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At least 703 records · Page 39

Far-forward neutrinos at the Large Hadron Collider

We present a new calculation of the energy distribution of high-energy neutrinos from the decay of charm and bottom hadrons produced at the Large Hadron Collider (LHC). In the kinematical region of very forward rapidities, heavy-flavor production and decay is a source of tau neutrinos that leads to thousands of charged-current tau neutrino events in a 1 m long, 1 m radius lead neutrino detector at a distance of 480 m from the interaction region. In our computation, next-to-leading order QCD radiative corrections are accounted for in the production cross-sections. Non-perturbative intrinsic-k T effects are approximated by a simple phenomenological model introducing a Gaussian k T -smearing of the parton distribution functions, which might also mimic perturbative effects due to multiple initial-state soft-gluon emissions. The transition from partonic to hadronic states is described by phenomenological fragmentation functions. To study the effect of various input parameters, theoretical predictions for $D^{±}_s$ production are compared with LHCb data on double-differential cross-sections in transverse momentum and rapidity. The uncertainties related to the choice of the input parameter values, ultimately affecting the predictions of the tau neutrino event distributions, are discussed. We consider a 3+1 neutrino mixing scenario to illustrate the potential for a neutrino experiment to constrain the 3+1 parameter space using tau neutrinos and antineutrinos. We find large theoretical uncertainties in the predictions of the neutrino fluxes in the far-forward region. Untangling the effects of tau neutrino oscillations into sterile neutrinos and distinguishing a 3+1 scenario from the standard scenario with three active neutrino flavours, will be challenging due to the large theoretical uncertainties from QCD.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Payload Utilization in NASA's Space Launch System

A revitalized National Space Council has directed NASA to return to the moon, with a series of preparatory missions paving the way for eventual human exploration. NASA's new deep space exploration system -- the heavy-lift Space Launch System (SLS), the Orion crew spacecraft and revitalized launch facilities at Kennedy Space Center -- will enable NASA and its commercial and international partners to meet these goals for human deep space exploration. SLS will be the most capable launch vehicle for these efforts, with an initial Block 1 capability of at least 26 metric tons (t) to trans-lunar injection (TLI). A more powerful Block 1B, available in crew and cargo configurations, with have the power to loft more than 37 t to TLI; the ultimate Block 2 variant will lift more than 45 t to TLI. For payload utilization, the Block 1 vehicle will carry 13 6U CubeSats as secondary payloads while the Block 1B crew vehicle will provide as much volume as the space shuttle payload bay in a Universal Stage Adapter (USA). Block 1B cargo vehicles will offer 8.4 m fairings in 19.1 m and 27.4 m lengths, with enough volume to accommodate habitat modules and landers. For missions beyond the Earth-moon system, SLS offers greater characteristic energy (C3), enabling faster transit or heavier payloads to the outer planets. The first mission of SLS and Orion, launching no earlier than December 2019, will send Orion into lunar distant retrograde orbit (DRO) on an approximately 25-day shakedown cruise known as Exploration Mission-1 (EM-1), enabling NASA to verify and validate new systems before sending astronauts to deep space on the next exploration mission. The SLS program and its prime contractors have made significant progress toward first launch, with several major components of the vehicle completed and delivered to the Exploration Ground Systems (EGS) Program at Kennedy Space Center. Major forward work includes integrating tanks, engines and other major sections into the EM-1 core stage at Michoud Assembly Facility and then shipping the entire core stage assembly to Stennis Space Center. There, it will be installed in the refurbished B-2 test stand for a series of integrated stage tests culminating in a green run hotfire test. The Program's Spacecraft Payload Integration and Evolution (SPIE) Office, responsible for the in-space stage, adapters and payload interfaces, has largely completed its effort on the Block 1 vehicle and is supporting manufacture of the first Block 1B vehicle. This paper will provide an overview of the Block 1 vehicle, its expected capabilities, secondary payload accommodations and manufacturing status, including structural testing and the challenges of developing a new launch vehicle. A lookahead to the Block 1B vehicle and the payload utilization opportunities it will provide in the 2020s will also be discussed, including the unique capabilities of the vehicle.

Creech, Stephen D.↗

Three-dimensional plasmoid-mediated reconnection and turbulence in Hall magnetohydrodynamics

Plasmoid instability accelerates reconnection in collisional plasmas by transforming a laminar reconnection layer into numerous plasmoids connected by secondary current sheets in two dimensions (2D) and by fostering self-generated turbulent reconnection in three dimensions (3D). In large-scale astrophysical and space systems, plasmoid instability likely initiates in the collisional regime but may transition into the collisionless regime as the fragmentation of the current sheet progresses toward kinetic scales. Hall magnetohydrodynamics (MHD) models are widely regarded as a simplified yet effective representation of the transition from collisional to collisionless reconnection. However, plasmoid instability in 2D Hall MHD simulations often leads to a single-X-line reconnection configuration, which significantly differs from fully kinetic particle-in-cell simulation results. This study shows that single-X-line reconnection is less likely to occur in 3D compared to 2D. Moreover, depending on the Lundquist number and the ratio between the system size and the kinetic scale, Hall MHD can also realize 3D self-generated turbulent reconnection. We analyze the features of the self-generated turbulent state, including the energy power spectra and the scale dependence of turbulent eddy anisotropy.

Physics↗

Simulations of Solar Jets Confined by Coronal Loops

Coronal jets are collimated, dynamic events that occur over a broad range of spatial scales in the solar corona. In the open magnetic field of coronal holes, jets form quasi-radial spires that can extend far out into the heliosphere, while in closed-field regions the jet outflows are confined to the corona. We explore the application of the embedded-bipole model to jets occurring in closed coronal loops. In this model, magnetic free energy is injected slowly by footpoint motions that introduce twist within the closed dome of the jet source region, and is released rapidly by the onset of an ideal kink-like instability. Two length scales characterize the system: the width (N) of the jet source region and the footpoint separation (L) of the coronal loop that envelops the jet source. We find that both the conditions for initiation and the subsequent dynamics are highly sensitive to the ratio L/N. The longest-lasting and most energetic jets occur along long coronal loops with large L/N ratios, and share many of the features of open-field jets, while smaller L/N ratios produce shorter-duration, less energetic jets that are affected by reflections from the far-loop footpoint. We quantify the transition between these behaviors and show that our model replicates key qualitative and quantitative aspects of both quiet Sun and active-region loop jets. We also find that there connection between the closed dome and surrounding coronal loop is very extensive: the cumulative reconnected flux at least matches the total flux beneath the dome for small L/N, and is more than double that value for large L/N.

Wyper, P. F.↗

A Circular Economy for Lithium-Ion Batteries Used in Mobile and Stationary Energy Storage: Drivers, Barriers, Enablers, and U.S. Policy Considerations

As large-format battery energy storage (BES) capacity increases in the United States, so will the volume of spent lithium-ion batteries (LiBs) (Bade 2019). Estimates based on a 10-year lifetime assumption found that the volume of LiBs that have reached the end of their utility for electric vehicle (EV) applications could total two million units (four million metric tons) annually by 2040 in the United States (Richa et al. 2014; Ai and Borucki 2018). Although there is currently no publicly available decommissioning or end-of-life (EoL) projection for stationary BES systems, the U.S. energy storage market is expected to grow from an annual deployment of 523 megawatts in 2013 to 7.3 gigawatts in 2025 (Wood MacKenzie and ESA 2020; Wesoff 2020). Despite potential secondary market opportunities and the potential benefits associated with the reuse/recovery of LiB material, anecdotal evidence suggests that in the United States most decommissioned LiBs from EVs are landfilled or otherwise disposed of (Steward et al. 2019; Salim et al. 2019; CPUC 2019; DTSC 2019d; NREL 2019b; Jacoby 2019; DOE 2019). The reuse of large-format LiBs is not at commercial scale and to date consists of only a handful of U.S.-led pilot projects. Similarly, less than 5% of LiBs from EVs are sent to recycling facilities in the United States (Steward et al. 2019; Jacoby 2019; America Made 2019; Patel 2017). As awareness of current practices grows, and the demand for critical LiB materials increases, U.S. industry stakeholders, regulators, and policymakers are starting to (1) consider solutions to drive and enable environmentally sustainable materials management decisions and behaviors and (2) identify barriers to a circular economy for LiBs (Figure 1). Circular economy principles (Figure 1) attempt to transition from a “take-make-consume-dispose” linear economic system to a circular system that allows for the long life, high performance, and the reuse/recovery of products and materials (Ellen MacArthur Foundation 2016). We begin this report by summarizing drivers, barriers, and enablers to a circular economy for LiBs used in mobile and stationary BES systems in the United States. We then report on our analysis of federal and state regulatory considerations that may impact the reuse/recovery and disposal of LiBs, and potential civil and criminal liabilities associated with noncompliance. We conclude by highlighting state policies and initiatives in the United States that expressly address reuse/recovery and disposal of large-format LiBs. Our results are based on legal and literature-based research and interviews with mobile and stationary BES industry stakeholders, regulators, and policymakers. While this report addresses stationary BES, as well as mobile BES, much of the information and experience with LiB decommissioning and EoL material management is derived from the increasing management of spent EV LiBs in the United States.

25 ENERGY STORAGE↗

Numerical simulation of laminar-turbulent transition in a spatially-developing flat plate wake

Laminar-turbulent transition of an incompressible flat-plate wake is investigated by direct numerical integration of the Navier-Stokes equations. For the numerical integration, a combination of finite-difference and spectral methods along with an ADI/Crank-Nicolson/Adams-Bashforth time integration scheme is employed. Subject to 2D forcing, the wake exhibited a rapidly-growing fundamental disturbance that quickly saturated. This saturation was due partly to the stabilizing effect of the mean flow distortion. Downstream of the saturation point, disturbance energy was concentrated in the fundamental disturbance, the second harmonic, and the mean flow distortion component. At large amplitude levels, a Karman vortex street formed. Variations in the 2D forcing level did not alter the qualitative behavior of the disturbances. Simulations of 3D breakdown indicates that the presence of large-amplitude, 2D disturbances tends to initially suppress small-amplitude 3D disturbance growth. Following this initial suppression, a resumption of 3D growth is observed that may have been due to a secondary instability mechanism. For high levels of 3D disturbance energy, lambda-shaped vortical structures formed between adjacent Karman vortices.

Dratler, D. I.↗

Overview of NASA GRC Stirling Technology Development

The Stirling Radioisotope Generator (SRG) is currently being developed by Lockheed Martin Astronautics (LMA) under contract to the Depar1ment of Energy (DOE). The generator will be a high efficiency electric power source for NASA Space Science missions with the capability to operate in the vacuum of deep space or in an atmosphere such as on the surface of Mars. High system efficiency is obtained through the use of free-piston Stirling power conversion technology. Power output of the generator will be greater than 100 watts at the beginning of life with the decline in power being largely due to the decay of the plutonium heat source. In suppOl1 of the DOE SRG project, the NASA Glenn Research Center (GRC) has established a near-term technology effort to provide some of the critical data to ensure a successful transition to flight for what will be the first dynamic power system used in space. Initially, a limited number of technical areas were selected for the GRC effort, however this is now being expanded to more thoroughly cover a range of technical issues. The tasks include in-house testing of Stirling convertors and controllers, materials evaluation and heater head life assessment, structural dynamics, electromagnetic interference, organics evaluation, and reliability analysis. Most of these high-level tasks have several subtasks within. There is also an advanced technology effort that is complementary near-term technology effort. Many of the tests make use of the 55-We Technology Demonstration Convel10r (TDC). There have been multiple controller tests to support the LMA flight controller design effort. Preparation is continuing for a thermal/vacuum system demonstration. A pair of flight prototype TDC's have recently been placed on an extended test with unattended, continuous operation. Heater head life assessment efforts continue, with the material data being refined and the analysis moving toward the system perspective. Long-term magnet aging tests are continuing to characterize any possible aging in the strength or demagnetization resistance of the permanent magnets used in the linear alternator. In a parallel effort, higher performance magnets are also being evaluated. A reliability effort is being initiated that will help to guide the development activities with an increased focus on the necessary components and subsystems. Some other disciplines that are active in the GRC technology effort include structural dynamics, linear alternator analysis, EMI/EMC, controls, and mechanical design evaluation. This paper will provide an overview of some of the GRC technical efforts, including the current status, and a description of future efforts.

Schreiber, Jeffrey↗

Flame acceleration and transition to detonation in a pre-/main-chamber combustion system

Numerical simulations are performed to study the mechanism of deflagration to detonation transition (DDT) in a pre-/main-chamber combustion system with a stoichiometric ethylene–oxygen mixture. A Godunov algorithm, fifth-order in space, and third-order in time, is used to solve the fully compressible Navier–Stokes equations on a dynamically adapting mesh. A single-step, calibrated chemical diffusive model described by Arrhenius kinetics is used for energy release and conservation between the fuel and the product. The two-dimensional simulation shows that a laminar flame grows in the pre-chamber and then develops into a jet flame as it passes through the orifice. A strong shock forms immediately ahead of the flame, reflecting off the walls and interacting with the flame front. The shock–flame interactions are crucial for the development of flame instabilities, which trigger the subsequent flame development. The DDT arises due to a shock-focusing mechanism, where multiple shocks collide at the flame front. A chemical explosive mode analysis (CEMA) criterion is developed to study the DDT ignition mode. Preliminary one-dimensional computations for a laminar propagating flame, a fast flame deflagration, and a Chapman–Jouguet detonation are conducted to demonstrate the validity of CEMA on the chemical-diffusive model, as well as to determine the proper conditioning value for CEMA diagnostic. The two-dimensional analysis with CEMA indicates that the DDT initiated by the shock-focusing mechanism can form a strong thermal expansion region at the flame front that features large positive eigenvalues for the chemical explosive mode and dominance of the local autoignition mode. Thus, the CEMA criterion proposed in this study provides a robust diagnostic for identifying autoignition-supported DDT, of which the emergence of excessive local autoignition mode is found to be a precursor. The effect of grid size, initial temperature, and orifice size are then evaluated, and results show that although the close-chamber DDT is highly stochastic, the detonation initiation mechanism remains robust.

42 ENGINEERING↗

2014-2015 Puget Sound Regional Travel Study

The 2014-2015 Puget Sound Regional Travel Study collected information about household and individual travel patterns for residents throughout a four-county region in Washington State. Study results were used to update the region's travel and land-use models and to calibrate local traffic and travel models. The study also helped the Puget Sound Regional Council (PSRC) and its regional partners develop plans that accommodate the diverse travel needs and preferences of residents. The Resource Systems Group administered the study on behalf of PSRC. Global positioning system (GPS)-equipped smartphones were used to provide data pertaining to the daily travel of 547 individual participants. Because the region's university students may have been underrepresented in the initial 2014 household travel study, the PSRC added a college-population travel survey in fall 2014. In spring 2015, a second household data collection effort was conducted to increase the frequency of data collection and to collect GPS data as well as a sample of longitudinal data from households that completed the 2014 survey.

1Hz data↗

Baseline Testing of the EV Global E-Bike SX

The NASA John H. Glenn Research Center initiated baseline testing of the EV Global E-Bike SX as an update of the state of the art in hybrid electric bicycles. The E-bike is seen as a way to reduce pollution in urban areas, reduce fossil fuel consumption, and reduce operating costs for transportation systems. The work was done under the Hybrid Power Management (HPM) Program, which includes the Hybrid Electric Transit Bus (HETB). The SX is a high performance, state of the art, ground up, hybrid electric bicycle. Unique features of the SX's 36 V power system include the use of an efficient, 400 W, electric hub motor, and a seven-speed derailleur system that permits operation as fully electric, fully pedal, or a combination of the two. Other innovative features, such as regenerative braking through ultracapacitor energy storage, are planned. Regenerative braking recovers much of the kinetic energy of the vehicle during deceleration. The E-Bike is an inexpensive approach to advance the state of the art in hybrid technology in a practical application. The project transfers space technology to terrestrial use via nontraditional partners, and provides power system data valuable for future space applications. A description of the SX, the results of performance testing, and future vehicle development plans are given in this report. The report concludes that the SX provides excellent performance, and that the implementation of ultracapacitors in the power system can provide significant performance improvements.

Eichenherg, Dennis J.↗

1997 Broward Travel Characteristics Study

The Broward Travel Characteristics Study was initiated in February 1996 to identify localized socioeconomic and travel characteristics that could be used to improve the travel forecasting accuracy of the Florida Standard Urban Transportation Model System for Broward County. The survey recruited 2,625 households. Of these, 880 households completed the survey, indicating household demographic and socioeconomic characteristics (household verification survey). 33% of the households also completed a Direct Utility Assessment survey used to estimate the propensity for using transit. A total of 1,651 daily trips were extracted from the travel log survey over a 2-week period.

1Hz data↗

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of quantum dot-like emitters in programmable arrays of nanowrinkles of 1L-WSe2

When combined with nanostructured substrates, two-dimensional semiconductors can be engineered with strain to tailor light–matter interactions on the nanoscale. Recently, room-temperature nanoscale exciton localization with controllable wrinkling in 1L-WSe2 was achieved using arrays of gold nanocones. Here, the characterization of quantum dot-like states and single-photon emitters in the 1L-WSe2/nanocone system is reported. The nanocones induce a wide range of strains, and as a result, a diverse ensemble of narrowband, potential single-photon emitters is observed. The distribution of emitter energies reveals that most reside in two spectrally isolated bands, leaving a less populated intermediate band that is spectrally isolated from the ensembles. The spectral isolation is advantageous for high-purity quantum light emitters, and anti-bunched emission from one of these states is confirmed up to 25 K. Although the spatial distribution of strain is expected to influence the orientation of the transition dipoles of the emitters, multimodal emission polarization anisotropy and atomic force microscopy reveal that the macroscopic orientation of the wrinkles is not a good predictor of dipole orientation. Finally, the emission is found to change with thermal cycling from 4 to 290 K and back to 4 K, highlighting the need to control factors such as temperature-induced strain to enhance the robustness of this quantum emitter platform. The initial characterization here shows that controlled nanowrinkles of 1L-WSe2 generate quantum light in addition to uncovering potential challenges that need to be addressed for their adoption into quantum photonic technologies.

Physics↗

Analysis of Composite Panel-Stiffener Debonding Using a Shell/3D Modeling Technique

Interlaminar fracture mechanics has proven useful for characterizing the onset of delaminations in composites and has been used successfully primarily to investigate onset in fracture toughness specimens and laboratory size coupon type specimens. Future acceptance of the methodology by industry and certification authorities, however, requires the successful demonstration of the methodology on the structural level. For this purpose, a panel was selected that is reinforced with stiffeners. Shear loading causes the panel to buckle, and the resulting out-of-plane deformations initiate skin/stiffener separation at the location of an embedded defect. A small section of the stiffener foot, web and noodle as well as the panel skin in the vicinity of the delamination front were modeled with a local 3D solid model. Across the width of the stiffener foot, the mixedmode strain energy release rates were calculated using the virtual crack closure technique. A failure index was calculated by correlating the results with a mixed-mode failure criterion of the graphite/epoxy material. Computed failure indices were compared to corresponding results where the entire web was modeled with shell elements and only a small section of the stiffener foot and panel were modeled locally with solid elements. Including the stiffener web in the local 3D solid model increased the computed failure index. Further including the noodle and transition radius in the local 3D solid model changed the local distribution across the width. The magnitude of the failure index decreased with increasing transition radius and noodle area. For the transition radii modeled, the material properties used for the noodle area had a negligible effect on the results. The results of this study are intended to be used as a guide for conducting finite element and fracture mechanics analyses of delamination and debonding in complex structures such as integrally stiffened panels.

Krueger, Ronald↗

Novel solid-infused durable nonwetting surfaces for sustained condensation heat transfer enhancement

Here, in this article, we report novel nonwetting solid-infused surfaces that are easily fabricated using industrially widely adopted methods such as chemical etching or electrodeposition and exhibit sustained dropwise condensation performance durably than superhydrophobic and lubricant-infused surfaces. Solid-infused surfaces demonstrate fourfold larger condensation heat transfer coefficient and 25% better condensation effectiveness when compared to superhydrophobic surface and conventional filmwise condensation. Although the condensation heat transfer coefficient of lubricant-infused surface initially matches that of solid-infused surface, it is shown through durability studies that the wettability characteristic that underpins the performance of lubricant-infused surfaces degrades quickly with time as the lubricant depletes and lubricant-infused surface transitions to superhydrophobic surface. Solid-infused surface, on the other hand, retains its steadfast superior dropwise condensation effectiveness in the long run, overcoming the challenges of droplet pinning, surface inundation, cloaking, and lubricant depletion that eventually deteriorate condensation on conventional nonwetting superhydrophobic and lubricant-infused surfaces.

42 ENGINEERING↗

Sintered Cathodes for All-Solid-State Structural Lithium-Ion Batteries

All-solid-state structural lithium ion batteries serve as both structural load-bearing components and as electrical energy storage devices to achieve system level weight savings in aerospace and other transportation applications. This multifunctional design goal is critical for the realization of next generation hybrid or all-electric propulsion systems. Additionally, transitioning to solid state technology improves upon battery safety from previous volatile architectures. This research established baseline solid state processing conditions and performance benchmarks for intercalation-type layered oxide materials for multifunctional application. Under consideration were lithium cobalt oxide and lithium nickel manganese cobalt oxide. Pertinent characteristics such as electrical conductivity, strength, chemical stability, and microstructure were characterized for future application in all-solid-state structural battery cathodes. The study includes characterization by XRD, ICP, SEM, ring-on-ring mechanical testing, and electrical impedance spectroscopy to elucidate optimal processing parameters, material characteristics, and multifunctional performance benchmarks. These findings provide initial conditions for implementing existing cathode materials in load bearing applications.

Ceramics↗

Formation and surface melting of nanoparticle superlattices in a solution

The wisdom in the saying of “There are no two snowflakes alike” lies in the importance of history or kinetic pathways in the phase transitions of solids. Likewise, “artificial solids,” namely superlattices consisting of functional nanoparticles, have lattice size, surface morphology, crystallinity, symmetry, and structural reconfiguration (for example, transition into a disordered state) highly dependent on the kinetic pathways as the nanoparticles interact with each other in solution [1]. Great progresses have been made in understanding the formation pathways of superlattices using liquid-phase transmission electron microscopy (TEM) [2-4]. For example, by tracking single nanoparticle’s trajectories, especially aided by U-net neural network-based machine learning, previous studies mapped the fundamental nanoparticle interactions at nanometer resolution [5]. Nonclassical, two-step nucleation pathway has also been elucidated in the system of nanoprisms, by optimizing protocols such as loading nanoparticle suspensions over the supersaturation threshold and minimizing particle‒substrate interaction [2]. Surface morphologies or exposed facets of superlattices have been shown to follow the principles of Wulff construction rule, where the facet-dependent surface energy can be measured based on the capillary wave theory [4]. However, the reverse process of crystallization of superlattices, the conversion from crystalline to disordered state, has been much less explored. On one hand, the melting of nanoparticle superlattices can provide a preferred pathway to induce structural reorganization or shuffling of building blocks for them to transform into different types of crystal structures. On the other hand, understanding nanoscale superlattice melting and comparing such behaviors with the prevailing surface melting theories developed for atomic/molecular solids can provide a potent way to engineer phase transitions of supra- and hierarchical structures constructed from nanoscale entities (e.g., DNA-coated nanoparticles, proteins), for their applications in reprogrammable and switchable materials with multifunctional properties [6, 7]. The experimental challenges to observe melting of superlattices are twofold. Practically it is difficult to load the initial superlattice form, in an intact manner, into the highly confined liquid-phase TEM chamber for in-situ observation. Here, the triggering of melting also needs meticulous manipulation of nanoparticle concentration, interparticle interaction, and solution environment.

Kim, Ahyoung↗

Low temperature, ambient pressure electrochemical ammonia synthesis in alkaline media — Mechanistic studies and catalyst design. Final Report

Ammonia synthesis via the Haber-Bosch process is a pillar of modern agriculture, which converts the abundant but inert dinitrogen in the atmosphere to nitrogen-based fertilizers. Despite more than a century of optimization, the Haber-Bosch process remains energy intensive and reliant on fossil fuels and produces large amounts of CO 2 . Distributed and modular ammonia synthesis via the electrochemical nitrogen reduction reaction (ENRR) at or close to ambient conditions, powered by renewable electricity is an attractive alternative because it allows as needed production of ammonia, and in turn fertilizers. However, selective ENRR catalysts remain lacking. In this project, we systematically investigated two categories of catalytic materials, i.e., precious metals and transition metal nitrides, in the ENRR. Precious metals exhibit low activity and selectivity in the ENRR, which is in agreement with recent computational studies. Transition metal nitrides, especially VN, has been demonstrated as active and selective ENRR catalysts. We developed the first quantitative method to determine the amount of ammonia produced in the ENRR on N-containing containing catalysts in the membrane electrode assembly configuration. An initial ammonia production rate of 6.6 × 10 -10 mol s -1 mg -1 and a Faradaic efficiency of 6.0% at -0.1 V were reached on VN. After the initial deactivation, VN was shown to be stable in the ENRR for 116 hours with a steady state ammonia production rate of 1.1 × 10 -10 mol s -1 cm -2 . A vanadium oxynitride species was identified as the active phase in the ENRR via a combination of operando and ex situ characterization techniques. In addition, we established that the ENRR proceeded on transition metal nitrides via the Mars van Krevelen mechanism and determined the initial and steady state active site densities by developing a quantitative isotopic exchange method.

42 ENGINEERING↗