Machine-learning-assisted elucidation of ion transport mechanism in heterogeneous interphases formed at the electrolyte-electrode interfaces
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Energy - Storage↗
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Results for “Heterogeneity”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species
Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
Gao, Jiaxin↗
Formation of a Strong Heterogeneous Aluminum Lewis Acid on Silica
Abstract Al(OC(CF 3 ) 3 )(PhF) reacts with silanols present on partially dehydroxylated silica to form well‐defined ≡SiOAl(OC(CF 3 ) 3 ) 2 (O(Si≡) 2 ) ( 1 ). 27 Al NMR and DFT calculations with a small cluster model to approximate the silica surface show that the aluminum in 1 adopts a distorted trigonal bipyramidal coordination geometry by coordinating to a nearby siloxane bridge and a fluorine from the alkoxide. Fluoride ion affinity (FIA) calculations follow experimental trends and show that 1 is a stronger Lewis acid than B(C 6 F 5 ) 3 and Al(OC(CF 3 ) 3 )(PhF) but is weaker than Al(OC(CF 3 ) 3 ) and i Pr 3 Si + . Cp 2 Zr(CH 3 ) 2 reacts with 1 to form [Cp 2 ZrCH 3 ][≡SiOAl(OC(CF 3 ) 3 ) 2 (CH 3 )] ( 3 ) by methide abstraction. This reactivity pattern is similar to reactions of organometallics with the proposed strong Lewis acid sites present on Al 2 O 3 .
Samudrala, Kavyasripriya K.↗
Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO2 Reduction
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99 GENERAL AND MISCELLANEOUS↗
Reshaping the Cathodic Catalyst Layer for Anion Exchange Membrane Fuel Cells: From Heterogeneous Catalysis to Homogeneous Catalysis
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99 GENERAL AND MISCELLANEOUS↗
Functional Porphyrinic Metal?Organic Framework as a New Class of Heterogeneous Halogen-Bond-Donor Ca
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Zhang, Weijie↗
Formation of a Strong Heterogeneous Aluminum Lewis Acid on Silica
Abstract Al(OC(CF 3 ) 3 )(PhF) reacts with silanols present on partially dehydroxylated silica to form well‐defined ≡SiOAl(OC(CF 3 ) 3 ) 2 (O(Si≡) 2 ) ( 1 ). 27 Al NMR and DFT calculations with a small cluster model to approximate the silica surface show that the aluminum in 1 adopts a distorted trigonal bipyramidal coordination geometry by coordinating to a nearby siloxane bridge and a fluorine from the alkoxide. Fluoride ion affinity (FIA) calculations follow experimental trends and show that 1 is a stronger Lewis acid than B(C 6 F 5 ) 3 and Al(OC(CF 3 ) 3 )(PhF) but is weaker than Al(OC(CF 3 ) 3 ) and i Pr 3 Si + . Cp 2 Zr(CH 3 ) 2 reacts with 1 to form [Cp 2 ZrCH 3 ][≡SiOAl(OC(CF 3 ) 3 ) 2 (CH 3 )] ( 3 ) by methide abstraction. This reactivity pattern is similar to reactions of organometallics with the proposed strong Lewis acid sites present on Al 2 O 3 .
Samudrala, Kavyasripriya K.↗
Models for Single–Site Heterogeneous Catalysts on Carbon: MoO 2 Epoxidation Catalyst Anchored to a Fullerene
Single-site molybdenum dioxo catalysts, fullerenol/MoO 2 , are prepared via grafting precursor (DME)MoO 2 Cl 2 onto a highly polyhydroxylated fullerene (ful) and an isomerically-pure and well-defined fullerene (ful*). These catalyst structures are characterized by ICP-OES, XPS, XANES, EXAFS, DRIFT, Raman, and NMR spectroscopy, and DFT. Mo 3d 5/2 XPS and Mo K-edge XANES assign the oxidation state as Mo(VI). Mo EXAFS data fitting reveals two Mo=O double and two Mo–O single bonds at distances of 1.7 and 1.9 Å, respectively, while an Mo=O stretchingl mode is observed at ~950 cm –1 by DRIFT and Raman spectroscopy. These data align well with DFT computational results, supporting the proposed catalyst structure as Fullerene(-μ-O-) 2 M(=O) 2 . Additionally, DFT provides insight into the energetically favorable grafting sites for an isomerically pure fullerenol. The scope of fullerenol/MoO 2 mediated alkene epoxidation includes abiotic alkenes, natural occurring terpenes, and conjugated olefins. For cyclooctene the rate law is first-order in [Mo], near first order in [olefin] and zero-order in [t-butyl hydroperoxide]. A plausible reaction mechanism involves peroxide addition first and then cyclooctene addition directly across the peroxo bond forming the epoxide product, consistent with DFT computation. Overall, fullerenol/MoO 2 shows promise as a sustainable and structurally well-defined system with versatile catalytic activity and good epoxidation recyclability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Elucidation of Design Criteria for V‐based Redox Mediators: Structure‐Function Relationships that Dictate Rates of Heterogeneous Electron Transfer
Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac) 3 ], [V 6 O 7 (OMe) 12 ], [ n Bu 4 N] 3 [V 6 O 13 (TRIS NO2 ) 2 ], and [ n Bu 4 N] 5 [V 18 O 46 (NO 3 )] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria – (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. In conclusion, our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantifying the Site Heterogeneities of Non‐Uniform Catalysts Using QuantEXAFS
Abstract We present the Multi‐site (MS) QuantEXAFS approach, designed to model the EXAFS data from samples containing an element in different local bonding geometries. Building upon our QuantEXAFS method, which maps experimental extended X‐ray absorption fine structures (EXAFS) data to DFT‐optimized structures, MS‐QuantEXAFS introduces the key capability to probe fractional contributions of multiple sites that may be present in an experimental sample. Specifically, we demonstrate effectiveness of this technique by investigating mixed samples containing known fractions of site‐isolated subsurface Pt/MgO with Pt nanoparticles uniformly supported on MgO. The ‘site‐fractions’ obtained through MS‐QuantEXAFS closely match (i. e., ±6%) the known fractions of the physically mixed samples. This approach has been generalized to other oxides, and thus represents an important advance in quantifying the speciation of non‐uniform catalyst samples.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Experiences in porting mini-applications to OpenACC and OpenMP on heterogeneous systems
This article studies mini-applications—Minisweep, GenASiS , GPP, and FF—that use computational methods commonly encountered in HPC. We have ported these applications to develop OpenACC and OpenMP versions, and evaluated their performance on Titan (Cray XK7 with K20x GPUs), Cori (Cray XC40 with Intel KNL), Summit (IBM AC922 with Volta GPUs), and Cori-GPU (Cray CS-Storm 500NX with Intel Skylake and Volta GPUs). Our goals are for these new ports to be useful to both application and compiler developers, to document and describe the lessons learned and the methodology to create optimized OpenMP and OpenACC versions, and to provide a description of possible migration paths between the two specifications. Cases where specific directives or code patterns result in improved performance for a given architecture are highlighted. Here, we also include discussions of the functionality and maturity of the latest compilers available on the above platforms with respect to OpenACC or OpenMP implementations.
97 MATHEMATICS AND COMPUTING↗
Rational Control of Off‐State Heterogeneity in a Photoswitchable Fluorescent Protein Provides Switching Contrast Enhancement**
Abstract Reversibly photoswitchable fluorescent proteins are essential markers for advanced biological imaging, and optimization of their photophysical properties underlies improved performance and novel applications. Here we establish a link between photoswitching contrast, one of the key parameters that dictate the achievable resolution in nanoscopy applications, and chromophore conformation in the non‐fluorescent state of rsEGFP2, a widely employed label in REversible Saturable OpticaL Fluorescence Transitions (RESOLFT) microscopy. Upon illumination, the cis chromophore of rsEGFP2 isomerizes to two distinct off ‐state conformations, trans1 and trans2 , located on either side of the V151 side chain. Reducing or enlarging the side chain at this position (V151A and V151L variants) leads to single off ‐state conformations that exhibit higher and lower switching contrast, respectively, compared to the rsEGFP2 parent. The combination of structural information obtained by serial femtosecond crystallography with high‐level quantum chemical calculations and with spectroscopic and photophysical data determined in vitro suggests that the changes in switching contrast arise from blue‐ and red‐shifts of the absorption bands associated to trans1 and trans2 , respectively. Thus, due to elimination of trans2 , the V151A variants of rsEGFP2 and its superfolding variant rsFolder2 display a more than two‐fold higher switching contrast than their respective parent proteins, both in vitro and in E. coli cells. The application of the rsFolder2‐V151A variant is demonstrated in RESOLFT nanoscopy. Our study rationalizes the connection between structural and photophysical chromophore properties and suggests a means to rationally improve fluorescent proteins for nanoscopy applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Resident and transient coyotes exhibit differential patterns of movement behavior across heterogeneous landscapes in the southeastern United States
Coyotes (Canis latrans) are a highly adaptable canid species whose behavioral plasticity has allowed them to persist in a wide array of habitats throughout North America. As generalists, coyotes can alter movement patterns and change territorial strategies between residency (high site fidelity) and transiency (low site fidelity) to maximize fitness. Uncertainty remains about resident and transient coyote movement patterns and habitat use because research has reached conflicting conclusions regarding patterns of habitat use by both groups. We quantified effects of habitat on resident and transient coyote movement behavior using first passage time (FPT) analysis, which assesses recursive movement along an individual's movement path to delineate where they exhibit area-restricted search (ARS) behaviors relative to habitat attributes. We quantified monthly movement rates for 171 coyotes (76 residents and 53 transients) and then used estimated FPT values in generalized linear mixed models to quantify monthly habitat use for resident and transient coyotes. Transients had greater movement rates than residents across all months except January. Resident FPT values were positively correlated with agricultural land cover during fall and winter, but negatively correlated with agriculture during spring. Resident FPT values were also negatively correlated with developed habitats during May–August, deciduous land cover during June–August, and wetlands during September–January except November. FPT values of transient coyotes were positively correlated with developed areas throughout much of the year and near wetlands during July–September. Transient FPT values were negatively correlated with agriculture during all months except June and July. High FPT values (ARS behavior) of residents and transients were generally correlated with greater densities of edge habitat. Although we observed high individual variation in space use, our study found substantive differences in habitat use between residents and transients, providing further evidence that complexity and plasticity of coyote habitat use is influenced by territorial strategy.
54 ENVIRONMENTAL SCIENCES↗
Nitrogen fixation as NO x using air plasma coupled with heterogeneous catalysis at atmospheric pressure
Here, this study presents insights into the use of activated Al 2 O 3 catalysts to improve the energy efficiency of NO x production in atmospheric pressure air plasma. The introduction of catalysts in the direct current glow discharge system reduces the energy cost of NO x production by up to 45% at low gas flow rates. Notably, even when positioned away from the plasma zone, the catalyst enhanced NO x production, suggesting a significant role for the catalytic activation of downstream neutral species. The study also introduced a novel approach involving an air plasma jet infused with floating catalyst powder. This method significantly increased energy efficiency at higher discharge currents, with an associated energy cost of 2.9 MJ/mol for NO x production.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Porous Salts as Platforms for Heterogeneous Catalysis
In this study, the preparation of a new class of reactive porous solids, prepared via straightforward salt metathesis reactions, is described here. Reaction of the dimethylammonium salt of a magnesium-based porous coordination cage with the chloride salt of [Cr II Cl(Me 4 cyclam)] + affords a porous solid with concomitant removal of dimethylammonium chloride. The salt consists of the ions combined in the expected ratio based on their charge as confirmed by UV–vis and X-ray photoelectron spectroscopies, ion chromatography (IC), and inductively coupled plasma mass spectrometry (ICP-MS). The porous salt boasts a Brunauer-Emmett-Teller (BET) surface area of 213 m 2 g -1 . Single crystal X-ray diffraction reveals the chromium(II) cations in the structure reside in the interstitial space between porous cages. Importantly, the chromium(II) centers, previously shown to react with O 2 to afford reactive chromium(III)-superoxide adducts, are still accessible in the solid state as confirmed by UV–vis spectroscopy. The site-isolated reactive centers have competence toward hydrogen atom abstraction chemistry and display significantly increased stability and reactivity as compared to dissolved ions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Regulating Li Nucleation and Growth Heterogeneities via Near-Surface Lithium-Ion Irrigation for Stable Anode-Less Lithium Metal Batteries
The inhomogeneous nucleation and growth of Li dendrite combined with the spontaneous side reactions with the electrolytes dramatically challenge the stability and safety of Li metal anode (LMA). Despite tremendous endeavors, current success relies on the use of significant excess of Li to compensate the loss of active Li during cycling. Herein, a near-surface Li + irrigation strategy is developed to regulate the inhomogeneous Li deposition behavior and suppress the consequent side reactions under limited Li excess condition. The conformal polypyrrole (PPy) coating layer on Cu surface via oxidative chemical vapor deposition technique can induce the migration of Li + to the interregional space between PPy and Cu, creating a near-surface Li + -rich region to smooth diffusion of ion flux and uniform the deposition. Moreover, as evidenced by multiscale characterizations including synchrotron high-energy X-ray diffraction scanning, a robust N-rich solid-electrolyte interface (SEI) is formed on the PPy skeleton to effectively suppress the undesired SEI formation/dissolution process. Strikingly, stable Li metal cycling performance under a high areal capacity of 10 mAh cm -2 at 2.0 mA cm -2 with merely 0.5 × Li excess is achieved. The findings not only resolve the long-standing poor LMA stability/safety issues, but also deepen the mechanism understanding of Li deposition process.
25 ENERGY STORAGE↗
Adrastea: An Efficient FPGA Design Environment for Heterogeneous Scientific Computing and Machine Learning
We present Adrastea, an efficient FPGA design environment for developing scientific machine learning applications. FPGA development is challenging, from deployment, proper toolchain setup, programming methods, interfacing FPGA kernels, and more importantly, the need to explore design space choices to get the best performance and area usage from the FPGA kernel design. Adrastea provides an automated and scalable design flow to parameterize, implement, and optimize complex FPGA kernels and associated interfaces. We show how virtualization of the development environment via virtual machines is leveraged to simplify the setup of the FPGA toolchain while deploying the FPGA boards and while scaling up the automated design space exploration to leverage multiple machines concurrently. Adrastea provides an automated build and test environment of FPGA kernels. By exposing design space hyper-parameters, Adrastea can automatically search the design space in parallel to optimize the FPGA design for a given metric, usually performance or area. Adrastea simplifies the task of interfacing with the FPGA kernels with a simplified interface API. To demonstrate the capabilities of Adrastea, we implement a complex random forest machine learning kernel with 10,000 input features while achieving extremely low computing latency without loss of prediction accuracy, which is required by a scientific edge application at SNS. We also demonstrate Adrastea using an FFT kernel and show that for both applications Adrastea is able to systematically and efficiently evaluate different design options, which reduced the time and effort required to develop the kernel from months of manual work to days of automatic builds.
Young, Aaron↗