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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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At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Crystallization Physics in Biomacromolecular Systems

The crystals are built of molecules of protein, nucleic acid and their complexes, like viruses, approx. 5x10(exp 3)+ 3x10(exp 6) Da in weight and 2 + 20 nm in effective diameter. This size strongly exceeds action range of molecular forces and makes a big difference with inorganic crystals. Intermolecular contacts form patches on the biomacromolecular surface. Each patch may occupy only a small percent of the whole surface and vary from polymorph to polymorph of the same protein. Thus, under different conditions (pH, solution chemistry, temperature, any area on the macromolecular surface may form a contact. The crystal Young moduli, E approx. equals 0.1 + 0.5 GPa are more than 10 times lower than that of inorganics and the biomolecules themselves. Water within biocrystals (30-70%) is unable to flow unless typical deformation time is longer than approx. 10(exp -5)s. This explains the discrepancy between light scattering and static measurements of E. Nucleation and Growth requires typically concentrations exceeding the equilibrium ones up to 100 times - because of the new size scale results in 10 - 10(exp 3) times lower kinetic coefficients than that needed for inorganic solution growth. All phenomena observed in the latter occur with protein crystallization and are even better studied by AFM. Crystals are typically facetted. Among unexpected findings of general significance are - net molecular exchange flux at kinks is much lower than that expected from supersaturation, steps with low (< approx. 10(exp -2)) kink density at steps follow Gibbs-Thomson law only at very low supersaturations, step segment growth rate may be independent of step energy. Crystal perfection is a must of biocrystallization to achieve the major goal to find 3-D atomic structure of biomacromolecules by x-ray diffraction. Poor diffraction resolution (> 3Angstrom) makes crystallization a bottleneck for structural biology. All defects typical of small molecule crystals are found in biocrystals, but the defects responsible for poor resolution are not identified. Conformational changes are one of them. Biocrystallization in microgravity reportedly results in 20% cases of better crystals. The mechanism of how lack of convection can do this is still not clear. Lower supersaturation, self-purification &om preferentially trapped homologous impurities and step bunching are viable hypotheses.

Chernov, A. A.↗
DOE OSTI2020

Relationship between the Nature of Monovalent Cations and Charge Recombination in Metal Halide Perovskites

We report charge recombination rates in lead iodide perovskites with alloys of formamidinium (FA) and methylammonium (MA) cations, FA x MA 1–x PbI 3 , 0 ≤ x ≤ 0.9, prepared through ion exchange with minimal differences in morphology and charge trap density. Our results show that the trap-mediated recombination rate increases over 2 orders of magnitude with decreasing MA content. These results are consistent with a proposed mechanism that MA molecules are more effective in screening charged defects. In contrast, band-to-band charge recombination rates are minimized at an intermediate alloy composition. Here, these findings reveal that the monovalent cations impact recombination processes through different mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Coupling between interfacial charge and mechanical deformation at high temperatures in ceramics. Final report

Basic research, under this project, has led to new fundamental discoveries in the effect of electric field (and temperature) on diffusion kinetics, electroluminescence and electronic conductivity in ceramic materials. For example, yttria stabilized zirconia sinters in just seconds well below 1000°C, while, at the same time, exhibiting a highly non-linear rise in conductivity, and intense electroluminescence. The phenomenon has been shown to occur in nearly all ceramics whether they are ionic or electronic conductors, or insulators. The rise in conductivity leads to Joule heating but in-situ measurements with a platinum standard at APS and Brookhaven (NSLS-II) have shown that the temperatures are much below what would have been needed to sinter in a few seconds. We have explored the hypothesis that huge concentrations of Frenkel pairs of vacancies and interstitials are produced. While these point defects accelerate sintering (by the interstitials being transported to the pores and the vacancies to the grain boundaries), they may also produce electron-hole pairs which can impart high electrical conductivity or recombine to emit photons. Many measurements, including in-situ measurements of lattice expansion are consistent with this hypothesis. However, the energy barrier for generating Frenkels in zirconia for example is much larger than can be expected at temperature and electrical fields in these experiments. Most recent work suggests that short wavelength phonons play a critical role in the genesis of the “flash” phenomenon. For example, the Debye temperature has been shown to be the lower bound for initiating flash. Molecular dynamics simulations have shown that large concentrations of Frenkel pairs can form under the proliferation of “optical” phonons at the edge of the Brillouin zone, that is with a wavelength at or below the lattice parameter. This project has led to the development of new experimental techniques as well as a software hardware interface for process and control and data analysis in real time, with a time scale of less than one second. This approach spells a new paradigm in materials science research. It potential impact on high rate manufacturing is self evident.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electron/hole selectivity in organic semiconductor contacts for solar energy conversion (Final Report)

Four major and accomplishments for the project "Electron/hole selectivity in organic semiconductor contacts for solar energy conversion.'' are reported. The first is a development of a model describing the contact-determined behavior of a solar cell. The most basic solar cell consists of an intrinsic (pure) semiconductor that acts as an absorber to which contacts are made that provide the asymmetry needed to create a driving force (voltage) for the directional flow of electrons (current), in other words, to convert sunlight into electrical energy. The asymmetry at the contacts comes from the different rate at which electrons and holes, the charge carriers generated by illumination, are collected. We developed a model that describes the ideal current-voltage, and hence energy converting properties, of an ideal photovoltaic that is entirely determined by the kinetics for these charge collection processes. Second, we measured how organic semiconductor interfacial layers impact contact electron and hole transfer rates at semiconductor interfaces and described how these concepts do or do not determine the open-circuit voltage of a solar cell. The work clearly controverts common general misconceptions about the action of contact interfacial layers, such as the idea that improved selectivity for one carrier over the other results from decreased recombination, and quantitatively demonstrates how specific interfacial layer materials act to improve the efficiency of a solar cell. Third, we measured the sub-band gap external quantum efficiency (EQE) of a series of organometal halide perovskite (“perovskite”) solar cells. These measurements quantified band-tailing and revealed defect states, which can cause recombination, that correlate with composition, performance, and hysteresis. Finally, we developed a semiconductor bipolar membrane that uses light to pump ions. This structure is unique among systems that drive ion gradients using light in that it is designed to pump salt rather than one sign of ion; it is a photochemical salt pump.

14 SOLAR ENERGY↗
DOE OSTI2026

Temperature-Dependent Sn Incorporation and Defect Formation in Pseudomorphic SiSn Layers on Si (001) via Molecular Beam Epitaxy

SiSn alloys have attracted growing interest for group-IV bandgap engineering, although their epitaxial growth remains challenging due to the extremely low equilibrium solubility of Sn in Si. In this work, fully strained (pseudomorphic) SiSn epitaxial layers were grown on Si (001) substrates by means of molecular beam epitaxy. A systematic investigation reveals a strong inverse correlation between growth temperature and Sn incorporation efficiency. Despite a constant Sn flux, the incorporated Sn composition decreases from 5.5% to 3.2% as the growth temperature increases, indicating a pronounced temperature dependence of Sn incorporation. Reflection high-energy electron diffraction indicates a gradual transition of the growth from two-dimensional to three-dimensional with increasing film thickness. Structural characterization by means of X-ray diffraction, atomic force microscopy, and transmission electron microscopy confirms the pseudomorphic growth and smooth surface morphology and reveals twins and stacking faults near the surface region. These results establish a quantitative reference for SiSn growth kinetics and provide guidance for future studies of SiSn and SiGeSn alloys in silicon-compatible electronic and optoelectronic applications.

SiSn alloys↗
DOE OSTI2024

Role of Short-Range Order on Diffusion Coefficients in the Li–Mg Alloy

Li–Mg alloys are important because of their beneficial role in fostering uniform plating and stripping of lithium in all-solid-state batteries. The alloy Li x Mg 1–x forms a solid solution on the BCC crystal structure when the lithium content is greater than x ≈ 0.3. The activation barriers of lithium and magnesium exchanges with a vacancy, crucial for substitutional diffusion, are predicted to be exceptionally low and almost identical, with negligible dependence on the alloy composition. The equilibrium vacancy concentration at room temperature is predicted to be very low, and it also remains almost constant with no dependence on Mg content in the alloy (for x Li ≥ 0.5). Nevertheless, both experiments and kinetic Monte Carlo simulations indicate that the tracer diffusion coefficients decrease by almost an order of magnitude with the addition of Mg to the alloy. In this contribution, the crucial role that chemical short-range order plays in affecting the diffusion coefficients is studied. Chemical short-range order is found to increase the effective activation barrier for lithium and magnesium diffusion by making successive atomic hops with vacancies correlated.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of Confinement of SIA Cluster Diffusion by Impurities on Radiation Defect Accumulation due to 14MeV neutrons in Tungsten

Impurities acting as traps, reduce the self-interstitial atom (SIA) cluster mobility, thereby increasing recombination and in turn enhancing radiation-resistance of polycrystalline materials. However, at elevated temperatures, depending on SIA-trap (impurity) binding energy, SIA clusters may trap and detrap (detach) numerous times. In tungsten, SIA clusters of all sizes glide one-dimensionally (1D) along their Burgers vector direction. Hence, detrapped SIAs would retrace their path, confining their 1D-glide between traps. However, small SIA clusters can change the direction of their 1D-glide by overcoming a rotation barrier. In addition, impurities or solutes are known to reduce this barrier. A lower rotation barrier can result in detrapped SIA clusters that diffuse in a random 1D direction, effectively leading to 3D (net-3D) diffusion. Here we investigate the effect of two cases of SIA diffusion, namely confined-1D diffusion and net-3D diffusion, on the damage accumulation in polycrystalline tungsten under 14 MeV neutron irradiation using the object kinetic Monte Carlo method. Simulations were performed using cascade debris obtained from molecular dynamics simulations with primary knock-on atom (PKA) energies corresponding to 14 MeV neutrons. In the simulations with net-3D diffusion, SIA clusters of all sizes diffuse in a random 1D direction after the clusters detrap. While for the confined 1D diffusion case, SIA clusters larger than size 5 retain their original direction of 1D-glide. In both types of simulations, trapped vacancies are assumed to be permanently immobilized. Unexpectedly, the damage accumulation was lower with confined 1D diffusion than that with net-3D. We present a systematic comparison of the influence of the two cases of SIA diffusion on the radiation damage accumulation as a function of dose rate, detrapping barrier, and impurity concentration at 1025 K.

Accumulation and recovery of lattice damage, tungs↗
DOE OSTI2026

Self‐Limiting Polymerization‐Induced Crystallization‐Driven Self‐Assembly (SL‐PI‐CDSA) Enables Templated Synthesis of Chiral Plasmonic, Hybrid 2D Hexagonal Assemblies

Examples of self-regulating synthetic self-assembly are relatively few, with most known chemical systems relying on kinetic rather than thermodynamic control. Herein, we demonstrate the rapid generation (t ≤ 5 min) of size-tunable ultralow dispersity (Ð ≤ 1.01) 2D hexagonal nanosheets governed by self-limiting self-assembly (SLSA). Self-assembly in natural systems occurs with exquisite control of structure, function, and dimension. We demonstrate that key aspects of biological assembly can be rationally applied toward the development of bottom-up approaches for the construction of chiral nanomaterials. To this end, self-limiting polymerization-induced crystallization-driven self-assembly (SL-PI-CDSA) of modular and templating aryl isocyanide (AIC) monomers yields functional 2D assemblies permitting post-polymerization/assembly modifications. Detailed study of the internal and external structure of the hexagonal nanosheets reveals topological defects which offer mechanistic insights into both their assembly and subsequent utilization. Specifically, these features enable fabrication of chiral hybrid organic–inorganic nanomaterials incorporating chiral plasmonic metal nanoparticles (MNPs). Our results suggest that the synergistic interplay of template-driven confinement and hierarchical chirality induce symmetry breaking of in situ-generated gold MNPs. We anticipate that the platform presented will facilitate fabrication of new hybrid, chiral organic–inorganic nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Synthesizing intermetallic thermoelectric materials using metal flux growth method

With zero energy poverty by 2050 goals, exploring innovative energy technologies is essential. Thermoelectric materials (TEMs) have the potential to harness waste heat and convert it to electricity (e.g., for spacecraft power, sensors, and cryogenic cooling). Two limitations of thermoelectric compounds are their low efficiency and limited pool of materials. Optimizing the efficiency of TEMs is challenging due to the interdependent relationship between electrical and thermal conductivity. A deeper understanding of electronic properties and lattice thermal conductivity is necessary to “understand, predict and ultimately control” the thermoelectric properties of TEMs. Understanding the influence of light-atom-doping and intrinsic defects on the electronic properties of the f-element containing TEMs are important questions that need to be answered to design and synthesize TEMs with optimal parameters. The purpose of this work is to understand how doping f-element based TEMs with light elements, such as carbon and boron, would impact the crystal structure, bond lengths, band gaps, and thermoelectric characteristics. High-quality f¬-element containing intermetallic single crystals are grown in metal flux media. In molten metal flux growth method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. As these are solution-state reactions, we can use lower temperatures than solid-state reactions and isolate the kinetic products instead of the thermodynamically stable compound. Then these are characterized using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, magnetization, electrical and thermal conductivities, and thermoelectric power.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2020

A quantitative phase-field model for gas bubble evolution in UO2

Due to the large formation energy of vacancies and noble gas atoms in the form of interstitials or substitutional atoms in nuclear fuel (UO2), the thermodynamic equilibrium concentrations of these species are very low in the nuclear fuel matrix even at very high temperatures, which imposes difficulties upon the quantitative study of bubble evolution via the phase-field method. In this study, a quantitative phase-field model is proposed to deal with this problem. The system’s free energy density is derived according to the principles of thermodynamics, with consideration of the elastic effect and with the use of real material parameters from experiments. The model is useful for the study of the kinetics of gas bubble growth with very dilute concentrations of vacancy and gas atoms in the matrix. This model is applied to study single bubble growth and multiple bubble growth under various concentrations of vacancy and gas atoms and at various temperatures. The elastic effect and the effects of the generation rate of vacancies and gas atoms on bubble growth are analyzed.

low defect concentration, nuclear fuel, gas bubble↗
DOE OSTI2024

Materials genome innovation for computational software (magics) center

Functional layered material (LM) architectures will dominate nanomaterials science in this century. We have developed theory, modeling, simulation, and software and data tools that enhance understanding and AI guide synthesis, enable characterization of complex structures, and improve capabilities in the predictive design and growth of LMs. Research at the Center has focused on: Computational synthesis and characterization: AI guided synthesis and experimental synthesis of stacked LMs with tailored properties via optimized chemical vapor deposition (CVD) growth and liquid-phase exfoliation; study defects, edges, grain boundaries, wrinkling of atomic layers and their effects on chemical, mechanical, electrical, and optical properties. Far-from-equilibrium processes: Joint experimental and simulation based probe of electronic processes with NAQMD and ultrafast X-ray free-electron laser (XFEL) and ultrafast electron diffraction (UED) facilities at Stanford. Experimentally validate NAQMD by ultrafast electron diffraction and X-ray spectroscopy studies of structural and excited state dynamics, shape fluctuations, and phonon dynamics. Scalable software: Simulation engines for desktop-to-exascale platforms using low-overhead, linear-scaling QMD algorithms; divide-conquer-recombine NAQMD with electronic excitations; extended-Lagrangian reactive molecular dynamics (RMD), machine learning (ML) based neural-network quantum molecular dynamics (NNQMD), and super-state accelerated molecular dynamics (AMD) and kinetic Monte Carlo codes; thermal and electrical transport software; and design 3D architectures of LMs with desired functionality using scalable software. Distribution of software and data, and training: Software and simulation-experimental data generated within the Center are distributed to the materials science community via Berkeley Materials Project (MP) framework. We have also organized three workshops for software distribution and training at USC (Nov. 2017, Mar. 2018) and Gaithersburg, MD (Nov. 2018) to train researchers, with the last one in focused on underrepresented groups, in collaboration with Howard University which is one of the largest HBCUs. The Center supported a total of 46 personnel and 6 undergraduate students. These include 14 faculty, 11 postdoctoral research associates, 20 graduate research assistants, and mentored 6 undergraduate students. This resulted in the publications of 63 research papers that include 46 publications on Reactive and Quantum Dynamics Simulations, 13 publications on Machine Learning for Quantum Materials, and 4 publications on Quantum Computing.

2D Materials↗
NASA NTRS2020

Desorption Kinetics of O and CO from Graphitic Carbon Surfaces

The desorption of O/CO from graphitic carbon surfaces is investigated using a one-dimensional model describing the adsorbate interactions with the surface phonon bath. The kinetics of desorption are described through the solution of a master equation for the time-dependent population of the adsorbate in an oscillator state, which is modified through thermal fluctuations at the surface. The interaction of the adsorbate with the surface phonons is explicitly captured by using the computed phonon density Of states (PDOS) of the surface. The coupling of the adsorbate with the phonon bath results in the transition of the adsorbate up and down a vibrational ladder. The adsorbate-surface interaction is represented in the model using a Morse potential, which allows for the desorption process to be directly modeled as a transition from bound to free (continuum) state. The PDOS is a property of the material and the lattice; and is highly sensitive to the presence of defects. The effect of etch pits along with random surface defects on the PDOS is considered in the present work. The presence of defects causes a redshift and broadening of the PDOS, which in turn changes the phonon frequency modes available for adsorbate coupling at the surface. Using the realistic PDOS distributions, the phonon-induced desorption (PID) model was used to compute the transition and desorption rates for both pristine and defective systems. Mathissen’s rule is used to compute the phonon relaxation time for pristine and defective systems based on the phonon scattering times for each of the different scattering processes. First, the desorption rates of the pristine system is fitted against the experimental values to obtain the Morse potential parameters for each of the observed adatoms. These Morse potential parameters are used along with the defective PDOS and phonon relaxation time to compute the desorption rates for the defective system. The defective system rates (both transition and desorption) were consistently lower in comparison with the pristine system. The difference between the transition rates is more significant at lower initial states due to higher energy spacing between the levels. In the case of the desorption rates, the difference between the defective and pristine system is more significant at higher temperatures. The desorption rates for each of the system shows an order of magnitude decrease with the strongly bound systems exhibiting the greatest reduction in the desorption rates.

Swaminathan-Gopalan, Krishnan↗
DOE OSTI2021

Selective Methane Oxidation to Methanol on ZnO/Cu 2 O/Cu(111) Catalysts: Multiple Site-Dependent Behaviors

Due to the abundance of natural gas in our planet, a major goal is to achieve a direct methane to methanol conversion at medium to low temperatures using mixtures of methane and oxygen. Here, we report an efficient catalyst, ZnO/Cu 2 O/Cu(111), for this process investigated using a combination of reactor testing, scanning tunneling microscopy, ambient-pressure x-ray photoemission spectroscopy, density functional calculations, and kinetic Monte Carlo simulations. The catalyst is capable of methane activation at room temperature and transforms mixtures of methane and oxygen to methanol at 450 K with a selectivity of ~30%. This performance is not seen for other heterogenous catalysts which usually require the addition of water to enable a significant conversion of methane to methanol. The unique coarse structure of the ZnO islands supported on a Cu 2 O/Cu(111) substrate provides a collection of multiple centers that display different catalytic activity during the reaction. ZnO-Cu 2 O step sites are active centers for methanol synthesis when exposed to CH 4 and O 2 due to an effective O-O bond dissociation, which enables a methane-to-methanol conversion with a reasonable selectivity. Upon addition of water, the defected O-rich ZnO sites, introduced by Zn vacancies, show superior behavior towards methane conversion and enhance the overall methanol selectivity to over 80%. Thus, in this case, the surface sites involved in a direct CH 4 → to CH 3 OH conversion are different from those engaged in methanol formation without water. Furthermore, the identification of the site-dependent behavior of ZnO/Cu 2 O/Cu(111) opens a design strategy for guiding efficient methane reforming with high methanol selectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Local Background Hole Density Drives Nonradiative Recombination in Tin Halide Perovskites

In this study, we use multimodal microscopy to study carrier recombination in semiconducting tin halide perovskite films based on PEA 0.2 FA 0.8 SnI 3 (PEA = phenethylammonium; FA = formamidinium). We use the observation of pseudo-first-order photoluminescence (PL) decay kinetics to establish a method for quantifying the hole dopant level and nonradiative recombination rate constant. We find that untreated PEA 0.2 FA 0.8 SnI 3 films exhibit large hole doping concentrations of p 0 ≈ 10 19 cm –3 , which is reduced to p 0 ≈ 10 16 cm –3 after SnF 2 treatment. While it is well-known that the radiative recombination rates are increased with p 0 , we reveal that the nonradiative rate is also increased. We find that p-type regions in untreated PEA 0.2 FA 0.8 SnI 3 films are centers for nonradiative recombination, which are diminished in films with p 0 ≈ 10 16 cm –3 . We discover significant PL heterogeneity even in PEA 0.2 FA 0.8 SnI 3 films with moderate dopant levels, suggesting that new strategies to eliminate deleterious defects in PEA 0.2 FA 0.8 SnI 3 must be developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Development of an MKID frequency-to-pixel LED mapper for SPT-3G+

SPT-3G+ is the next-generation camera for the South Pole Telescope (SPT). SPT is designed to measure the cosmic microwave background (CMB) and the mm/sub-mm sky. The planned focal plane consists of 34,000 microwave kinetic inductance detectors (MKIDs), divided among three observing bands centered at 220, 285, and 345 GHz. Each readout line is designed to measure 800 MKIDs over a 500 MHz bandwidth, which places stringent constraints on the accuracy of the frequency placement required to limit resonator collisions that reduce the overall detector yield. To meet this constraint, we are developing a two-step process that first optically maps the resonance to a physical pixel location, and then next trims the interdigitated capacitor (IDC) to adjust the resonator frequency. We present a cryogenic LED apparatus operable at 300 mK for the optical illumination of SPT-3G+ detector arrays. We demonstrate integration of the LED controls with the GHz readout electronics (RF-ICE) to take data on an array of prototype SPT-3G+ detectors. We show that this technique is useful for characterizing defects in the resonator frequency across the detector array and will allow for improvements in the detector yield.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Improving Photostability of Cesium-Doped Formamidinium Lead Triiodide Perovskite

Using time-resolved in situ X-ray photoelectron spectroscopy, we identify and suppress rapid degradation mechanisms for cesium-stabilized formamidinium lead iodide perovskite materials used in state-of-the-art photovoltaics. Accelerated degradation under high light intensity and heating reveals a photocatalytic reaction pathway responsible for rapid decomposition in iodide-rich compositions and a slower pathway for more stoichiometric samples. Using Avrami–Erofe’ev kinetic analysis, we find that the fast process is consistent with a 2D crystallization and growth mechanism fueled by excess halide salt at grain boundaries and surfaces. Moreover, the rate of decomposition varies dramatically with the wavelength of light used to illuminate the thin films. Furthermore, our results reveal the photodegradation mechanisms of PbI 2 and excess iodide and provide a path to increasing perovskite stability under photoexcitation.

14 SOLAR ENERGY↗
DOE OSTI2025

Rational Selection of Transition-Metal Oxide Electrocatalysts from Structure Electronic Structure-Activity Relations: The Role of Defects, Strain, and Sub-Surface Layering

This BES research investigates the physicochemical properties of metal oxides and how they affect electrocatalytic functionalities. The goal is to develop a predictive framework for realizing top-performing electrocatalytic materials for energy-critical reactions. The hypothesis is that well-defined thin films allow detailed mapping of structural-activity relationships because flat surfaces are more straightforward to characterize. Furthermore, the well-defined nature of thin-film metal oxides allows precise tuning of structural and chemical variables for structure-activity-relationship mapping. The proposed research has two technical objectives. The first is to experimentally assess whether the binding energies of surface oxygen can serve as an activity descriptor for oxygen electrocatalysis on metal oxides and then how to control them by tuning the structure and chemical variables. The second is to find the rate-limiting process in oxygen electrocatalysis and other small-molecule reactions. Similar mechanistic insights have been developed on well-defined platinum surfaces but not yet on oxides. This research addresses this gap and uses electrochemistry and X-ray photoemission spectroscopy to study oxide surface chemistry. The obtained insights are collectively analyzed to reveal how the oxides’ structural and chemical variables affect kinetics and can be used to design more active electrocatalysts for energy-critical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Facile Interfacial Reduction Suppresses Redox Chemical Expansion and Promotes the Polaronic to Ionic Transition in Mixed Conducting (Pr,Ce)O 2−δ Nanoparticles

Mixed ionic/electronic conductors (MIECs) are essential components of solid-state electrochemical devices, such as solid oxide fuel/electrolysis cells. For efficient performance, MIECs are typically nanostructured, to enhance the reaction kinetics. However, the effect of nanostructuring on MIEC chemo-mechanical coupling and transport properties, which also impact cell durability and efficiency, has not yet been well understood. Here, in this work, Pr 0.2 Ce 0.8 O 2−δ (PCO20) nanopowders were prepared by coprecipitation, then sintered in a modified dilatometer at three different temperatures (600, 725, and 850 °C) for microstructure evolution, resulting in three samples with different average particle sizes (23, 30, and 53 nm). The chemical strain and electronic/ionic conductivity were then measured simultaneously on stable nanostructures in four isotherms from 550 to 400 °C with steps in pO 2 (1 to 10 –4 atm O 2 ). A microcrystalline bar was prepared and measured for comparison. Particle size reduction led to a monotonically decreasing isothermal redox chemical strain, confirmed by in situ high-temperature, controlled-atmosphere XRD measurements. The corresponding conductivity measurements provided defect chemical insight into the particle size-dependent chemical expansion behavior. The significant weakening of the pO 2 dependence and decreased activation energy for electrical conduction with decreasing particle size indicated a decrease in the reduction enthalpy of PCO, shifting the transition from (Pr) polaronic to ionic behavior to higher pO 2 . STEM-EELS measurements confirmed the majority of Pr was reduced to 3+ in the nanoparticles, while Ce remained 4+. These results demonstrate suppression of deleterious chemical expansion and tailoring of the dominant charge carrier simply through controlling the particle size, providing insights for MIEC microstructural design.

ceria↗