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At least 631 records · Page 35

Mechanism and kinetic study of rare earth extraction from allanite by direct acid leaching

Direct acid leaching was conducted to recover rare earth elements (REEs) from an allanite ore assaying 9,861.4 ppm of REEs. The effects of operational variables such as acid type, sulfuric acid (H 2 SO 4 ) concentration, temperature, solid/liquid (S/L) ratio, and particle size on the total REE (TREE) recovery were systematically examined. The REE mineralogy and the involved leaching mechanisms were investigated by microscopic characterization and residue re-leaching tests. It was found that approximately 80% of REEs was extracted using 1 M H 2 SO 4 at 75 °C for 2 h. Increasing temperature significantly improved the REE extraction, while changing acid type, H 2 SO 4 concentration, and particle size did not. The TREE recovery also gradually decreased at higher S/L ratios. The low fraction of Si leached (<4.0%) suggested that the extraction did not significantly alter the crystal structure of the dominant mineral. The leaching kinetics of REEs were fast within the first 10 min, followed by a much slower stage (i.e., 10-120 min). The kinetic modeling results showed that each stage may be controlled by both chemical reaction and diffusion (i.e., mix control). The activation energies for REE leaching using 1 M H 2 SO 4 in the 0-10 min and 10-120 min were determined to be 20.3 and 10.8 kJ/mol, respectively. Finally, the residue re-leaching results suggested that the fast leaching kinetics at the beginning may be explained by the preferential decomposition of metamict allanite rather than the formation of silica gel, while the following slower leaching stage was due to the dissolution of difficult-to-leach REE-bearing minerals such as well-crystallized allanite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective dopant segregation modulates mesoscale reaction kinetics in layered transition metal oxide

Incorporation of foreign elements into the cathode material is broadly adopted by both academia and industry to improve the battery performance. The lack of an in-depth understanding for the underlying mechanism, however, makes it a largely try-and-error process with unsatisfactory efficiency and effectiveness. This is particularly true for the electrochemical reaction kinetics that is heterogeneous over a broad range of length scales and is determined collectively by the cathode’s electronic structure, lattice configuration, and micro-morphology. In this work, we unveiled a facet-dependent dopant segregation effect in Zr-modified single-crystal LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode. By forming kinetically favored corners on the cathode particles, the presence of a trace amount of Zr critically modulates the mesoscale reaction kinetics. Our findings suggest that a delicately controlled dopant distribution is a viable strategy for designing the next-generation battery cathode with superior structural and chemical robustness.

36 MATERIALS SCIENCE↗

Simulation of edge localized mode heat pulse using drift-kinetic ions and Boltzmann electrons

This article reports on 1D+2V heat pulse propagation studies using the COGENT guiding center kinetic code. The model uses magnetized kinetic ions and a simple Boltzmann electron model. Results agree with previous kinetic and fluid modeling benchmark studies that correspond to the parameters of edge localized modes (ELMs) observed on the JET tokamak. The plasma parameters for the edge pedestal and ensuing ELM dynamics are in the low collisionality regime. Hence, the dominant balance between the assumed Maxwellian ELM source and collisionless parallel advection causes the ion PDF to develop a significantly anisotropic velocity distribution. Adding nonlinear Coulomb ion-ion collisions to the model acts to smooth the sharp features of the ion distribution function, but the anisotropy remains robust due to the low collisionality.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Combustion chemistry in the twenty-first century: Developing theory-informed chemical kinetics models

Over the past 20 to 25 years theoretical chemistry (particularly theoretical chemical kinetics) has played an increasingly important role in developing chemical kinetics models for combustion. Theoretical methods of obtaining rate parameters are now competitive in accuracy with experiment, particularly for small molecules. Moreover, theoretical methods can deal with conditions that experiments frequently cannot. In addition to increased accuracy, theory has rejuvenated methods and discovered phenomena that were completely unappreciated, or at least underappreciated, in the 20th century. Our primary interest here is in molecular-level issues, i.e. in calculating rate and transport parameters. However, dealing with kinetics models that involve thousands of reactions and hundreds of species is important for practical applications and is relatively new to the 21st century. Theory, in a general sense, and theoretical methods development have a role to play here too. We discuss in this review all these topics in some detail with an emphasis on issues and methods that have emerged in the last 20 years or so. Even so, our review is selective, rather than comprehensive, out of necessity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic modeling of ignition in miniature shock tube

The ignition delay times of toluene, n-heptane/iso-octane primary reference fuel blends, and toluene/n-heptane/iso-octane toluene primary reference fuel blends were studied in the miniature high repetition rate shock tube (HRRST). In the HRRST, the temperature and pressure change during the test time, complicating interpretation of ignition delay times. Two methods of chemical kinetic modeling were employed in order to account for the changing thermodynamic states in the HRRST. One was based on direct modeling using the pressure profile and the kinetic mechanism, and the other was based on a Livengood-Wu type approach using modeled constant volume ignition delay times. Two different kinetic mechanisms were used in modeling the data. Both methods showed agreement with experimental data over a range of temperatures, pressures, and blends. While overall agreement was fair, agreement was poorer for one of the mechanisms for the primary reference fuel blends. An evaluation of the ignition delay iso-contours from these mechanisms for representative HRRST experiment thermodynamic trajectories revealed that the HRRST measured IDTs are controlled by the high temperature chemistry and are more sensitive to temperature. Furthermore, the different performance of mechanisms is therefore attributed to their different high temperature reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An improved semi-global intrinsic kinetics model for high temperature carbon oxidation

Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.

33 ADVANCED PROPULSION SYSTEMS↗

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface oxygen exchange kinetics of mixed conducting oxides: Dilatometric vs electrical conductivity relaxation study

The surface oxygen exchange kinetics of mixed ionic-electronic conducting (MIEC) oxides play a crucial role in a variety of applications, including solid oxide fuel/electrolysis cells (SOFCs/SOECs), permeation membranes and sensors. To date, a variety of methods, including isotope exchange, electrical conductivity, optical absorptivity and thermogravimetry relaxation, and impedance spectroscopy have been used to measure the oxygen exchange coefficient of MIEC oxides. Each of these methods have their advantages and limitations, depending on the physical and chemical properties of the investigated materials and their sample dimensions and densities. Here, we demonstrate the ability to precisely measure the surface oxygen exchange coefficient (k chem ) of MIEC model material Pr 0.1 Ce 0.9 O 2-δ (PCO) by use of dilatometric relaxation measurements, particularly of interest for materials that exhibit larger chemical expansion coefficients. This is achieved by use of porous bulk specimens to ensure that the contribution of oxygen exchange to the overall kinetics is dominant. We demonstrate that k chem values extracted from chemical expansion relaxation measurements on PCO are nearly identical to those derived from electrical conductivity relaxation measurements. As a result, this provides the opportunity to precisely investigate the oxygen exchange and chemical expansion kinetics of a wide range of materials used in high-temperature applications, particularly where more conventional methods are difficult or inappropriate to apply.

(Pr,Ce)O2-x↗

Uniformity of GaAs solar cells grown in a kinetically-limited regime by dynamic hydride vapor phase epitaxy

We demonstrate solar cell devices grown on 50 mm diameter GaAs substrates by dynamic hydride vapor phase epitaxy (D-HVPE). In contrast to our prior D-HVPE devices, grown at 650 °C in a transport-limited regime, these devices were grown at 700 °C in a kinetically-limited growth regime in which the growth rate uniformity is controlled by thermally-activated surface reactions. These devices exhibit open-circuit voltages up to 1.07 V, nearly identical performance to the devices grown at lower temperature in a different growth regime. We evaluate the uniformity of device performance and find only a 1% variation in absolute, device efficiency across the majority of the wafer in devices without anti-reflection coating. We analyze the GaAs and GaInP thickness uniformity and GaInP compositional uniformity, using high-tresolution x-ray diffraction mapping, and find that any non-uniformity in device efficiency is not related to variations in these structural parameters. We combine three-dimensional computational fluid dynamics modeling of our reactor with a kinetic model for GaAs growth, and use the combined model to predict spatial GaAs growth rate over a 50 mm wafer area. We compare these predictions with experimental data from our D-HVPE reactor and find excellent agreement. We use the model to the gain insight into the specific mechanisms that control GaAs spatial uniformity in the kinetically-limitedgrowth regime. Furthermore, these results suggest a large parameter window for the growth of high-performance optoelectronic devices by D-HVPE, possibly with large area uniformity.

14 SOLAR ENERGY↗

A dynamic kinetic model captures cell-free metabolism for improved butanol production

Cell-free systems are useful tools for prototyping metabolic pathways and optimizing the production of various bioproducts. Mechanistically-based kinetic models are uniquely suited to analyze dynamic experimental data collected from cell-free systems and provide vital qualitative insight. However, to date, dynamic kinetic models have not been applied with rigorous biological constraints or trained on adequate experimental data to the degree that they would give high confidence in predictions and broadly demonstrate the potential for widespread use of such kinetic models. In this work, we construct a large-scale dynamic model of cell-free metabolism with the goal of understanding and optimizing butanol production in a cell-free system. Using a combination of parameterization methods, the resultant model captures experimental metabolite measurements across two experimental conditions for nine metabolites at timepoints between 0 and 24 hours. Here, we present analysis of the model predictions, provide recommendations for butanol optimization, and identify the aldehyde/alcohol dehydrogenase as the primary bottleneck in butanol production. Sensitivity analysis further reveals the extent to which various parameters are constrained, and our approach for probing valid parameter ranges can be applied to other modeling efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of Stepwise Ultrafast Crystallization Kinetics of Donor–Acceptor Conjugated Polymers and Correlation with Field Effect Mobility

The semicrystalline microstructures of donor-acceptor conjugated polymers strongly impact their optoelectronic properties. The control of the microstructure relies on the understandings of the crystallization processes in these polymers, from packing structures to crystallization kinetics. How fast these conjugated polymer chains crystallize and how their chemical structures and pre-existing microstructure history influence their crystallization have so far remained unclear, due to the fast crystallization rate caused by chain rigid structures and strong interactions. Here, ultrafast scanning calorimetry (FSC) is employed to reveal the crystallization behaviors of high perform- ance diketopyrrolopyrrole (DPP)-based conjugated polymers with scanning rates up to 500 000 K/s. Through elaborately designed nonisothermal and isothermal crystallization studies, we probed the fast crystallization kinetics and extracted the two-step crystallization process of these polymers quantitatively. We found that both the rigidity of the chain backbones and the preinduced crystalline microstructures can influence the crystallization rate over an order of magnitude at the same degree of undercooling. We further demonstrated the manipulated crystallization kinetics in the DPP-based polymer films with different amounts of preinduced crystallites and correlate it to the polymers’ charge transport mobility.

36 MATERIALS SCIENCE↗

High-Temperature Fe-Based Fischer–Tropsch Synthesis: Experimentally Validated Kinetic Models Implemented at Pellet and Reactor Scales

Pellet- and reactor-scale models for Fischer–Tropsch synthesis (FTS) with a Fe–K/silica catalyst were developed to investigate the sensitivity of the hydrocarbon products and carbon dioxide selectivity to process conditions and feed composition at high temperature (350–400 °C), moderate pressure (1–10 bar), and a range of H 2 /CO ratios (3–1). The major objective of this paper is to develop, validate, and evaluate a high-temperature FTS model that is then used to assess the feasibility of process integration with syngas production. Since there is limited kinetic data available, in literature at these conditions, bench-scale reactor tests were conducted to obtain operational data for parameter fitting of kinetic expressions used in the model. This resulting kinetic model demonstrated agreement with the experimental data with an R 2 of 0.97 to the testing data set and, thus, was feasible to apply at pellet and reactor scales. Here, multiple pellet sizes were modeled to detail the role of transport limitations as the sphere’s diameter approached and exceeded 1 mm. Application of the reactor model indicated that hydrocarbon selectivity depended strongly on temperature, whereas the ratio of olefin to paraffin products decreased with increasing temperature, pressure, and H 2 /CO ratio. Product selectivity was not sensitive to the conversion of carbon monoxide. Furthermore, the roles of the pressure and H 2 /CO ratio were closely coupled. At a H 2 /CO ratio of 3, only slight variations in selectivity occurred over a pressure range of 1–20 bar, whereas at a ratio of 1, selectivity could vary by as much as 30% over the same pressure range. At pressures below 5 bar and temperatures above 350 °C, minimal selectivity to heavy hydrocarbons (C 12+ ) is obtained, and selectivity to midrange products (C 5–11 ) rapidly declined as pressure dropped below 5 bar, which indicated that an operational pressure of at least 5 bar is needed to achieve reasonable yields in this temperature range. These results, while tentative, provide guidelines for further experimentation and evaluation of integrated FTS processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Molecule Kinetics of Styrene Hydrogenation on Silica-Supported Vanadium: The Role of Disorder for Single-Atom Catalysts

We report a theoretical approach for the study of supported atom catalysis is developed based on recent advances in the study of single-molecule kinetics. This view is particularly useful in exhibiting the role of disorder in single-atom and single-site catalysts on amorphous supports. The distribution of passage times (or waiting times) through a complex catalytic network originating from a set of coupled active sites is described by a probability distribution function (PDF), f(t), that reflects the local environment of the reaction center. An efficient algorithm is developed based on the linear algebra of the Markov transition matrix that produces f(t) or its moments. The kinetics of the hydrogenation reaction of styrene on an organovanadium(III) catalyst supported on amorphous silica is studied. A kinetic model consisting of three intertwined catalytic cycles emanating from three chemically distinct active sites is proposed to describe the chemistry. Density functional theory (DFT) calculations are employed to determine the free energy barriers of the reactions, which are used to construct the rate coefficient matrix. The disorder induced by the amorphous support material is divided into a low-dimensional short-range component reflecting the covalent structures near the reaction center and a weaker long-range component modeling the bulk randomness. The results are computed and analyzed for a wide range of concentration values and disorder scenarios. The unusual structure in the f(t) PDF is found to occur for certain cases that reveal the contribution of multiple catalytic pathways acting in concert.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing the Influence of Binding Motifs on Electron Transfer and Recombination Kinetics for CdSe Quantum Dots Functionalized with a Modified Viologen

Anchoring of molecules to the surfaces of semiconductor nanocrystals (NCs) presents an opportunity to leverage the precise synthetic tunability of molecular function and the remarkable light harvesting properties of NCs to drive photochemical reactions. However, charge transfer between the two species depends not only on the energy level alignments but also on the details of their binding interactions, which are difficult to probe. Here, in this work, we characterize the binding between CdSe quantum dots (QDs) and a new phosphonated derivative of the electron acceptor methyl viologen, designed to attach to the QD surface via the phosphonate group. We use isothermal titration calorimetry to probe the thermodynamics of the QD–molecule interaction and use the parameters determined therein to analyze transient absorption spectroscopy measurements of forward and back electron transfer from QDs to the viologen. We find that the ligand-like phosphonate binding leads to an electron-transfer rate constant that is 3 orders of magnitude smaller than that for the face-on binding of the bipyridine ring of methyl viologen. Back electron transfer is also significantly slower in the derivative. Interestingly, a minor fraction of the phosphonated derivative also binds in the face-on configuration, with similar forward and back electron transfer kinetics as methyl viologen. Numerical simulations show that the ligand-like binding will lead to significantly improved quantum yields of photocatalysis over a wide range of reaction rates. By independently characterizing binding thermodynamics and charge transfer kinetics, this work reveals how the complexities underlying electron transfer at the NC–molecule interface determine photocatalytic outcomes. This work also represents a step toward controlling forward and back electron transfer kinetics via rational molecular design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Atom Doping at the Molecule–Metal Interface: How Rh Affects Surface Explosion Kinetics

Controlling chemical reactions at interfaces is central to many fields, including atmospheric, environmental, and biological chemistry as well as catalysis and corrosion. We performed a fundamental study of how catalytically active Rh atoms placed at and above a molecule-metal interface influence the surface reaction kinetics of tartaric acid (TA) decomposition. Specifically, TA decomposition on Cu(100) exhibits autocatalytic decomposition kinetics involving a slow initiation step followed by fast decomposition of the molecular layer. These so-called “surface explosions” are extremely sensitive to initial conditions, making it fundamentally interesting to study how the placement of reactive atoms affects the reaction rate. Temperature-programmed reaction (TPR) experiments reveal that Rh atoms embedded in the Cu(100) surface beneath TA (TA/Rh/Cu) or atop the TA layer (Rh/TA/Cu) reduce the decomposition temperature and modify the reaction rate constants. Isothermal TPR analysis reveals that Rh enhances both the initiation rate constant, k i , and the explosion rate constant, k e , facilitating explosive decomposition at lower temperatures. This result provides evidence that both the initiation and explosion steps occur at the metal-molecule interface and are accelerated by the presence of Rh at this interface. This study illustrates how small amounts of reactive elements may be used to control nonlinear kinetic processes at interfaces.

desorption↗

Transient Kinetic Selectivity in Nanotubes Growth on Solid Co–W Catalyst

Solid Co–W catalysts have been shown to yield single-walled carbon nanotubes (CNT) with high selectivity, simplistically attributed to CNT-catalyst symmetry match for certain chiral indices (n,m). Here, based on large-scale first-principles calculations combined with kinetic Monte Carlo simulations, we show instead that such selectivity arises from a complex kinetics of growth. The solid Co7W6 catalyst strongly favors a restructured, asymmetric CNT edge which entails preferential nucleation of tubes with 2m < n but much faster growth of chiral tubes with n ≤ 2m. We uncover a tendency of interface defects formation that, although rare, drive CNT type change from smaller to larger chiral angles (zigzag to armchair). Furthermore, being both least prone to defects and fast growing, the (12,6) CNT appears as a transient, kinetics-selected type reaching highest abundance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the Microscale Behavior and Phase Separation Kinetics of Thermally Responsive Ionic Liquid–Water Mixtures

Thermally responsive ionic liquids (ILs) exhibit liquid-liquid phase separation into a water-rich (WR) and ionic-liquid-rich (ILR) phase when heated above a lower critical solution temperature (LCST). This phase behavior has been leveraged for applications ranging from forward osmosis (FO) desalination, where the IL acts as a draw solute, to refrigeration and dehumidification cycles, where the IL acts as a liquid desiccant. While significant effort has been devoted to characterizing the thermodynamic and thermophysical properties of LCST ILs, their phase separation kinetics have not been investigated. In this work, we describe the macroscale phase separation kinetics (phase separation time) by gleaning insight into the microscale colloidal behavior of aqueous mixtures of four different materials, P 4444 TFA (tetrabutylphosphonium-2,4-trifluoroacetate), P 4444 DMBS (tetrabutylphosphonium-2,4-dimethyl-benzenesulfonate), N 4444 Sal (tetrabutylammonium salicylate), and P 4444 Sal (tetrabutylphosphonium salicylate) as a function of IL concentration at a separation temperature of 70 °C. We report the discontinuous microscale size distributions for each material and correlate their theoretical settling velocities to experimental phase separation times. The results indicate that a simple Stokes' law model can predict the phase separation time within reasonable accuracy. Overall, this work lays the foundation for understanding the micro- to macroscale phase separation behavior and kinetics of LCST ILs for various water-energy applications.

LCST↗

Methanol Decomposition on Copper Surfaces under Ambient Conditions: Mechanism, Surface Kinetics, and Structure Sensitivity

Here, we study the adsorption of methanol vapor under ambient pressure and temperature conditions on low-index Cu surfaces using surface-sensitive infrared (IR) and X-ray spectroscopy techniques. The first step of methanol decomposition, i.e. , breaking of the O—H bond to form surface-bound methoxy, readily occurs under ambient conditions. Time-lapse IR spectra clearly indicate a gradually decreasing methoxy coverage, which does not obey well established kinetic models. We rationalize the initial temperature-independent, high, nonequilibrium coverage of methoxy by a H-bonded methanol assembly in the precursor state. A temperature-dependent equilibrium coverage is achieved as the excess methoxy is eliminated gradually via further dehydrogenation to CO that desorbs to the gas phase. The kinetics of this process displays a significant structure sensitivity with considerably faster kinetics on the Cu(110) surface compared to Cu(111) and Cu(100) surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗