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At least 631 records · Page 35

Enhancing Direct Electrochemical CO 2 Electrolysis by Introducing A-Site Deficiency for the Dual-Phase Pr(Ca)Fe(Ni)O 3-δ Cathode

High-temperature CO 2 electrolysis via solid oxide electrolysis cells (CO 2 –SOECs) has drawn special attention due to the high energy convention efficiency, fast electrode kinetics, and great potential in carbon cycling. However, the development of cathode materials with high catalytic activity and chemical stability for pure CO 2 electrolysis is still a great challenge. In this work, A-site cation deficient dual-phase material, namely (Pr 0.4 Ca 0.6 ) x Fe 0.8 Ni 0.2 O 3-δ (PCFN, x = 1, 0.95, and 0.9), has been designed as the fuel electrode for a pure CO 2 –SOEC, which presents superior electrochemical performance. Among all these compositions, (Pr 0.4 Ca 0.6 ) 0.95 Fe 0.8 Ni 0.2 O 3-δ (PCFN95) exhibited the lowest polarization resistance of 0.458 Ω cm 2 at open-circuit voltage and 800 °C. The application of PCFN95 as the cathode in a single cell yields an impressive electrolysis current density of 1.76 A cm -2 at 1.5 V and 800 °C, which is 76% higher than that of single cells with stoichiometric Pr 0.4 Ca 0.6 Fe 0.8 Ni 0.2 O 3-δ (PCFN100) cathode. The effects of A-site deficiency on materials' phase structure and physicochemical properties are also systematically investigated. Such an enhancement in electrochemical performance is attributed to the promotion of effective CO 2 adsorption, as well as the improved electrode kinetics resulting from the A-site deficiency.

30 DIRECT ENERGY CONVERSION↗

Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate

Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn -conformers are observed; anti -conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn -MVK-oxide with SO 2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO 3 and identifying organic hydroperoxide formation from reaction with SO 2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

09 BIOMASS FUELS↗

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

The following list summarizes the most important results that have been consistently reported for glass forming melts in microgravity: (1) Glass formation is enhanced for melts prepared in space; (2) Glasses prepared in microgravity are more chemically homogeneous and contain fewer and smaller chemically heterogeneous regions than identical glasses prepared on earth; (3) Heterogeneities that are deliberately introduced such as Pt particles are more uniformly distributed in a glass melted in space than in a glass melted on earth; (4) Glasses prepared in microgravity are more resistant to crystallization and have a higher mechanical strength and threshold energy for radiation damage; and (5) Glasses crystallized in space have a different microstructure, finer grains more uniformly distributed, than equivalent samples crystallized on earth. The preceding results are not only scientifically interesting, but they have considerable practical implications. These results suggest that the microgravity environment is advantageous for developing new and improved glasses and glass-ceramics that are difficult to prepare on earth. However, there is no suitable explanation at this time for why a glass melted in microgravity will be more chemically homogeneous and more resistant to crystallization than a glass melted on earth. A fundamental investigation of melt homogenization, nucleation, and crystal growth processes in glass forming melts in microgravity is important to understanding these consistently observed, but yet unexplained results. This is the objective of the present research. A lithium disilicate (Li2O.2SiO2) glass will be used for this investigation, since it is a well studied system, and the relevant thermodynamic and kinetic parameters for nucleation and crystal growth at 1-g are available. The results from this research are expected to improve our present understanding of the fundamental mechanism of nucleation and crystal growth in melts and liquids, and to lead improvements in glass processing technology on earth, with the potential for creating new high performance glasses and glass-ceramics.

Day, Delbert E.↗

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Most photochemistry occurs in the regime of weak light–matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light–matter interactions between an optical field and multiple molecules lead to collective hybrid light–matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. Here, the effect of strong light–matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light–matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

Cavities↗

Active Site Dynamics in Molybdenum-Based Silica-Supported Olefin Metathesis Catalysts: Site Renewal and Decay Beyond the Chauvin Cycle

Heterogeneous olefin metathesis catalysts exhibit low active site densities and unpredictable kinetics due to dynamic active site formation and decay processes. Here, in this study, we establish a quantitative framework that captures active site generation, renewal, and decay in olefin metathesis over silica-supported molybdenum oxide catalysts, enabling a mechanistic explanation of catalytic behavior and strategies to achieve high, stable activity. Steady-state active site titrations reveal that 2,3-dimethyl-butene isomers (4MEs) cofeeding increases active site density by up to 4.3-fold, directly correlating with enhanced metathesis rates. Spectroscopic studies demonstrate that 4MEs facilitate Mo(VI) reduction to Mo(IV) and interact strongly with surface Si–OH groups, generating labile protons that promote active site formation via a 1,2-proton shift mechanism. Kinetic modeling indicates that ethylene acts as a decay promoter, shifting kinetic control away from the Chauvin cycle and suppressing metathesis activity. Comparative studies on catalysts with varying Mo loading reveal that promotion is most effective for dispersed molybdate species, with a decline at higher Mo loadings. These findings provide a unified mechanistic framework for heterogeneous olefin metathesis, offering new strategies to enhance active site accessibility, mitigate deactivation, and optimize catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced gravitropism of roots with a disrupted cap actin cytoskeleton

The actin cytoskeleton has been proposed to be a major player in plant gravitropism. However, understanding the role of actin in this process is far from complete. To address this problem, we conducted an analysis of the effect of Latrunculin B (Lat B), a potent actin-disrupting drug, on root gravitropism using various parameters that included detailed curvature kinetics, estimation of gravitropic sensitivity, and monitoring of curvature development after extended clinorotation. Lat B treatment resulted in a promotion of root curvature after a 90 degrees reorientation in three plant species tested. More significantly, the sensitivity of maize (Zea mays) roots to gravity was enhanced after actin disruption, as determined from a comparison of presentation time of Lat B-treated versus untreated roots. A short 10-min gravistimulus followed by extended rotation on a 1-rpm clinostat resulted in extensive gravitropic responses, manifested as curvature that often exceeded 90 degrees. Application of Lat B to the cap or elongation zone of maize roots resulted in the disruption of the actin cytoskeleton, which was confined to the area of localized Lat B application. Only roots with Lat B applied to the cap displayed the strong curvature responses after extended clinorotation. Our study demonstrates that disrupting the actin cytoskeleton in the cap leads to the persistence of a signal established by a previous gravistimulus. Therefore, actin could function in root gravitropism by providing a mechanism to regulate the proliferation of a gravitropic signal originating from the cap to allow the root to attain its correct orientation or set point angle.

NASA Discipline Plant Biology↗

Remobilizing the Interface of Thermocapillary Driven Bubbles Retarded By the Adsorption of a Surfactant Impurity on the Bubble Surface

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow that propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillary to direct the movement of bubbles in space is the fact that surfactant impurities, which are unavoidably present in the continuous phase, can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. (This can also be the case if kinetic desorption of surfactant at the back end of the bubble is much slower than convection.) For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like and bubbles translate as solid particles). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature-induced tension gradient, and can decrease to near zero the bubble's thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have be retarded by the adsorption onto the bubble surface of a surfactant impurity. Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble surface much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition, the rapid kinetic exchange and high bulk concentration maintain a saturated surface with uniform surface concentrations. This prevents retarding surface tension gradients and keeps the thermocapillary velocity high. In our reports over the first 2 years, we presented numerical simulations of the bubble motion and surfactant transport which verified theoretically the concept of remobilization, and the development of an apparatus to track and measure the velocity of rising bubbles in a glycerol/water surfactant solution. This year, we detail experimental observations of remobilization. Two polyethylene oxide surfactants were studied, C12E6 (CH3(CH2)11(OCH2)6OH) and C10E8 (CH3(CH2)4(OCH2CH2)8OH). Measurements of the kinetic exchange for these surfactants show that the one with the longer hydrophobe chain C12E6 has a lower rate of kinetic exchange. In addition, this surfactant is much less soluble in the glycerol/water mixture because of the shorter ethoxylate chain. As a result, we found that C12E6 had only a very limited ability to remobilize rising bubbles because of the limited kinetic exchange and reduced solubility. However, C10E8, with its higher solubility and more rapid exchange was found to dramatically remobilize rising bubbles. We also compared our theoretical calculations to the experimental measurements of velocity for both the non-remobilizing and remobilizing surfactants and found excellent agreement. We further observed that for C10E8 at high concentrations, which exceeded the critical micelle concentrations, additional remobilization was measured. In this case the rapid exchange of monomer between micelle and surfactant provides an additional mechanism for maintaining a uniform surface concentrations.

Palaparthi, Ravi↗

Increasing the Pressure‐Free Stripping Capacity of the Lithium Metal Anode in Solid‐State‐Batteries by Carbon Nanotubes

Abstract Lithium metal is the key anode material for solid‐state‐batteries as its successful implementation will drastically increase their energy and power densities. However, anode contact loss during stripping leads to dendrites upon plating and subsequent cell failure. Design strategies to mitigate these issues are crucial to enable the use of lithium metal anodes. This paper reports the dissolution kinetics of composite anodes made of lithium metal and carbon nanotubes (CNTs) with a garnet‐type solid electrolyte (SE). In addition to an enhancement of the effective diffusion within the anode, its dissolution is fundamentally changed from being 2D to 3D. By maintaining contact with the SE, the CNTs facilitate lithium transport to the interface, which yields more than 20 mAh cm −2 discharge capacity at 100 µ A cm −2 without the application of external stack pressure ( > 1 MPa). Conclusions drawn from electrochemical data on the anode microstructure are validated using cryo‐focused‐ion‐beam scanning electron microscopy and correlated with the mechanical properties. Micro‐indentation, acoustic analysis, and stress–strain testing show that mechanical properties of the anode, like yield strength and hardness, are adjustable. Overall, it is shown that the mechanical and electrochemical properties of Li–CNT composite electrodes can be tailored to suit the requirements of a practical cell.

Fuchs, Till↗

Data‐driven variational method for discrepancy modeling: Dynamics with small‐strain nonlinear elasticity and viscoelasticity

Abstract The effective inclusion of a priori knowledge when embedding known data in physics‐based models of dynamical systems can ensure that the reconstructed model respects physical principles, while simultaneously improving the accuracy of the solution in the previously unseen regions of state space. This paper presents a physics‐constrained data‐driven discrepancy modeling method that variationally embeds known data in the modeling framework. The hierarchical structure of the method yields fine scale variational equations that facilitate the derivation of residuals which are comprised of the first‐principles theory and sensor‐based data from the dynamical system. The embedding of the sensor data via residual terms leads to discrepancy‐informed closure models that yield a method which is driven not only by boundary and initial conditions, but also by measurements that are taken at only a few observation points in the target system. Specifically, the data‐embedding term serves as residual‐based least‐squares loss function, thus retaining variational consistency. Another important relation arises from the interpretation of the stabilization tensor as a kernel function, thereby incorporating a priori knowledge of the problem and adding computational intelligence to the modeling framework. Numerical test cases show that when known data is taken into account, the data driven variational (DDV) method can correctly predict the system response in the presence of several types of discrepancies. Specifically, the damped solution and correct energy time histories are recovered by including known data in the undamped situation. Morlet wavelet analyses reveal that the surrogate problem with embedded data recovers the fundamental frequency band of the target system. The enhanced stability and accuracy of the DDV method is manifested via reconstructed displacement and velocity fields that yield time histories of strain and kinetic energies which match the target systems. The proposed DDV method also serves as a procedure for restoring eigenvalues and eigenvectors of a deficient dynamical system when known data is taken into account, as shown in the numerical test cases presented here.

Masud, Arif↗

Towards extreme fast charging of 4.6V LiCoO 2 via mitigating high-voltage kinetic hindrance

High-voltage LiCoO 2 (LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries (LIBs) in the 3C markets. However, the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability. Herein, combining experiments with density functional theory (DFT) calculations, we demonstrate that the kinetic limitations can be mitigated by a facial Mg 2+ +Gd 3+ co-doping method. The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage, making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process. The homogeneity enables the structural stability of LCO at a high-rate current density, inhibiting stress accumulation and irreversible phase transition. When used in combination with a Li metal anode, the doped LCO shows an extreme fast charging (XFC) capability, with a superior high capacity of 193.1 mAhg -1 even at the current density of 20C and high-rate capacity retention of 91.3% after 100 cycles at 5C. In conclusion, this work provides a new insight to prepare XFC high-voltage LCO cathode materials.

25 ENERGY STORAGE↗

Computational simulation of asymmetric phase transformation in cracked Li₇La₃Zr₂O₁₂: Variant selection and chemo-mechanical implications

Coupling between microcracks and phase transformation in ion-conducting ceramics can jointly affect mechanical responses and ion transport. In this work we investigate the cubic-to-tetragonal phase transformation in Li₇La₃Zr₂O₁₂ in the presence of a microcrack under hydrostatic loading and quantify its implications for crack-tip stress concentration and Li-ion transport using phase-field and molecular dynamics simulations. The phase transformation exhibits a strong asymmetry between hydrostatic tension and compression. Under tension, the crack edge nucleates one tetragonal variant that amplifies the crack-tip stress intensity and promotes crack opening. Under compression, the crack tip nucleates a different tetragonal variant that enhances the stress-induced crack-closure tendency. Effective Li diffusivity analysis shows faster transport degradation under compression due to accelerated transformation kinetics, exposing a trade-off between mechanical stability and ionic conductivity. These results highlight the intertwined nature of cracking, phase transformation, and ionic transport in ion-conducting oxides and provide mechanistic insights into chemo-mechanical degradation of solid electrolytes.

36 MATERIALS SCIENCE↗

Surface-Modified Pd/CeO 2 Single-Atom Catalyst Shows Increased Activity for Suzuki Cross-Coupling

Single-atom catalysts (SACs) comprise catalytically active atoms dispersed on supports; they combine the high activity and site uniformity of homogeneous catalysts with the ease of separability of heterogeneous catalysts. However, SACs lack fine control over the active site, provided by ligands in homogeneous catalysts. In this work, we demonstrate that modification of the support with an organic monolayer is a viable approach to improving the catalytic performance. Here, the addition of catechol-type monolayers to a Pd/CeO 2 SAC increases its catalytic activity for Suzuki cross-coupling, a central reaction in the synthesis of fine chemicals and pharmaceuticals. Kinetic trials reveal that the coating reduces the activation energy from 49 ± 9 to 22 ± 5 kJ/mol and produces a 4-fold rate enhancement at 25 °C, an effect we attribute to π-π interactions between the reactant and the catechol coating. Further development of this approach could vastly increase the utility of SACs in organic synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An ignition criterion for inertial fusion boosted by microturbulence

Turbulence on fine spatial scales enhances fusion reactivity, enabling ignition at lower temperature. A modified Lawson-like ignition criterion is derived for inertially confined plasmas harboring turbulent kinetic energy. For some turbulent energy spectra, hot spots ignite at lower energy density and smaller volume. While detrimental mixing effects typically accompany turbulence and obscure these advantages, targets might be engineered to drive flow in regions where it is beneficial. The optimal length scale for this driving is identified, typically lying in the micrometer range.

Alpha particles↗

Toroidal modeling of energetic passing particle drift kinetic effects on tearing mode stability

Abstract Drift kinetic effects of the neutral beam injection induced passing energetic particles (EPs) on the linear stability of the n = 1 tearing mode (TM) (with the dominant poloidal harmonic of m = 2) are numerically investigated utilizing the MARS-K code (Liu et al 2008 Phys. Plasmas 15 112503), in a tokamak plasma with finite equilibrium pressure and anisotropic thermal transport. In the low plasma pressure regime, it is found that co- (counter-) passing EPs stabilize (destabilize) the TM, agreeing with previous studies. However, as the plasma pressure increases beyond a critical value, it is found that co-passing EPs also destabilize the mode. An in-depth analysis reveals that the net effect of co-passing EPs is a result of competition between the stabilizing contribution from the non-adiabatic drift kinetic terms and the destabilizing contribution associated with adiabatic terms, with the latter becoming more dominant at higher equilibrium pressure. Non-perturbative magnetohydrodynamic-kinetic hybrid modeling also finds that co- and counter-passing EPs modify the TM eigenfunction differently, with the counter-passing EPs enhancing the sideband harmonics. Furthermore, effects of the plasma resistivity and toroidal rotation, as well as that of the equilibrium distribution of EPs in the particle pitch angle space, are also investigated, showing asymmetric results on the TM stability between the co- and counter-passing EPs. The first order finite orbit width correction is found to be stabilizing with co-passing EPs and destabilizing with counter-passing particles. Finally, drift resonances between passing EPs and the TM induce finite frequency to the mode and generate finite net torques inside the plasma, due to the neoclassical toroidal viscosity and the Reynolds stress associated with 3D perturbations.

Physics↗

Diamond formation kinetics in shock-compressed C$-$H$-$O samples recorded by small-angle x-ray scattering and x-ray diffraction

Extreme conditions inside ice giants such as Uranus and Neptune can result in peculiar chemistry and structural transitions, e.g., the precipitation of diamonds or superionic water, as so far experimentally observed only for pure C$-$H and H 2 O systems, respectively. Here, we investigate a stoichiometric mixture of C and H 2 O by shock-compressing polyethylene terephthalate (PET) plastics and performing in situ x-ray probing. We observe diamond formation at pressures between 72 ± 7 and 125 ± 13 GPa at temperatures ranging from ~3500 to ~6000 K. Combining x-ray diffraction and small-angle x-ray scattering, we access the kinetics of this exotic reaction. The observed demixing of C and H 2 O suggests that diamond precipitation inside the ice giants is enhanced by oxygen, which can lead to isolated water and thus the formation of superionic structures relevant to the planets’ magnetic fields. Moreover, our measurements indicate a way of producing nanodiamonds by simple laser-driven shock compression of cheap PET plastics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-Dependent Corrosion Behavior of Aluminum Using Advanced Electrochemical and Characterization Techniques

The time-dependent corrosion behavior of pure aluminum (Al) in a chloride-containing environment was investigated using various electrochemical and characterization techniques for up to 336 h. Transmission electron microscopic and secondary ion mass spectroscopic analysis revealed the continuous dissolution of the surface film over the immersion time. In the meantime, the increasing passive oxide thickness resulted in the surface film resistance enhancement over the immersion time, as indicated by the electrochemical impedance spectroscopic analysis. The electrochemical noise measurements showed an increase in the corrosion kinetics with immersion time until 60 h because of the accelerated localized corrosion in the early stage of immersion. However, an inhibition in corrosion kinetics occurred after longer immersion times due to corrosion product deposition inside the pit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of laser energy to gas kinetic energy

Techniques for the gas-phase absorption of laser energy with ultimate conversion to heat or directed kinetic energy are reviewed. It is shown that the efficiency of resonance absorption by the vibration/rotation bands of the working gas can be enhanced by operating at sufficiently high pressures so that the linewidths of the absorbing transition exceed the line spacing. Within this limit, the gas can absorb continuously over the full spectral region of the band, and bleaching can be minimized since the manifold of molecular vibrational levels can simultaneously absorb the laser radiation.

Caledonia, G. E.↗

A possible explanation of the electron temperature enhancement in the wake of a satellite

A numerical simulation was performed in an attempt to explain the enhancement of electron temperature in the wake of an ionospheric satellite in terms of counterstreaming plasma expansions. The simulation was conducted using full kinetic treatments (Vlasov-Poisson code) for both the plasma electrons and ions. The calculations indicated that at a distance of a few Debye lengths from the surface of the body the wake/ambient electron-temperature ratio reaches a value of about 2. This result is in good agreement with some in situ and laboratory experimental results.

Singh, Nagendra↗