observed seismicity. A maximum mss of 420 bar was calculated in the Kermadec-Tonga Trench region at a depth of 28 km. Two additional zones with more than 300 bar mss were also observed in the Kermadec-Tonga Trench study. Comparison of the calculated mss field with the observed seismicity in the Kermadec-Tonga showed two zones of well correlated activity. The Rio Grande Rift results showed a maximum mss of 700 bar occurring east of the rift and at a depth of 6 km. Recorded seismicity in the region was primarily constrained to a depth of approximately 5 km, correlating well to the results of the stress calculations. Two areas of high mss are found in the Apennine region: 120 bar at a depth of 55 km, and 149 bar at the surface. Seismic events observed in the Apennine area compare favorably with the mss field calculated, exhibiting two zones of activity. The case of loading by seamounts and icecaps are also simulated. Results for this study show that the mss reaches a maximum of about 1/3 that of the applied surface stress for both cases, and is located at a depth related to the diameter of the surface mass anomaly.

Caputo, Michele↗

Adsorption isotherm, kinetic modeling and mechanism of tetracycline on Pinus taeda-derived activated biochar

The objective of this study was to evaluate the adsorption of tetracycline (TC) on the Pinus taeda-derived activated biochar (BC). Here, after NaOH activation, the well-developed porous surface structure was observed with a significantly increase in surface area (959.9 m 2 /g). The kinetic and isotherm studies indicated that hydrogen bonding and π-π interaction on the heterogeneous surface would be the possible mechanisms, while intra-particle diffusion was considered as the major limitation for the adsorption of TC on the activated BC. The maximum adsorption capacity of the activated BC (274.8 mg TC/g BC) was higher than those of various activated BCs from the previous studies while it was similar to those of commercial activated carbons. It indicated that the activated BC had the high potential for TC removal in water.

59 BASIC BIOLOGICAL SCIENCES↗

Enhanced photocatalytic performance of g-C{sub 3}N{sub 4} with BiOCl quantum dots modification

Highlights: • Novel BiOCl quantum dots modified g-C{sub 3}N{sub 4} photocatalyst was synthesized. • BiOCl-g-C{sub 3}N{sub 4} showed much higher photocatalytic activity than pure g-C{sub 3}N{sub 4} and BiOCl. • High separation efficiency of photoinduced carriers results in the enhanced performance. - Abstract: Novel BiOCl quantum dots modified g-C{sub 3}N{sub 4} photocatalyst was synthesized by a one-step chemical bath method at low temperature. The photocatalyst was characterized using X-ray diffraction, high-resolution transmission microscopy UV–visible light diffusion reflectance spectrometry, and photoluminescence spectroscopy. The results indicated that BiOCl quantum dots were dispersed on g-C{sub 3}N{sub 4} to form heterojunction structures with high specific surface area. BiOCl-g-C{sub 3}N{sub 4} showed much higher photocatalytic activity than pure g-C{sub 3}N{sub 4} and BiOCl for rhodamine B degradation. The enhanced performance was induced by the high separation efficiency of photoinduced carriers.

36 MATERIALS SCIENCE↗

Specialized activities and expression differences for Clostridium thermocellum biofilm and planktonic cells

Clostridium thermocellum forms biofilms adherent to lignocellulosic feedstock in a typical continuous cell-monolayer to efficiently break down and uptake cellulose hydrolysates. The sessile cells of biofilms may revert to non-adherent planktonic cells through generation of offspring cells or microenvironment constraints such as limited surface area. These interdependent cell populations co-exist and have different contributions to culture activity and growth. Here, we developed a novel bioreactor design to rapidly harvest sessile and planktonic cell populations for omics studies. In RNA-seq analyses, within 3299 protein coding genes, 59% (or 1958 genes) were differentially expressed with a minimum two-fold change between the two cell populations isolated simultaneously at high culture activity. Furthermore, sessile cells had definitive greater expression of genes involved in catabolism of carbohydrates by glycolysis and pyruvate fermentation, ATP generation by proton gradient, the anabolism of proteins and lipids and cellular functions critical for cell division; planktonic cells had notably higher gene expression for flagellar motility and chemotaxis, cellulosomal cellulases and anchoring scaffoldins, and a range of stress induced homeostasis mechanisms such as oxidative stress protection by antioxidants and flavoprotein co-factors, methionine repair, Fe-S cluster assembly and repair in redox proteins, cell growth control through tRNA thiolation, recovery of damaged DNA by nucleotide excision repair and removal of terminal proteins by proteases. Our knowledge of these cellular adaptations will aid the engineering of industrially relevant strains for consolidated bioprocessing of solid lignocellulosic biomass

59 BASIC BIOLOGICAL SCIENCES↗

Carbon-Nanotube-Based Electrodes for Biomedical Applications

A nanotube array based on vertically aligned nanotubes or carbon nanofibers has been invented for use in localized electrical stimulation and recording of electrical responses in selected regions of an animal body, especially including the brain. There are numerous established, emerging, and potential applications for localized electrical stimulation and/or recording, including treatment of Parkinson s disease, Tourette s syndrome, and chronic pain, and research on electrochemical effects involved in neurotransmission. Carbon-nanotube-based electrodes offer potential advantages over metal macroelectrodes (having diameters of the order of a millimeter) and microelectrodes (having various diameters ranging down to tens of microns) heretofore used in such applications. These advantages include the following: a) Stimuli and responses could be localized at finer scales of spatial and temporal resolution, which is at subcellular level, with fewer disturbances to, and less interference from, adjacent regions. b) There would be less risk of hemorrhage on implantation because nano-electrode-based probe tips could be configured to be less traumatic. c) Being more biocompatible than are metal electrodes, carbon-nanotube-based electrodes and arrays would be more suitable for long-term or permanent implantation. d) Unlike macro- and microelectrodes, a nano-electrode could penetrate a cell membrane with minimal disruption. Thus, for example, a nanoelectrode could be used to generate an action potential inside a neuron or in proximity of an active neuron zone. Such stimulation may be much more effective than is extra- or intracellular stimulation via a macro- or microelectrode. e) The large surface area of an array at a micron-scale footprint of non-insulated nanoelectrodes coated with a suitable electrochemically active material containing redox ingredients would make it possible to obtain a pseudocapacitance large enough to dissipate a relatively large amount of electric charge, so that a large stimulation current could be applied at a micron-scale region without exhausting the redox ingredients. f) Carbon nanotube array is more compatible with the three-dimensional network of tissues. Particularly, a better electrical-neural interface can be formed. g) A carbon nanotube array inlaid in insulating materials with only the ends exposed is an extremely sensitive electro-analysis tool that can measure the local neurotransmitter signal at extremely high sensitivity and temporal resolution.

Li, Jun↗

Design and synthesis of highly active MoVTeNb-oxides for ethane oxidative dehydrogenation

Ethane oxidative dehydrogenation (ODH) is an alternative route for ethene production. Crystalline M1 phase of Mo-V mixed metal oxide is an excellent catalyst for this reaction. Here we show a hydrothermal synthesis method that generates M1 phases with high surface areas starting from poorly soluble metal oxides. Use of organic additives allows control of the concentration of metals in aqueous suspension. Reactions leading to crystalline M1 take place at 190 °C, i.e., approximately 400 °C lower than under current synthesis conditions. The evolution of solvated polyoxometalate ions and crystalline phases in the solid is monitored by spectroscopies. Catalysts prepared by this route show higher ODH activity compared to conventionally prepared catalysts. The higher activity is due not only to the high specific surface area but also to the corrugated lateral termination of the M1 crystals, as seen by atomic resolution electron microscopy, exposing a high concentration of catalytically active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic flux transport and the sunspot-cycle evolution of coronal holes and their wind streams

The relationships between magnetic flux transport from active regions and the formation and evolution of coronal holes are examined through numerical simulations. The model utilized is based on the assumption that coronal holes represent open field regions, and that the solar-wind speed at 1 AU is universely correlated with the divergence rate of the coronal field. The evolution of coronal holes and wind streams during 1980 - 1990 is discussed, along with flux transport and the evolution of open field regions, and focus is placed on declining, rising, and maximum phases. It is concluded that supergranular diffusion spreads active region flux over the solar surface and wipes out pockets of mixed polarity, thus creating unipolar areas containing open field lines; differential rotation spreads flux in longitude and it combines with diffusion to create axisymmetric polar holes from the original active-region fields; and meridional flow accelerates the decay of low-latitude holes by carrying flux to midlatitudes.

Wang, Y.-M.↗

Preparation and photocatalytic property of porous α-Fe2O3 nanoflowers

Highlights: • Porous α-Fe{sub 2}O{sub 3} nanoflowers were successfully prepared by calcining Fe{sub 3}S{sub 4} precursor. • The crystal structures, pore sizes and surface areas could be tuned through changing heat-treating temperatures. • The highest MO photocatalytic degradation efficiency could be up to more than 99% within 40 min. - Abstract: Porous α-Fe{sub 2}O{sub 3} nanoflowers were successfully prepared by calcining Fe{sub 3}S{sub 4} precursor. The crystal structures, pore sizes and surface areas of the samples could be tuned through changing heat-treating temperatures. The samples calcined at 600 °C exhibited the highest photocatalytic activity for the degradation of methyl orange (MO) under visible light irradiation, which showed a degradation efficiency of more than 99% within 40 min. The enhanced photocatalytic activity could be attributed to its porous hierarchical structure which could promote light absorption efficiency, largely decrease the distance of charge carriers moving to solution and enlarge its specific surface area. This simple and scalable strategy can also be extended to other porous metal oxide nanostructures for photocatalytic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Porous Enzymatic Membrane for Nanotextured Glucose Sweat Sensors with High Stability toward Reliable Noninvasive Health Monitoring

Development of reliable glucose sensors for noninvasive monitoring without interruption or limiting users' mobility is highly desirable, especially for diabetes diagnostics, which requires routine/long-term monitoring. However, their applications are largely limited by the relatively poor stability. In this paper, a porous membrane is synthesized for effective enzyme immobilization and it is robustly anchored to the modified nanotextured electrode solid contacts, so as to realize glucose sensors with significantly enhanced sensing stability and mechanical robustness. To the best of our knowledge, this is the first report of utilizing such nanoporous membranes for electrochemical sensor applications, which eliminates enzyme escape and provides a sufficient surface area for molecular/ion diffusion and interactions, thus ensuring the sustainable catalytic activities of the sensors and generating reliable measureable signals during noninvasive monitoring. The as-assembled nanostructured glucose sensors demonstrate reliable long-term stable monitoring with a minimal response drift for up to 20 h, which delivers a remarkable enhancement. Moreover, they can be integrated into a microfluidic sensing patch for noninvasive sweat glucose monitoring. The as-synthesized nanostructured glucose sensors with remarkable stability can inspire developments of various enzymatic biosensors for reliable noninvasive composition analysis and their ultimate applications in predictive clinical diagnostics, personalized health-care monitoring, and chronic diseases management.

36 MATERIALS SCIENCE↗

Building Reconfigurable Devices Using Complex Liquid–Fluid Interfaces

Liquid-fluid interfaces provide a platform both for structuring liquids into complex shapes and assembling dimensionally confined, functional nanomaterials. Historically, attention in this area has focused on simple emulsions and foams, in which surface-active materials such as surfactants or colloids stabilize structures against coalescence and alter the mechanical properties of the interface. In recent decades, however, a growing body of work has begun to demonstrate the full potential of the assembly of nanomaterials at liquid-fluid interfaces to generate functionally advanced, biomimetic systems. In this work, a broad overview is given, from fundamentals to applications, of the use of liquid-fluid interfaces to generate complex, all-liquid devices with a myriad of potential applications.

36 MATERIALS SCIENCE↗

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-defined model system of battery materials. Here, we report the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. Finally, the intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.

36 MATERIALS SCIENCE↗

Highly Efficient and Uniform 1 cm 2 Perovskite Solar Cells with an Electrochemically Deposited NiO x Hole-Extraction Layer

Here, given that the highest certified conversion efficiency of the organic-inorganic perovskite solar cell (PSC) already exceeds 22%, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large-area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large-area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiO x layer prepared by electrochemical deposition is reported as an efficient hole-extraction layer of a p-i-n-type planar PSC with a large active area of >1 cm 2 . It is demonstrated that the increased surface roughness of the NiO x layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiO x , and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiO x layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large-area PSCs. As a result, the p-i-n-type planar PSC with an area of 1.084 cm 2 exhibits a stable conversion efficiency of 17.0% (19.2% for 0.1 cm 2 ) without showing hysteresis effects.

14 SOLAR ENERGY↗

Comparative Study of Flash and Acid Hydrolysis of Microalgae (Scenedesmus sp.) for the Recovery of Biochemicals and Production of Porous Biocarbon Nanosheets

An integrated biorefinery concept is a novel and economical process intensification methodology for efficient utilization of biomass components. In this research, microalgae (Scenedesmus sp.) slurry with biomass concentration of 8.5 wt.% was parallelly fractionated using two techniques: 'flash hydrolysis (FH)' and 'acid hydrolysis (AH)'. FH was performed at 240 degrees C with a residence time of 10 +/- 2 s in a continuous flow reactor, whereas AH was performed at 155 degrees C and reaction time of 15 min in a batch reactor. About 63% of microalgal biomass was solubilized in liquid hydrolysate through both FH and AH. However, AH had an advantage over FH in recovering microalgae proteins and carbohydrates. FAME recovery through solvent extraction from FH and AH derived wet solids (insoluble microalgae) was 40 and 63%, respectively. Finally, the FH- and AH-derived post extraction solid residue was thermally activated using K2CO3 to produce highly microporous biocarbon nanosheets with BET surface areas of 712 and 1289 m2 g-1, respectively. Overall, an integrated process was developed using two potential hydrolysis techniques to maximize utilization of microalgae components.

BASIC BIOLOGICAL SCIENCES,BIOMASS FUELS↗

Fischer-Tropsch synthesis: Direct cobalt nitrate reduction of promoted Co/Al 2 O 3 catalysts

Direct reduction of cobalt nitrate versus conventional calcination/reduction treatment was conducted using alumina with identical methodology as previously applied to SiO 2 and TiO 2 . Similar BET surface areas, pore volumes and pore size distributions were obtained for the activated calcined and uncalcined catalysts indicating no significant difference on morphological properties. However, the reducibility slightly increases and Co crystallite size is smaller for activated uncalcined samples. Reduction phenomena were analyzed by TPR-MS and TPR-EXAFS/XANES. Combining these techniques allows an explanation of the complex phenomena occurring during the direct reduction of cobalt nitrate, as both nitrate decomposition and cobalt oxide reduction are involved. Cobalt nitrate species are converted to CoO x intermediates. These species are oxidized by NO X (from nitrate decomposition) to Co 3 O 4 spinel, which is converted to CoO prior to Co 0 formation. Noble metals (Pt, Re, Ru and Ag) improve cobalt oxide reducibility, especially for the final reduction step (i.e., CoO to Co 0 ). The effect of direct nitrate reduction on FT activity was investigated using a 1 L CSTR. Activated unpromoted and Pt-promoted uncalcined catalysts achieved higher initial and steady-state CO conversions in comparison to the corresponding calcined catalysts. The best performance was achieved with direct reduction of uncalcined 0.5%Pt-25%Co/Al 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells

Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO 2 ) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO 2 -ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OH ad provided by CeO 2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m 2 g -1 ), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol -1 ) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO 2 -ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power density of 91 mW cm -2 . Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO 2 ) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm -2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH 2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.

25 ENERGY STORAGE↗