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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Quantifying the Decomposition Kinetics of Linear C 2 –C 4 Perfluoroalkanes

The pyrolysis of C 2 –C 4 linear perfluoroalkanes was investigated using laser schlieren densitometry (LS) in a diaphragmless shock tube. Mixtures of 1, 2, and 4% perfluoroethane (PFE), perfluoropropane (PFP), and perfluorobutane (PFB) in excess krypton were shock-heated to 1400–2500 K at pressures of 60, 120, and 240 Torr. The initiation step for all perfluoroalkanes involved carbon–carbon bond fission. The rate constants for unimolecular decomposition were computed using microcanonical rate theory, and these rate constants were combined into a detailed chemical kinetic mechanism. For PFE and PFP, there was one dissociation channel, while PFB dissociated via two competing bond-fission reactions. The perfluoroalkyl radicals subsequently recombined or underwent further unimolecular decomposition. In conclusion, the kinetic model accurately simulated the density gradient profiles of all perfluoroalkanes.

Guzman, Eduardo H. [Brown Univ., Providence, RI (U↗
DOE OSTI2020

Diffusivity and Structure of Room Temperature Ionic Liquid in Various Organic Solvents

Room-temperature ionic liquids (RTILs) hold promise for applications in electric double layer capacitors (EDLCs), owing to a much wider potential window, lower vapor pressure, and better thermal and chemical stabilities compared to conventional aqueous and organic electrolytes. However, because the low diffusivity of ions in neat RTILs negates the EDLCs’ advantage of high power density, the ionic liquids are often used in mixture with organic solvents. In this study, we measured the diffusivity of cations and anions in RTIL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) ([BMIM + ][TFSI – ]), mixed with 10 organic solvents, by using the pulsed-field gradient NMR method. The ion diffusivity was found to follow that of neat solvents and in most studied solvents showed an excellent agreement with the predicted values reported in the recent molecular dynamics (MD) study [Thompson, M. W.; J. Phys. Chem. B 2019, 123, 1340-1347]. In two solvents consisting of long-chain molecules, however, the MD simulations predictions slightly underestimated the ionic diffusivities. The degree of ion dissociation was also estimated for each solvent by comparing the ionic conductivity with the molar conductivity derived from the diffusion measurements. The degree of ion dissociation and the hydrodynamic radius of ions suggest that the ions are coordinated by ~1 solvent molecule. Finally, the scarcity of solvent–ion interactions explains the fact that the diffusivity of ions in the mixture significantly depends on the viscosity of the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Transition Path Sampling Study of the Feruloyl Esterase Mechanism

Serine hydrolases cleave peptide and ester bonds and are ubiquitous in nature, with applications in biotechnology, in materials, and as drug targets. The serine hydrolase two-step mechanism employs a serine–histidine–aspartate/glutamate catalytic triad, where the histidine residue acts as a base to activate poor nucleophiles (a serine residue or a water molecule) and as an acid to allow the dissociation of poor leaving groups. This mechanism has been the subject of debate regarding how histidine shuttles the proton from the nucleophile to the leaving group. To elucidate the reaction mechanism of serine hydrolases, we employ quantum mechanics/molecular mechanics-based transition path sampling to obtain the reaction coordinate using the Aspergillus niger feruloyl esterase A (AnFaeA) as a model enzyme. The optimal reaction coordinates include terms involving nucleophilic attack on the carbonyl carbon and proton transfer to, and dissociation of, the leaving group. During the reaction, the histidine residue undergoes a reorientation on the time scale of hundreds of femtoseconds that supports the “moving histidine” mechanism, thus calling into question the “ring flip” mechanism. We find a concerted mechanism, where the transition state coincides with the tetrahedral intermediate with the histidine residue pointed between the nucleophile and the leaving group. Moreover, motions of the catalytic aspartate toward the histidine occur concertedly with proton abstraction by the catalytic histidine and help stabilize the transition state, thus partially explaining how serine hydrolases enable poor nucleophiles to attack the substrate carbonyl carbon. Rate calculations indicate that the second step (deacylation) is rate-determining, with a calculated rate constant of 66 s –1 . Altogether, these results reveal the pivotal role of active-site dynamics in the catalytic mechanism of AnFaeA, which is likely similar in other serine hydrolases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Model for Atomic Precision p-Type Doping with Diborane on Si(100)-2×1

Diborane (B 2 H 6 ) is a promising molecular precursor for atomic precision p-type doping of silicon that has recently been experimentally demonstrated. In this study, we use density functional theory (DFT) calculations to determine the reaction pathway for diborane dissociating into a species that will incorporate as electrically active substitutional boron after adsorbing onto the Si(100)-2×1 surface. Our calculations indicate that diborane must overcome an energy barrier to adsorb, explaining the experimentally observed low sticking coefficient (<1 × 10 –4 at room temperature) and suggesting that heating can be used to increase the adsorption rate. Upon sticking, diborane has an ≈50% chance of splitting into two BH 3 fragments versus merely losing hydrogen to form a dimer such as B 2 H 4 . As boron dimers are likely electrically inactive, whether this latter reaction occurs is shown to be predictive of the incorporation rate. The dissociation process proceeds with significant energy barriers, necessitating the use of high temperatures for incorporation. Using the barriers calculated from DFT, we parameterize a Kinetic Monte Carlo model that predicts the incorporation statistics of boron as a function of the initial depassivation geometry, dose, and anneal temperature. Our results suggest that the dimer nature of diborane inherently limits its doping density as an acceptor precursor and furthermore that heating the boron dimers to split before exposure to silicon can lead to poor selectivity on hydrogen and halogen resists. This suggests that, while diborane works as an atomic precision acceptor precursor, other non-dimerized acceptor precursors may lead to higher incorporation rates at lower temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Probing Acid–Base Properties of Anatase TiO 2 Nanoparticles with Dominant {001} and {101} Facets Using Methanol Chemisorption and Surface Reactions

In the present study, we investigate the surface acid-base properties of anatase TiO 2 nanomaterials with dominant {101} and {001} facets via methanol titrations. Two anatase nanoparticles, TiO 2 (101) and TiO 2 (001), with well-defined morphology are prepared. TiO 2 (101) is predominantly enclosed by the {101} facets (> 90%), and TiO 2 (001) contains ~46% {001} facets and ~54% {101} facets. Upon adsorption of methanol 423 K, DRIFTS measurements show that both molecular and dissociative adsorption occurs on TiO 2 (101), while dissociative adsorption dominates on TiO 2 (001). During methanol TPD, TiO 2 (001) mainly generates acid-base product dimethyl ether and thermal cracking products CO and H 2 , as anticipated. In contrast, substantial amounts of formaldehyde and methane also desorb from TiO 2 (101), suggesting strong participation of surface defects (e.g., oxygen vacancies).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Computational Investigation of the Catalytic Hydrodeoxygenation of Propanoic Acid over a Cu(111) Surface

Cu-based alloy catalysts have recently been investigated experimentally for the hydrodeoxygenation (HDO) of biomass-derived organic acids. Here, the HDO of propanoic acid (PAc) has been studied over Cu(111) by mean-field microkinetic modeling based on parameters obtained from first-principles calculations. Models were developed for the gas- and liquid-phase HDO in condensed water and 1,4-dioxane. In agreement with experimental observations, the gas-phase PAc conversion rate is low at 573 K and increases in liquid water by 1 order of magnitude. In all reaction environments, the decarboxylation mechanism is dominant at low hydrogen partial pressures less than 0.1 bar, and the C–COO bond dissociation is the rate-controlling elementary step. This observation contrasts with the rate-controlling step identified over most group VIII metal surfaces, which is the C–OH bond dissociation in the decarbonylation mechanism. At high hydrogen (H 2 ) partial pressures greater than 10 bar, the HDO of PAc produces propionaldehyde that can readsorb and further react through decarbonylation to produce C 2 alkane products, which is conceptually different from the low H 2 partial pressure scenario. At high H 2 partial pressures, the initial hydrogenation at the carbonyl carbon of PAc becomes the rate-controlling elementary step.

Catalysts↗
DOE OSTI2022

Mechanistic Investigations of Gas-Phase Catalytic Hydrogenation in Metal–Organic Frameworks: Cooperative Activity of the Metal and Linker Sites in Cu x Rh 3– x (BTC) 2

We report the Cu x Rh 3–x (BTC) 2 catalyst (abbreviated CuRhBTC, BTC 3– = benzene tricarboxylate) provides excellent dispersion of active metal sites coupled with well-defined, robust structures for propylene hydrogenation reactions. This material therefore serves as a unique prototype for understanding catalytic activity in metal organic frameworks (MOFs). The mechanism of gas-phase hydrogenation at the bimetallic metal nodes of a MOF has been investigated in detail for the first time using in situ spectroscopy and diffraction experiments combined with density functional theory (DFT) calculations. The reaction occurs via a cooperative process in which the metal and linker sites play complementary roles; specifically, H 2 is dissociated at a Rh 2+ site with a missing Rh–O bond, while protonation of the decoordinated carboxylate linker stabilizes the active sites and promotes H 2 dissociation. In situ X-ray diffraction experiments show that the crystalline structure of the MOF is retained under reaction conditions at 20–100 °C. In situ Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments demonstrate that propylene adsorbs at both Rh 2+ and Cu 2+ sites via π bonding. Cu 2+ is catalytically inactive, but at Rh 2+ sites, a propyl intermediate is observed when H 2 is introduced into the propylene feed. Furthermore, the appearance of the O–H stretch of COOH at ~3690 cm –1 in the DRIFT spectra is characteristic of defects consisting of missing Rh–O bonds. These experimental results are in general agreement with a reaction mechanism proposed by DFT, in which the decoordinated carboxylate linker is protonated, and the active Rh 2+ site remains available for readsorption of reactants in the subsequent catalytic cycle.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Elucidating CO Oxidation Pathways on Rh Atoms and Clusters on the “29” Cu 2 O/Cu(111) Surface

We report single-atom catalysts have attracted a great deal of attention due to their distinct reactivity and potential for cost savings. However, despite the wealth of literature in recent years, identifying the exact nature of the active sites and associated reaction mechanisms remains challenging in many cases. Herein, we take a surface science approach to understand how Rh single atoms and small clusters behave on the thin film “29” Cu 2 O grown on Cu(111). We find that in contrast to Pt, which is present solely as single atoms on the “29” Cu 2 O surface, Rh atoms and clusters coexist and each enable low-temperature CO oxidation, but via different pathways. Specifically, the single Rh atoms produce CO 2 at 444 K via a Mars van Krevelen mechanism whereas the Rh clusters can also dissociate CO, as demonstrated via isotope labeling, and liberate CO 2 at 313 K. Density functional theory (DFT) calculations quantify the energetics of these different pathways and demonstrate that only extended Rh is capable of CO dissociation. Low-temperature scanning tunneling microscopy (STM) reveals that unlike Pt atoms on the same surface, which stay atomically dispersed, the distribution of Rh structures is dependent on pretreatment conditions. DFT calculations reveal the greater tendency of Rh atoms to cluster than Pt, and STM image simulations confirm the active sites. Ambient pressure X-ray photoelectron spectroscopy studies on the same single crystal model systems demonstrate that 1% of a monolayer of Rh on the “29” Cu 2 O thin film significantly accelerates its reduction by CO at 400 K, thus confirming the ultrahigh vacuum surface science findings. Together, these results illustrate how well-defined single crystal experiments are useful in building structure–function relationships that elucidate the reactivity of different ensemble sizes with a level of detail beyond what is possible with high surface area catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

CO 2 Hydrogenation to Methanol over Inverse ZrO 2 /Cu(111) Catalysts: The Fate of Methoxy under Dry and Wet Conditions

Understanding the surface chemistry of CH 3 O species is essential for the production of methanol by CO 2 hydrogenation over Cu-based heterogeneous catalysts, as it facilitates the rational design of more efficient conversion processes. Recent research has identified inverse ZrO 2 /Cu catalysts as highly active and selective systems for the transformation of CO 2 to methanol with a performance that can be better than that of commercial Cu/ZnO catalysts. Here, we employed synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and calculations based on density functional theory (DFT) to understand the fate of CH 3 O groups under dry and wet environments. AP-XPS spectra revealed that under CO 2 hydrogenation conditions, formate and methoxy are two key intermediates to produce methanol. Furthermore, there are three different types of reactive sites on the surface: One is active for methoxy adsorption, which is stable and responsible for the methanol synthesis; Another one transforms CO 2 into CO; and a third one is active for CO 2 and methoxy dissociation, leading to C and methane formation. The theoretical calculations indicate that CH 3 OH readily dissociates to CH 3 O species following a highly exothermic (ΔE = -20.99 kcal/mol) and barrierless process. The water produced by the reverse water-gas shift reaction (CO 2 + H 2 → H 2 O + CO) can prevent the decomposition of CH 3 O species. We discovered that by introducing a tiny amount of water vapor (2 × 10 -6 Torr) into the reaction chamber, the energy barrier for the reaction CH 3 O(ads) + H(ads) → CH 3 OH(gas) is dramatically reduced. AP-XPS and computational modelling showed that water is quite capable of extracting adsorbed methoxy to form gaseous methanol. With this in mind, one could boost the methanol selectivity by adding appropriate amounts of water or steam, which is an inexpensive and feasible solution for industrial operations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unraveling 1-Hexene Hydrogenation over Dilute Pd-in-Au Alloys

Dilute Pd-in-Au alloys are valuable materials for selectively hydrogenating alkynes and isomerizing alkenes. By diluting Pd in a Au host, the selectivity toward semihydrogenated alkene isomers can be significantly enhanced and the unfavorable overhydrogenation to alkanes is suppressed. However, a detailed mechanistic study on the origin of the enhanced alkene selectivity over dilute alloy catalysts is still missing. Here, we combine experiment and theory to unravel the reaction mechanism, identifying rate-limiting and selectivity-controlling steps in 1-hexene hydrogenation over dilute Pd-in-Au catalysts. Using isotope-exchange hydrogenation experiments, we show that 1-hexene and hydrogen over a bimetallic Pd4Au96 in silica catalyst preferentially form 1-hexene isomers, (trans and cis) 2- and 3-hexene and only a small amounts of hexane. The reaction is consistent with a Horiuti–Polanyi mechanism, similar to a monometallic Pd nanoparticle catalyst. Computation of the free-energy profiles for 1-hexene hydrogenation and isomerization over a single Pd atom in a Au surface using first principles calculations indicated that the isomerization of 1-hexene to 2-hexene is energetically favorable due to the relatively large barrier for H2 dissociation preventing hydrogenation to n-hexane. Microkinetic modeling established that H2 dissociation on the single-atom Pd sites and H spillover from these sites onto the Au host are rate-limiting and key in steering the selectivity of dilute Pd-in-Au alloys toward the hexene isomers. Furthermore, the mechanistic insights from this study contribute to the rational design of optimized dilute alloy catalysts for selective alkene isomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Measuring Relative Energies of Ligand Binding Conformations on Nanocluster Surfaces with Temperature-Dependent FTIR Spectroscopy

We present a method to measure relative energies between binding conformations of carboxylate ligands on InP magic-sized clusters in solution. Using Markov chain Monte Carlo global fitting analysis on temperature-dependent vibrational spectra of cluster-bound ligands, we observe significantly different relative energies between various bidentate and monodentate binding motifs. Relative to the monodentate motif, the chelating conformation is 0.7 ± 0.3 kcal/mol more stable and the syn–syn bridging conformation is 1.1 ± 0.5 kcal/mol more stable, but the syn–anti bridging conformation exhibits no significant difference. Our results demonstrate that the relative energy between monodentate-bound carboxylates and unbound carboxylic acids is 4.52 ± 0.05 kcal/mol, or 1582 ± 19 cm –1 , nearly identical to the carboxylate asymmetric stretching frequency. Here, we suggest that the ligand vibrational energy may play a key role in ligand dissociation by compensating for energy differences between bound and dissociated ligand states. This approach gives important experimental insights into ligand binding and can inform future nanocrystal surface engineering.

Conformation↗
DOE OSTI2024

MgO Nanostructures on Cu(111): Understanding Size- and Morphology-Dependent CO 2 Binding and Hydrogenation

To design and optimize cost-effective technologies for the capture, utilization, and storage of carbon dioxide (CO 2 ), we need a fundamental knowledge and control of chemical interactions associated with the capture and conversion of the molecule into high-value chemicals, minerals, and all kinds of materials. Bulk magnesium oxide (MgO) is frequently used for the trapping and storage of CO 2 by generation of magnesium carbonates. In this study, the growth and reactivity of MgO nanostructures on a Cu 2 O/Cu(111) substrate were investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). For extremely small concentrations of Mg (~ 0.01 monolayer (ML)), a well-ordered film of copper oxide with small clusters (0.2-0.5 nm in width, 0.4-0.6 Å in height) of embedded MgO was seen. At a coverage of 0.1 ML, MgO nanoparticles with a width of 0.4 to 1 nm and a height of ~ 1.5 Å were randomly distributed on the copper oxide. Further, random distribution was also observed when the MgO coverage was raised to 0.25 ML, with the width of the MgO particles increasing to 2-2.5 nm and the height reaching 2 Å. These oxide nanostructures displayed a high reactivity towards CO 2 and H 2 that is not seen for bulk MgO. Dissociation of H 2 was observed at room temperature with reaction of the H adatoms with CuO x and C-containing groups. On the small MgO nanostructures (< 1 nm in width), instead of plain carbonate formation, there was dissociation of CO 2 into CO and C species, opening reaction channels for the conversion of this harmful molecule into oxygenates and light alkanes.

03 NATURAL GAS↗
DOE OSTI2025

Toward a Better Understanding of Ni Coarsening in Solid Oxide Cells: NiH on Ni (111) Examined Using a Combined Theoretical Approach

The coarsening of the Ni particles in the hydrogen electrode of solid oxide cells (SOCs) is an important degradation mechanism. Here, in this paper, density-functional theory and kinetic Monte Carlo methods are used to explore our recent hypothesis that the surface diffusion of NiH may cause faster Ni coarsening in electrolysis cell mode under an overpotential. Using both methods, the diffusion constant or diffusivity of NiH on Ni (111) is determined as the product of the surface coverage and single-molecule diffusivity for the first time considering all possible diffusion paths. It is then determined versus overpotential at the triple-phase boundary of the hydrogen electrode assuming a typical operating temperature of the SOC. Under a significant overpotential, the diffusivity of NiH is found to be sufficiently large to support the above hypothesis that NiH may promote Ni coarsening. However, based on the adsorption configurations identified, the dissociation and reformation of NiH on Ni (111) could occur. Thus, more work is needed to develop a model of Ni coarsening considering both molecular and dissociated forms of NiH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Low Temperature Oxygen Activation on the NiAg(100) Single-Atom Alloy Surface

Silver-catalyzed ethylene epoxidation remains the only industrially viable route for ethylene oxide (EO) production. However, this process requires chlorine and other promoters to achieve a high EO selectivity while still generating substantial CO 2 emissions. A recent theory-guided approach identified Ni, in single-atom alloy (SAA) form, as a new promoter of this reaction. Specifically, the addition of Ni to Ag nanoparticles supported on α-Al 2 O 3 at a highly diluted ratio (1 Ni per 200 Ag atoms) increased catalyst selectivity to EO by ∼25%, the same increase afforded by the ubiquitous industrial promoter chlorine. To better understand the effect of Ni, we investigated the interaction of O 2 with NiAg(100) SAA surfaces by using scanning tunneling microscopy (STM) and density functional theory (DFT). While only molecular O 2 was present when pure Ag(100) was exposed to O 2 at 78 K, a distinct NiO 2 species, indicative of O 2 dissociation at Ni atom sites, was identified on the NiAg(100) SAA under the same conditions. High-resolution STM imaging backed by DFT simulations elucidated the formation of an O−Ni−O species with the oxygen atoms in 4-fold hollow sites. These findings provide direct experimental evidence that Ni atoms are very effective at O 2 activation, even at cryogenic temperatures. This suggests that, in addition to the known role of Ni in stabilizing the unselective nucleophilic oxygen on Ag, it could also accelerate O 2 dissociation, which can be rate limiting.

Catalysts↗
DOE OSTI2024

Self-Inhibition Phenomena in Cu 3 Pt Oxidation by CO 2

Here, this study investigates the oxidation behavior of Cu 3 Pt(100) in CO 2 using a combination of ambient-pressure X-ray photoelectron spectroscopy, mass spectroscopy, and density functional theory modeling. Our in situ measurements reveal the simultaneous oxidation and reduction of Cu 2 O due to the opposing effects of atomic oxygen and CO generated from dissociative CO 2 adsorption, leading to a dynamic equilibrium state of simultaneously occurring redox reactions. Complementary atomistic calculations elucidate the inhibitory effects of subsurface Pt enrichment and the counteracting roles of CO 2 and CO in surface oxidation and reduction. These results provide mechanistic insights into the dissociative pathway of CO 2 molecules and dynamic evolution of surface composition and reactivity of Cu-based alloy catalysts in CO 2 -rich environments, with broader implications for tuning gas–surface reactions by manipulating gas reactants or solid surface composition.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ultrafast Dynamics and Rearrangement of the EUV Photoacid Generator Phenyl Triflate

Extreme UV photolithography is a high-energy process crucial for modern computer chip fabrication, where photoacid generators (PAGs) enhance radiation exposure by producing reactive chemical species. This study investigates the ultrafast dissociative dynamics of phenyl triflate, a widely used PAG, under high-energy ionizing conditions. The dissociative ionization of the phenyl triflate cation, which includes a molecular rearrangement that releases SO 2 and forms the phenyl trifluoromethyl ether cation, is measured over the first 5 ps. These dynamics reveal vibrational coherence corresponding to a torsional mode of the cation, involving the twisting of the phenyl group into the O–S–C plane. Electronic structure calculations for the radical cation are in good agreement with the experimentally observed vibrational coherence. These findings provide valuable insights into the behavior of phenyl triflate under ionizing conditions similar to its industrial usage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cation Effects on CO 2 Delivery to Cu Electrode in Reactive Capture of CO 2

The direct electrochemical conversion of captured CO 2 , known as reactive capture of CO 2 (RCC), remains a formidable challenge in heterogeneous catalysis. Given that amines are one of the most widely used capture agents for CO 2 , it would be desirable to electrochemically reduce the resultant adducts, such as carbamate, directly in RCC. However, current understanding suggests that the primary species undergoing reduction in RCC with amines is the CO 2 dissociated from the sorbent. Herein, we employ ab initio molecular dynamics (AIMD) with DFT to analyze how the nature of alkali metal cations in the electrolyte affects carbamate at the Cu surface, thereby assessing the possibility of promoting RCC by cation effects. The simulations show that the carbamate’s orientation with respect to the electrode is governed by the optimal distance between the carbamate and the cation, specifically how this distance aligns with the cation’s hydration spheres. Moreover, the slow-growth AIMD results indicate that the CO 2 dissociation barrier correlates with the orientation of carbamate at the interface. When the carbamate resides beyond the cation’s first hydration sphere, it adopts a flat orientation with respect to the surface that promotes the release of CO 2 from the capture agent. In contrast, when the carbamate disrupts the first hydration sphere and exhibits a strong cation−π interaction, it adopts an upright orientation that is less conducive to CO 2 release. These findings reveal a nontrivial cation effect in RCC, suggesting that it should be possible to optimize RCC via the choice of the electrolyte.

ab initio molecular dynamics↗
DOE OSTI2020

Segmental Dynamics Measured by Quasi-Elastic Neutron Scattering and Ion Transport in Chemically Distinct Polymer Electrolytes

We investigate the segmental dynamics and ion transport in two chemically distinct polymer electrolytes, poly(2-cyanoethyl acrylate) (PCEA) and poly(ethylene oxide) (PEO), and their mixtures with lithium bis(trifluoromethane)sulfonimide (LiTFSI) salt. Quasi-elastic neutron scattering experiments reveal slow dynamics in PCEA/LiTFSI relative to that in PEO/LiTFSI, translating to monomeric friction coefficients that are orders of magnitude different. In spite of the enhanced salt dissociation in PCEA due to the presence of polar groups, ion transport is largely dominated by the effect of increased monomeric friction in the pure polymer. Conductivity in these systems is quantified through a simple expression combining salt dissociation, the monomeric friction in the pure polymer, and the effect of added salt on the monomeric friction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗