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At least 1,477 records · Page 82
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Single-Step Fabrication of Au-Fe-BaTiO3 Nanocomposite Thin Films Embedded with Non-Equilibrium Au-Fe Alloyed Nanostructures

Nanocomposite thin film materials present great opportunities in coupling materials and functionalities in unique nanostructures including nanoparticles-in-matrix, vertically aligned nanocomposites (VANs), and nanolayers. Interestingly the nanocomposites processed through a non-equilibrium processing method, e.g., pulsed laser deposition (PLD), often possess unique metastable phases and microstructures that could not achieve using equilibrium techniques, and thus lead to novel physical properties. In this work, a unique three-phase system composed of BaTiO3 (BTO), with two immiscible metals, Au and Fe, is demonstrated. By adjusting the deposition laser frequency from 2 Hz to 10 Hz, the phase and morphology of Au and Fe nanoparticles in BTO matrix vary from separated Au and Fe nanoparticles to well-mixed Au-Fe alloy pillars. This is attributed to the non-equilibrium process of PLD and the limited diffusion under high laser frequency (e.g., 10 Hz). The magnetic and optical properties are effectively tuned based on the morphology variation. This work demonstrates the stabilization of non-equilibrium alloy structures in the VAN form and allows for the exploration of new non-equilibrium materials systems and their properties that could not be easily achieved through traditional equilibrium methods.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation

Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystal symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries and the approach for tailoring the functionalities of material based on insertion of ions in the lattice.

electron transfer↗
DOE OSTI2024

Tailoring Growth Interfaces of Virtual Substrates for Power Electronics

Power electronics materials are poised to play a critical role in fulfilling next generation energy needs, with up to 90% of future energy demand predicted to flow through power electronics at some point. AlxGa1-xN ranks high among candidate materials, having bipolar dopability, thermal and chemical stability and an ultra-wide bandgap. However, AlGaN growth is limited by a lack of lattice-matched substrates, ultimately stunting material quality at higher thicknesses needed for power electronics applications. Further, high power applications increasingly call for fully vertical device structures, necessitating a conductive substrate. Recently our group identified the (111) plane of TaC as a conductive surface lattice-matched to Al0.55Ga0.45N, taking inspiration from prior work of AlN and GaN binaries on carbide and boride substrates. In this talk we demonstrate the growth of (111)-oriented TaC by RF sputtering. We investigate the interface of TaC with sapphire and SiC substrates and identify means to suppress competing Ta2C nucleation in order to stabilize (111)-oriented TaC. Potential stacking sequences are identified with respect to crystal structure and observed twinning in the TaC films. We next assess structural changes and film recrystallization that results from face-to-face annealing of TaC thin films at high temperatures above 1500 degrees C. Changes to grain structure and domain size are assessed by x-ray diffraction and surface morphology is explored using atomic force microscopy. Figure 1 shows significant improvements to in- and out-of-plane strain following annealing along with the formation of terraced step edges at the film surface. Strain as a function of material composition and thickness is considered, as this may play a major role in future nucleation of AlGaN layers. (1) R. J. in a face-to-face configuration, as illustrated in the schematic at left. Kaplar et al 2017, ECS J. Solid State Sci. Technol. 6 Q3061; (2) D. M. Roberts et al 2022, https://arxiv.org/abs/2208.11769; (3) T. Aizawa et al 2008, J Crys Growth 310, 1 22; (4) R. Liu et al 2002, Appl. Phys. Lett. 81, 3182-3184.

ENGINEERING↗
DOE OSTI2022

Descriptor Aided Bayesian Optimization for Many-Level Qualitative Variables With Materials Design Applications

Abstract Engineering design often involves qualitative and quantitative design variables, which requires systematic methods for the exploration of these mixed-variable design spaces. Expensive simulation techniques, such as those required to evaluate optimization objectives in materials design applications, constitute the main portion of the cost of the design process and underline the need for efficient search strategies—Bayesian optimization (BO) being one of the most widely adopted. Although recent developments in mixed-variable Bayesian optimization have shown promise, the effects of dimensionality of qualitative variables have not been well studied. High-dimensional qualitative variables, i.e., with many levels, impose a large design cost as they typically require a larger dataset to quantify the effect of each level on the optimization objective. We address this challenge by leveraging domain knowledge about underlying physical descriptors, which embody the physics of the underlying physical phenomena, to infer the effect of unobserved levels that have not been sampled yet. We show that physical descriptors can be intuitively embedded into the latent variable Gaussian process approach—a mixed-variable GP modeling technique—and used to selectively explore levels of qualitative variables in the Bayesian optimization framework. This physics-informed approach is particularly useful when one or more qualitative variables are high dimensional (many-level) and the modeling dataset is small, containing observations for only a subset of levels. Through a combination of mathematical test functions and materials design applications, our method is shown to be robust to certain types of incomplete domain knowledge and significantly reduces the design cost for problems with high-dimensional qualitative variables.

Engineering↗
DOE OSTI2023

Tailoring Growth Interfaces of Virtual Substrates for Power Electronics

Power electronics materials are poised to play a critical role in fulfilling next generation energy needs, with up to 90% of future energy demand predicted to flow through power electronics at some point.[1] Among a number of candidate materials, AlxGa1-xN is the strongest, having bipolar dopability, thermal and chemical stability, an ultra-wide bandgap, and demonstrated experimental feasibility. However, AlGaN growth is limited by a lack of lattice-matched substrates, ultimately stunting material quality at higher thicknesses needed for power electronics applications. Further, high power applications increasingly call for fully vertical device structures, necessitating a conductive substrate. [1] Recently our group identified the (111) plane of TaC as a conductive surface lattice-matched to Al0.55Ga0.45N, taking inspiration from prior work of AlN and GaN binaries on carbide and boride substrates. [2,3,4] In this talk we demonstrate the growth of (111)-oriented TaC by RF sputtering. We investigate the interface of TaC with sapphire and SiC substrates and identify means to suppress competing Ta2C nucleation in order to stabilize (111)-oriented TaC. Potential stacking sequences are identified with respect to crystal structure and observed twinning in the TaC films. We next assess structural changes and film recrystallization that results from face-to-face annealing of TaC thin films at high temperatures above 1500 degrees Celsius. Changes to grain structure and domain size are assessed by x-ray diffraction and surface morphology is explored using atomic force microscopy. Figure 1 shows significant improvements to in- and out-of-plane strain following annealing along with the formation of terraced step edges at the film surface. Strain as a function of material composition and thickness is considered, as this may play a major role in future nucleation of AlGaN layers.

CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SU↗
DOE OSTI2022

Low temperature CVD growth of WSe 2 enabled by moisture-assisted defects in the precursor powder

Two-dimensional transition metal dichalcogenides (TMDs) have been proposed for a wide variety of applications, such as neuromorphic computing, flexible field effect transistors, photonics, and solar cells, among others. However, for most of these applications to be feasible, it is necessary to integrate these materials with the current existing silicon technology. Although chemical vapor deposition is a promising method for the growth of high-quality and large-area TMD crystals, the high temperatures necessary for the growth make this technique incompatible with the processes used in the semiconductor industry. Herein, we demonstrate the possibility of low-temperature growth of TMDs, using tungsten selenide (WSe 2 ) as a model, by simply using moisture-assisted defective tungsten oxide (WO 3 ) precursor powders during the growth of these materials. Density functional theory calculations reveal the mechanism by which moisture promotes the defect formation on the precursor crystal structure and how it dictates the reduction of the temperature of the growth. The results were compared with the standard growth at high temperatures and with a precursor mixture with alkali salts to show the high quality of the WSe 2 grown at temperatures as low as 550 °C. To conclude, the work improves the understanding of nucleation and growth mechanisms of WSe 2 at low temperatures and provides a useful strategy for the growth of TMDs at temperatures required for the back-end-of-line compatibility with current silicon technology.

2D materials↗
DOE OSTI2023

Tracking of Marangoni driven motion during laser powder bed fusion

Laser Powder Bed Fusion (LPBF) can be used to create Functionally Graded Materials (FGMs) by selectively distributing property augmenting particles throughout the build matrix. With this method parts can be created with nonhomogeneous properties tuned to spatially varied, pre-determined design constraints. To unlock this capability, the fluid motion that occurs in the molten liquid phase must be thoroughly understood. More importantly, the actual tracking of motion during the LPBF process is needed. Further, a numerical model of heat transfer and fluid flow in LPBF process was created. Using results from the model the motion of particles starting at many different locations was tracked. The average change in position for these particles based on starting location was calculated. The effects of non-dimensional parameters on melt pool size were examined. These results were validated experimentally and compared to what is available in the literature.

42 ENGINEERING↗
DOE OSTI2016

Density functional theory for d- and f-electron materials and compounds

Here, the fundamental requirements for a computationally tractable Density Functional Theory-based method for relativistic f- and (nonrelativistic) d-electron materials and compounds are presented. The need for basing the Kohn–Sham equations on the Dirac equation is discussed. The full Dirac scheme needs exchange-correlation functionals in terms of four-currents, but ordinary functionals, using charge density and spin-magnetization, can be used in an approximate Dirac treatment. The construction of a functional that includes the additional confinement physics needed for these materials is illustrated using the subsystem-functional scheme. If future studies show that a full Dirac, four-current based, exchange-correlation functional is needed, the subsystem functional scheme is one of the few schemes that can still be used for constructing functional approximations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Synthesis of Mo 4 VAlC 4 MAX Phase and Two-Dimensional Mo 4 VC 4 MXene with Five Atomic Layers of Transition Metals

MXenes are a family of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides with a general formula of M n+1 X n T x , in which two, three, or four atomic layers of a transition metal (M: Ti, Nb, V, Cr, Mo, Ta, etc.) are interleaved with layers of C and/or N (shown as X), and T x represents surface termination groups such as –OH, =O, and –F. Here, we report the scalable synthesis and characterization of a MXene with five atomic layers of transition metals (Mo 4 VC 4 T x ), by synthesizing its Mo 4 VAlC 4 MAX phase precursor that contains no other MAX phase impurities. These phases display twinning at their central M layers which is not present in any other known MAX phases or MXenes. Transmission electron microscopy and X-ray diffraction were used to examine the structure of both phases. Energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy were used to study the composition of these materials. Density functional theory calculations indicate that other five transition metal-layer MAX phases (M' 4 M"AlC 4 ) may be possible, where M' and M" are two different transition metals. The predicted existence of additional Al-containing MAX phases suggests that more M 5 C 4 T x MXenes can be synthesized. Additionally, we characterized the optical, electronic, and thermal properties of Mo 4 VC 4 T x . Here, this study demonstrates the existence of an additional subfamily of M 5 X 4 T x MXenes as well as a twinned structure, allowing for a wider range of 2D structures and compositions for more control over properties, which could lead to many different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Exploiting pressure to induce a "guest-blocked" spin transition in a framework material

A new functionalized 1,2,4-trizole ligand 4-[(E)-2-(5-methyl-2-thienyl)vinyl]-1,2,4-triazole (thiome) was prepared to assess the structural and magnetic consequence of ligand steric bulk in the resultant framework material [FeIIPd(CN)4(thiome)2]·2(H2O) (A·2(H2O)). Structural studies reveal that the pore size is smaller than realted 2-D Hofmann-type materials and that the water molecules can be reversibly removed with retention of the porous host framework. Magnetic measurements show ‘on-off’ sensing to the presence of water. The hydrated phase is spin crossover (SCO) inactive whereas the dehydrated phase undergoes an abrupt and hysteretic one-step spin transition. Partial dehydration (A·n(H2O), 0 ≤ n ≤ 2) leads to systematically varying spin transition temperatures further demonstrating qualitative sensing. These studies suggest that the SCO properties are governed by internal lattice pressure effects. Variable pressure structure and magnetic studies on the hydrated phase, A·2(H2O), reveal that such internal guest pressure effects can be overcome with moderate external pressure application (0 – 0.68 GPa) resulting in a two-step spin transition at ambient temperatures at 0.68 GPa.

guest sensing↗
DOE OSTI2019

Assessment of the Viability of Scaled Annular Pellet Fabrication Technologies

The DOE-NE AFC program broadly supports the creation of novel fuel forms including intermetallics, composites, and dopants for high uranium density compounds. While data can be obtained for key performance indicators such as thermal expansion and oxidation resistance in steam, fuel qualification remains a time intensive process. As such, accelerated fuel qualification methods are a recent focus of the program. By first looking at systems with known historical irradiation testing information, like UO 2 , the method of accelerated burnup testing can be validated, followed by use on novel materials with less information available, like silicides and nitrides. The biggest time delay in doing irradiation testing is reaching a “high burnup” fuel, to effectively model how the fuel will behave when it has been fully used. Reaching this point conventionally could take upwards of 30 years. Accelerated burnup would be approaching the threshold of “high burnup”, something on the order or 50GWd/MTU, more quickly, which although achievable in test reactors requires a decade to achieve using current irradiation testing schemes. To achieve this faster rate, the fuel is likely going to be subject to thermal effects commiserate with the increased heat by more fission. In a normal fuel pellet, this increased temperature would operate less efficiently because the thermal diffusivity of the pellet only allows it to transfer heat so quickly, thus causing a high centerline temperature and noticeable stress along the diameter of the pellet. Solutions could include smaller pellets, which would have a greater surface area giving off heat relative to their volume, or “shaped” fuel designs modifying the thermal behavior. The concept that drives the annular pellet design is reduction of the thermal gradient caused from the high “centerline” temperature at the center of a normal pellet to its surface. By removing the center of the pellet, the new centerline will instead be closer to an edge (whether that be the inner or outer edge), allowing cooling to wick away more heat than the traditional design. In an ideal world, the center of the pellet could also have a heat wick running through it allowing heat to be transported away from throughout the pellet. This increase in heat removal would allow the pellet to be subjected to higher energy output, and thus accelerate the burn-up process. UO 2 has been the staple fuel form of nuclear energy for decades, and replacement of this functionally understood material can only be done with sufficient fuel qualification. Increasing the burnup allows us to characterize new fuels with limited to no operational experience behind them, including carbides, nitrides, and silicide’s. Production of the unique geometries detailed herein will allow us to cut qualification times from multi-decadal experiments into the sub-decadal range, vastly increasing the quantity and quality of information available.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films

Abstract Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO 2 ) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO 2 . It is found that UO 2+ x thin films are hypostoichiometric ( x <0) with in‐plane tensile strain, while they are hyperstoichiometric ( x >0) with in‐plane compressive strain. Different from strain engineering in non‐actinide oxide thin films, the epitaxial strain in UO 2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO 2+ x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A cost-effective all-in-one halide material for all-solid-state batteries

All-solid-state batteries require advanced cathode designs to realize their potential for high energy density and economic viability. Integrated all-in-one cathodes, which eliminate inactive conductive additives and heterogeneous interfaces, hold promise for substantial energy and stability gains but are hindered by materials lacking sufficient Li + /e − conductivity, mechanical robustness and structural stability. Here, in this work, we present Li 1.3 Fe 1.2 Cl 4 , a cost-effective halide material that overcomes these challenges. Leveraging reversible Fe 2+ /Fe 3+ redox and rapid Li + /e − transport within its framework, Li 1.3 Fe 1.2 Cl 4 achieves an electrode energy density of 529.3 Wh kg −1 versus Li + /Li. Critically, Li 1.3 Fe 1.2 Cl 4 shows unique dynamic properties during cycling, including reversible local Fe migration and a brittle-to-ductile transition that confers self-healing behaviour. This enables exceptional cycling stability, maintaining 90% capacity retention for 3,000 cycles at a rate of 5 C. Integration of Li 1.3 Fe 1.2 Cl 4 with a nickel-rich layered oxide further increases the energy density to 725.6 Wh kg −1 . By harnessing the advantageous dynamic mechanical and diffusion properties of all-in-one halides, this work establishes all-in-one halides as an avenue for energy-dense, durable cathodes in next-generation all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2010

Morphology and water resistance of mixed silane films of bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine

Functional organosilanes are powerful interface-active agents that find applications as adhesion promoters as well as optical, dielectric and protective coatings. Bis-silanes are of particular interest because they are highly crosslinked leading to very robust films. In almost all applications, the water resistance of the films is a critical performance measure. Here we use neutron reflectivity to address the effect of bridging group on the hydrothermal response of bis-silane films prepared using bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine. Neat and mixed films are examined as-prepared, after exposure to water vapor and then in the re-dried state. The bridging group is the key factor that controls the morphology and water resistance of silane films. Although bis-sulfur silane is not as condensed as bis-amino silane, bis-sulfur swells less in water because of the hydrophobic nature of bridging group. The reflectivity of bis-sulfur silane film is reversible after room-temperature water conditioning but not at 80 C, indicating chemical alternation of the film at 80 C. The water resistance of mixed silane is roughly that of both components weighted by their volume fraction. But based on the enhanced shrinkage that occurs following water-vapor conditioning of the mixed film, condensation is accelerated in the mixed silane. Regarding the precursor solution, bis-amino silane may act as a catalyst in the hydrolysis of bis-sulfur silane leading to more silanols in the solution and further condensation in the film. Variation in the structure normal to the substrate is also examined by swelling the film with d-nitrobenzene, a non-reacting swelling agent.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The 2022 magneto-optics roadmap

Abstract Magneto-optical (MO) effects, viz. magnetically induced changes in light intensity or polarization upon reflection from or transmission through a magnetic sample, were discovered over a century and a half ago. Initially they played a crucially relevant role in unveiling the fundamentals of electromagnetism and quantum mechanics. A more broad-based relevance and wide-spread use of MO methods, however, remained quite limited until the 1960s due to a lack of suitable, reliable and easy-to-operate light sources. The advent of Laser technology and the availability of other novel light sources led to an enormous expansion of MO measurement techniques and applications that continues to this day (see section 1). The here-assembled roadmap article is intended to provide a meaningful survey over many of the most relevant recent developments, advances, and emerging research directions in a rather condensed form, so that readers can easily access a significant overview about this very dynamic research field. While light source technology and other experimental developments were crucial in the establishment of today’s magneto-optics, progress also relies on an ever-increasing theoretical understanding of MO effects from a quantum mechanical perspective (see section 2), as well as using electromagnetic theory and modelling approaches (see section 3) to enable quantitatively reliable predictions for ever more complex materials, metamaterials, and device geometries. The latest advances in established MO methodologies and especially the utilization of the MO Kerr effect (MOKE) are presented in sections 4 (MOKE spectroscopy), 5 (higher order MOKE effects), 6 (MOKE microscopy), 8 (high sensitivity MOKE), 9 (generalized MO ellipsometry), and 20 (Cotton–Mouton effect in two-dimensional materials). In addition, MO effects are now being investigated and utilized in spectral ranges, to which they originally seemed completely foreign, as those of synchrotron radiation x-rays (see section 14 on three-dimensional magnetic characterization and section 16 on light beams carrying orbital angular momentum) and, very recently, the terahertz (THz) regime (see section 18 on THz MOKE and section 19 on THz ellipsometry for electron paramagnetic resonance detection). Magneto-optics also demonstrates its strength in a unique way when combined with femtosecond laser pulses (see section 10 on ultrafast MOKE and section 15 on magneto-optics using x-ray free electron lasers), facilitating the very active field of time-resolved MO spectroscopy that enables investigations of phenomena like spin relaxation of non-equilibrium photoexcited carriers, transient modifications of ferromagnetic order, and photo-induced dynamic phase transitions, to name a few. Recent progress in nanoscience and nanotechnology, which is intimately linked to the achieved impressive ability to reliably fabricate materials and functional structures at the nanoscale, now enables the exploitation of strongly enhanced MO effects induced by light–matter interaction at the nanoscale (see section 12 on magnetoplasmonics and section 13 on MO metasurfaces). MO effects are also at the very heart of powerful magnetic characterization techniques like Brillouin light scattering and time-resolved pump-probe measurements for the study of spin waves (see section 7), their interactions with acoustic waves (see section 11), and ultra-sensitive magnetic field sensing applications based on nitrogen-vacancy centres in diamond (see section 17). Despite our best attempt to represent the field of magneto-optics accurately and do justice to all its novel developments and its diversity, the research area is so extensive and active that there remains great latitude in deciding what to include in an article of this sort, which in turn means that some areas might not be adequately represented here. However, we feel that the 20 sections that form this 2022 magneto-optics roadmap article, each written by experts in the field and addressing a specific subject on only two pages, provide an accurate snapshot of where this research field stands today. Correspondingly, it should act as a valuable reference point and guideline for emerging research directions in modern magneto-optics, as well as illustrate the directions this research field might take in the foreseeable future.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Electrical conductivity of TaO x as function of composition and temperature

The ability to model the resistive switching devices depends on input material parameters and is particularly sensitive to values of electrical conductivity of the functional material as a function of composition and temperature. Here we report the results of conductivity measurements of TaO x with 0 AC ) changing from 0.34 eV at x=2.36 to 0.016 eV at x=1.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Covalent Surface Modification Effects on Single‐Walled Carbon Nanotubes for Targeted Sensing and Optical Imaging

Abstract Optical nanoscale technologies often implement covalent or noncovalent strategies for the modification of nanoparticles, whereby both functionalizations are leveraged for multimodal applications but can affect the intrinsic fluorescence of nanoparticles. Specifically, single‐walled carbon nanotubes (SWCNTs) can enable real‐time imaging and cellular delivery; however, the introduction of covalent SWCNT sidewall functionalizations often attenuates SWCNT fluorescence. Recent advances in SWCNT covalent functionalization chemistries preserve the SWCNT's pristine graphitic lattice and intrinsic fluorescence, and here, such covalently functionalized SWCNTs maintain intrinsic fluorescence‐based molecular recognition of neurotransmitter and protein analytes. The covalently modified SWCNT nanosensor preserves its fluorescence response towards its analyte for certain nanosensors, presumably dependent on the intermolecular interactions between SWCNTs or the steric hindrance introduced by the covalent functionalization that hinders noncovalent interactions with the SWCNT surface. These SWCNT nanosensors are further functionalized via their covalent handles with a targeting ligand, biotin, to self‐assemble on passivated microscopy slides, and these dual‐functionalized SWCNT materials are explored for future use in multiplexed sensing and imaging applications.

Chio, Linda↗
DOE OSTI2017

Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries

A critical bottleneck limiting the performance of rechargeable zinc-air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition-metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur-deficient cobalt oxysulfide single crystals and nitrogen-doped graphene nanomeshes (CoO 0.87 S 0.13 /GN). The defect chemistries of both oxygen-vacancy-rich, nonstoichiometric cobalt oxysulfides and edge-nitrogen-rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO 0.87 S 0.13 /GN exhibits strongly comparable catalytic activity to and much better stability than the best-known benchmark noble-metal catalysts. In application to quasi-solid-state zinc-air batteries, CoO 0.87 S 0.13 /GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge-charge voltage gap of 0.77 V at 20 mA cm(-2) under ambient conditions.

bifunctional electrocatalysts↗