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At least 1,423 records · Page 79

Solvent effects on the heterogeneous growth of TiO 2 nanostructure arrays by solvothermal synthesis

One-dimensional titanium dioxide (TiO 2 ) nanostructure arrays (nanoarrays) are important metal oxide nanomaterials that can be synthesized via facile solvothermal methods. The properties of the organic solvents can impose significant effects on the microstructures and properties of the final products. However, the discussions were limited to the homogeneously nucleated TiO 2 nanomaterials in free-standing powder form, while the solvent effects are less understood during the heterogeneous growth of TiO 2 nanoarrays on a substrate surface. In this work, six organic compounds, namely 2-butanone, n-decane, n-hexane, toluene, ethylene glycol and ethanol, were selected as the solvents for the solvothermal synthesis of TiO 2 nanoarrays on the cordierite monolithic substrates. Special attentions are paid to the morphology, crystallinity, specific surface area, and porosity of the samples. The heterogeneous growth of TiO 2 nanoarrays on substrate surfaces is found to favor the solvents with moderate dielectric constants, which can be partially dissolved in the aqueous solution and modulate the reaction rate during the solvothermal synthesis. Organic solvents with low dielectric constants may result in a complete separation between the precursors and aqueous solution, and therefore slow down the overall reaction, causing the insufficient growth of the nanoarrays. The TiO 2 nanoarrays are obtained with optimum morphology from the combination of 2-butanone and titanium (IV) butoxide as solvent and precusor, respectively, with a high specific surface area up to 56 m 2 /g including cordierite substrate given a micron thickness. When loaded with Pt catalyst, the TiO 2 nanoarray-based monolithic catalysts show excellent low-temperature catalytic activity and hydrothermal stability for the CO and hydrocarbon oxidation under the simulated exhausted conditions. This article shall shed light on a better understanding of the growth mechanism and rational design of TiO 2 nanoarrays for high-performance catalytic converters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phase-field modeling of the interactions between an edge dislocation and an array of obstacles

Obstacles, such as voids and precipitates, are prevalent in crystalline materials. They strengthen crystals by serving as barriers to dislocation glide. Here in this work, we develop a phase-field dislocation dynamics (PFDD) technique for investigating the interactions between dislocations and second-phase obstacles, which can be either voids or precipitates. The PFDD technique is constructed to account for elastic heterogeneity, elastic anisotropy, dissociation of the dislocation, and dislocation transmission across bicrystalline interfaces. Within the framework, we present a model for “pseudo-voids”, which are voids shearable by dislocations, in contrast to unphysical, unshearable voids in conventional phase-field dislocation formulations. We employ the PFDD technique to investigate the in-plane interactions between an edge dislocation and an array of nano-scale obstacles with different spacings. In this application, the interactions take place in glide planes of either a face-centered cubic (FCC) Cu or a body-centered cubic (BCC) Nb matrix, while the precipitates have a Cu 1-x Nb x composition, with x varying from 0.1 to 0.9. Our atomistic simulations find that the alloy precipitates can have an FCC, an amorphous, or a BCC phase, depending on the compositional ratio between Cu and Nb, i.e., value of x. Among all types of obstacles, the critical stresses for dislocation bypass are the highest for unshearable amorphous precipitates, followed by shearable crystalline precipitates, and then the pseudo-voids.

42 ENGINEERING↗

Optimal design of 3D borehole seismic arrays for microearthquake monitoring in anisotropic media during stimulations in the EGS collab project

Multiple U.S. national laboratories, universities and industrial collaborators are conducting collaborative research under the EGS Collab project supported by the U.S. Department of Energy, to understand the fracture creation and imaging during fracturing in enhanced geothermal systems. Microearthquake hypocenter locations and focal mechanisms are used to monitor hydraulic fracturing growth and characterization at the EGS Collab experimental site at the Sanford Underground Research Facility using seismic receivers in multiple monitoring wells. In this study, we develop a methodology for optimal design a 3D borehole seismic array for cost-effective seismic monitoring in anisotropic media using not only the relationship between receiver distributions and standard deviation errors of microearthquake hypocenter locations, but also that between receiver distributions and focal-mechanism inversion errors. Our results indicate that microearthquake hypocenter locations and focal mechanisms can be reasonably well reconstructed for the EGS Collab Experiment I using six monitoring wells, including four fracture-parallel monitoring wells and two orthogonal wells. Lastly, eight seismic receivers evenly distributed in four parallel monitoring wells or twelve receivers in all six monitoring wells are required for hypocenter location, and twelve receivers evenly distributed in six wells or sixteen receivers in four wells are needed for focal-mechanism inversion.

58 GEOSCIENCES↗

The STAG code: A fully relativistic super transition array calculation using Green’s functions

Calculating opacities for a wide range of plasma conditions (i.e. temperature, density, element) requires detailed knowledge of the plasma configuration space and electronic structure. For plasmas composed of heavier elements, relativistic effects are important in both the electronic structure and the details of opacity spectra. We extend our previously described superconfiguration and super transition array capabilities (Gill et al., 2023) to include a fully relativistic formalism. Further, the use of hybrid bound-continuum supershells in our superconfigurations demonstrates the importance of a consistent treatment of bound and continuum electrons in dense plasma opacities, and we expand the discussion of these consequences to include issues associated with equation of state and electron correlations between bound and continuum electrons.

74 ATOMIC AND MOLECULAR PHYSICS↗

A new approach to include electron interaction effects in super transition array opacity theory

A method is presented for the improved calculation of super-shell partition functions which include the repulsive electron–electron interaction energy terms in the Boltzmann factor. Heretofore these interaction terms were approximately treated via the use of Feynman–Jensen inequalities. Further, such investigations are of particular interest for the super-transition-array approach of hot-plasma radiative opacity.

74 ATOMIC AND MOLECULAR PHYSICS↗

Facile synthesis of Co(OH)2 nanoneedle arrays grown on stainless steel for industrial electrochemical oxygen evolution reaction

The electrochemical oxygen evolution reaction (OER) is a critical half-reaction in a variety of energy conversion and storage applications, however, OER suffers from sluggish kinetics due to the four proton-electron transfer processes. To remedy this, interfacial engineering proves an effective strategy to design high active OER catalysts. Herein, we report a facile synthesis of Co(OH)2 nanoneedle (Co-NN) arrays grown on stainless steel (SS) via a one-step hydrothermal reaction, and the resultant impressive OER performance. Particularly, the Co-NN/SS needs 267, 307, and 576 mV overpotentials to reach 10, 100, and 1000 mA cm−2 in 1 M KOH & room temperature, and the overpotentials drop to 199, 257, and 283 mV to achieve the same current densities in 30 wt% KOH & 80 °C. Additionally, an alkaline water electrolysis (AWE) cell coupled with Co-NN/SS anode and PtRu/NiMo cathode only requires 1.65 and 1.73 V iR-free cell voltage to reach 1.0 and 2.0 A cm−2, respectively. The sterling OER performance could be attributed to four possible reasons, the Fe in SS surface tailoring the electronic properties of Co(OH)2, the mixed metal oxides on SS surface accelerating surface reconstruction of Co(OH)2 nanoneedles into CoOOH active species, a Ni-rich surface layer formation cooperatively boosting the OER activity, and a local electric field effect concentrating reactants on the tip surface and accelerating the mass transfer. This work provides a facile approach for synthesizing highly efficient OER catalysts for industrial applications by interfacial engineering.

Lyu, Xiang [ORNL] (ORCID:0000000208673248)↗

Gap junctions fine-tune ganglion cell signals to equalize response kinetics within a given electrically coupled array

Retinal ganglion cells (RGCs) summate inputs and forward a spike train code to the brain in the form of either maintained spiking (sustained) or a quickly decaying brief spike burst (transient). We report diverse response transience values across the RGC population and, contrary to the conventional transient/sustained scheme, responses with intermediary characteristics are the most abundant. Pharmacological tests showed that besides GABAergic inhibition, gap junction (GJ)–mediated excitation also plays a pivotal role in shaping response transience and thus visual coding. More precisely GJs connecting RGCs to nearby amacrine and RGCs play a defining role in the process. These GJs equalize kinetic features, including the response transience of transient OFF alpha (tOFFα) RGCs across a coupled array. We propose that GJs in other coupled neuron ensembles in the brain are also critical in the harmonization of response kinetics to enhance the population code and suit a corresponding task.

59 BASIC BIOLOGICAL SCIENCES↗

Certified dual-corrected radiation patterns of phased antenna arrays by offline–online order reduction of finite-element models

This paper presents a fast numerical method for computing certified far-field patterns of phased antenna arrays over broad frequency bands as well as wide ranges of steering and look angles. The proposed scheme combines finite-element analysis, dual-corrected model-order reduction, and empirical interpolation. To assure the reliability of the results, improved a posteriori error bounds for the radiated power and directive gain are derived. Both the reduced-order model and the error-bounds algorithm feature offline–online decomposition. A real-world example is provided to demonstrate the efficiency and accuracy of the suggested approach.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Uniformly dispersed CdS nanoparticles sensitized TiO{sub 2} nanotube arrays with enhanced visible-light photocatalytic activity and stability

In this study, TiO{sub 2} nanotube arrays (TiO{sub 2}-NTs) with various intertube spaces were fabricated in the electrolyte with different water contents and the CdS nanoparticles (CdS NPs) were further deposited onto the TiO{sub 2}-NTs as a sensitizer via a sequential chemical bath deposition (S-CBD) method. The FE-SEM, TEM, XRD and XPS results demonstrated that the CdS NPs were uniformly deposited onto the surface of TiO{sub 2}-NTs. It was found that higher water content in electrolyte was in favor of large intertube space and pore size and the uniform deposition of CdS NPs. The photocatalytic degradation of methyl orange was tested with the as-prepared CdS/TiO{sub 2}-NTs under visible light (λ>400 nm). It was found that the photodegradation rate reached as high as 96.7% under visible irradiation for 180 min. In addition, a reasonable degradation rate of 75.8% was achieved even after 5 cycles, suggesting a good photocatalytic stability of the as-prepared CdS/TiO{sub 2}-NTs. - Graphical abstract: The whole sheet of CdS NPs sensitized TiO{sub 2}-NTs with the Ti subtract was used for degradation of methyl orange under visible light (λ>400 nm) on a XPA-7 photochemical reactor. - Highlights: • Intertube space, pore size were controlled by changing water content in electrolyte. • CdS nanoparticles were uniformly deposited onto the surface of TiO{sub 2} nanotubes. • The catalyst with Ti substrate used as a whole was very convenient for recycling. • Visible-light photocatalytic activity and stability were highly enhanced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

UV light-assisted fabrication of Cu{sub 0.91}In{sub 0.09}S microspheres sensitized TiO{sub 2} nanotube arrays and their photoelectrochemical properties

Highlights: • Cu{sub 0.91}In{sub 0.09}S microspheres were deposited on TiO{sub 2} NTs by a photodeposition method. • The average diameter of Cu{sub 0.91}In{sub 0.09}S microspheres is 600 nm. • The TiO{sub 2} NTs/CIS shows high photocurrents and visible photocatalytic activity. - Abstract: TiO{sub 2} nanotube arrays sensitized with Cu{sub 0.91}In{sub 0.09}S microspheres (TiO{sub 2} NTs/CIS) were successfully fabricated by a two-step process of anodization and followed by an in situ photodeposition method. The structural investigation by scanning electron microscopy and transmission electron microscopy indicated that the Cu{sub 0.91}In{sub 0.09}S microspheres with average diameter of 600 nm grew on the surface of the TiO{sub 2} nanotubes. The TiO{sub 2} NTs/CIS exhibited more excellent photoelectrochemical properties and photocatalytic activities than those of TiO{sub 2} NTs under visible light irradiation, and the corresponding electron transformation was proposed in detail.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Remarkably improved field emission of TiO{sub 2} nanotube arrays by annealing atmosphere engineering

Highlights: • TNAs were prepared by anodization and annealed in different atmospheres. • The crystal structure and electronic properties of the prepared TNAs were investigated. • The field emission of TNAs was highly dependent on annealing atmosphere. • A low turn-on of 2.44 V/μm was obtained for TNAs annealed in H{sub 2} atmosphere. - Abstract: Highly ordered TiO{sub 2} nanotube arrays (TNAs) were prepared by anodization, and followed by annealing in the atmospheres of Air, Vacuum, Ar, and H{sub 2}. The effect of annealing atmosphere on the crystal structure, composition, and electronic properties of TNAs were systematically investigated. Raman and EDS results indicated that the TNAs annealed in anaerobic atmospheres contained more oxygen vacancies, which result in the substantially improved electron transport properties and reduced work function. Moreover, it was found that the FE properties of TNAs were highly dependent on the annealing atmosphere. By engineering the annealing atmosphere, the turn-on field as low as 2.44 V/μm can be obtained from TNAs annealed in H{sub 2}, which was much lower than the value of 18.23 V/μm from the TNAs annealed in the commonly used atmosphere of Air. Our work suggests an instructive and attractive way to fabricate high performance TNAs field emitters.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Titania nanotube arrays surface-modified with ZnO for enhanced photocatalytic applications

Highlights: • Heterostructures of TNA/ZnO synthesised through potentiostatic anodisation followed by hydrothermal method. • Evaluation of morphological features of the heterostructure with hydrothermal processing time. • Correlation of photocatalytic activity of the hetrostructure with its morphology and surface texture. - Abstract: Well ordered titanium dioxide nanotube arrays (TNA) of average diameter 129 nm and wall thickness of 25 nm were fabricated through potentiostatic anodisation of titanium (Ti) metal substrates. Such TNA were subsequently surface-modified with various amounts of zinc oxide (ZnO) nanopowders using hydrothermal technique to obtain heterogeneous TNA/ZnO nanostructures. The crystalline phase and surface microstructure of the heterostructures were determined by X-ray diffraction, Raman spectroscopy and scanning electron microscopy respectively. The morphology of the heterostructures strongly depended on the hydrothermal conditions employed. The photocatalytic activity of the heterostructures have also been investigated and correlated with their surface morphology and texture.

36 MATERIALS SCIENCE↗

Wettability, structural and optical properties investigation of TiO{sub 2} nanotubular arrays

Graphical abstract: FESEM images of the TiO 2 nanotube layers formed at 0.5 wt% NH4F/ glycerol. - Highlights: • Structural property investigation of TiO{sub 2} nanotube. • Evaluation of wettability of TiO{sub 2} nanotube. • Study on optical properties of TiO{sub 2} nanotube. • The effect of anatase phase on optical and wettability properties of TiO{sub 2.} - Abstract: In this study, the effect of microstructural evolution of TiO{sub 2} nanotubular arrays on wettability and optical properties was investigated. Pure titanium was deposited on silica glass by PVD magnetron sputtering technique. The Ti coated substrates were anodized in an electrolyte containing NH{sub 4}F/glycerol. The structures of the ordered anodic TiO{sub 2} nanotubes (ATNs) as long as 175 nm were studied using field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD). The result shows a sharp peak in the optical absorbance spectra around the band gap energy, 3.49–3.42 eV for annealed and non-annealed respectively. The thermal process induced growth of the grain size, which influence on the density of particles and the index of refraction. Furthermore, the wettability tests' result displays that the contact angle of intact substrate (θ = 74.7°) was decreased to 31.4° and 17.4° after anodization for amorphous and heat treated (450 °C) ANTs coated substrate, respectively.

36 MATERIALS SCIENCE↗

Enhanced field emission properties of tilted graphene nanoribbons on aggregated TiO{sub 2} nanotube arrays

Highlights: • Graphene nanoribbons (GNBs) slanted on aggregate TiO{sub 2} nanotube (A-TNTs) as field-emitters. • Turn-on electric field and field enhancement factor β are dependent on the substrate morphology. • Various quantities of GNRs are deposited on top of A-TNTs (GNRs/A-TNTs) with different morphologies. • With an increase of GNBs compositions, the specimens' turn-on electric field is reduced to 2.8 V/μm. • The field enhancement factor increased rapidly to about 1964 with the addition of GNRs. - Abstract: Graphene nanoribbons (GNRs) slanted on aggregate TiO{sub 2} nanotube arrays (A-TNTs) with various compositions as field-emitters are reported. The morphology, crystalline structure, and composition of the as-obtained specimens were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and Raman spectrometry. The dependence of the turn-on electric field and the field enhancement factor β on substrate morphology was studied. An increase of GNRs reduces the specimens’ turn-on electric field to 2.8 V/μm and the field enhancement factor increased rapidly to about 1964 with the addition of GNRs. Results show a strong dependence of the field emission on GNR composition aligned with the gradient on the top of the A-TNT substrate. Enhanced FE properties of the modified TNTs can be mainly attributed to their improved electrical properties and rougher surface morphology.

36 MATERIALS SCIENCE↗

Fabrication of In2O3/TiO2 nanotube arrays hybrids with homogeneously developed nanostructure for photocatalytic degradation of Rhodamine B

Highlights: • A new class of plate-like In{sub 2}O{sub 3}/TNAs photocatalyst is successfully fabricated. • The obtained In{sub 2}O{sub 3}/TNAs hybrid presents a well-aligned nanotubular structure. • In{sub 2}O{sub 3} particles are dispersed homogeneously on TNAs without blocking the nozzles. • In{sub 2}O{sub 3}/TNAs hybrid shows a much enhanced Rhodamine B degradation efficiency. • In{sub 2}O{sub 3}/TNAs hybrid demonstrates an excellent recycling capability. - Abstract: To enhance the photocatalytic recycling capability of the TiO{sub 2}-based photocatalysts, a new kind of plate-like In{sub 2}O{sub 3}/TiO{sub 2} nanotube array (TNA) hybrids is fabricated herein by constructing TNAs via an anodization method followed by doping In{sub 2}O{sub 3} via a solvothermal method. The obtained In{sub 2}O{sub 3}/TNA hybrid demonstrates a well-aligned nanotubular structure with homogeneous dispersion of In{sub 2}O{sub 3} nanoparticles. It shows a much higher degradation rate of 77% after 2 h compared to TNA (37%). In addition, the plate-like feature endows the photocatalysts with an excellent recycling capability. These superior photocatalytic degradation performances can be ascribed to the following factors: (1) the enhanced light absorption ability and efficient separation of photoexcited electron-hole pairs derived from the formation of the heterostructure between the interface of TiO{sub 2} and In{sub 2}O{sub 3}; (2) the efficient transport of reactant molecules provided by the well-defined TNAs and the homogeneous distribution of the In{sub 2}O{sub 3} nanoparticles without blocking the nanotubes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Upconversion Er-doped TiO2 nanorod arrays for perovskite solar cells and the performance improvement

Highlights: • Er-doped TiO{sub 2} nanorod absorbs IR and converts into visible light. • The introduction of Er could make a positive shift in flat-band potential. • Er-doped TiO{sub 2} solar cells show a 20% increment in the current density. - Abstract: Upconversion erbium-doped rutile TiO{sub 2} nanorod arrays were synthesized by a facile process and applied in perovskite solar cells (PSCs). The structure was characterized by X-ray powder diffraction (XRD). Energy dispersive spectrometer (EDS) and Tauc plot indicated that Er was successfully introduced and changed TiO{sub 2} band gap from 3.00 eV to 3.07 eV. The incorporation of Er shifts the flat band potential positively and enhances the electron density. The Er-doped TiO{sub 2} nanorods have a broad absorption in the infrared light and up-convert it into visible light, which provides a possibility for PSCs to use NIR light for higher performance. A higher photocurrent density (J{sub sc}) of 22.97 mA/cm{sup 2} and a power conversion efficiency (PCE) of 10.6% were obtained, showing 20% and 16.5% increment in J{sub sc} and PCE, respectively, when compared with the un-doped device. The performance improvement was ascribed to the upconversion performance, enhanced electron-injection efficiency and reduced charge recombination.

14 SOLAR ENERGY↗

A new time calibration method for switched-capacitor-array-based waveform samplers

Here we have developed a new time calibration method for the DRS4 waveform sampler that enables us to precisely measure the non-uniform sampling interval inherent in the switched-capacitor cells of the DRS4. The method uses the proportionality between the differential amplitude and sampling interval of adjacent switched-capacitor cells responding to a sawtooth-shape pulse. In the experiment, a sawtooth-shape pulse with a 40 ns period generated by a Tektronix AWG7102 is fed to a DRS4 evaluation board for calibrating the sampling intervals of all 1024 cells individually. The electronic time resolution of the DRS4 evaluation board with the new time calibration is measured to be ~2.4 ps RMS by using two simultaneous Gaussian pulses with 2.35 ns full-width at half-maximum and applying a Gaussian fit. The time resolution dependencies on the time difference with the new time calibration are measured and compared to results obtained by another method. Ultimately, the new method could be applicable for other switched-capacitor-array technology-based waveform samplers for precise time calibration.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The performance of the γ-ray tracking array GRETINA for γ-ray spectroscopy with fast beams of rare isotopes

The gamma-ray tracking array GRETINA was coupled to the S800 magnetic spectrometer for spectroscopy with fast beams of rare isotopes at the National Superconducting Cyclotron Laboratory on the campus of Michigan State University. We describe the technical details of this powerful setup and report on GRETINA's performance achieved with source and in-beam measurements. The gamma-ray multiplicity encountered in experiments with fast beams is usually low, allowing for a simplified and efficient treatment of the data in the gamma-ray analysis in terms of Doppler reconstruction and spectral quality. Finally, the results reported in this work were obtained from GRETINA consisting of 8 detector modules hosting four high-purity germanium crystals each. Currently, GRETINA consists of 10 detector modules.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗