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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
DOE OSTI2023

Polysulfide regulation by defect-modulated Ta 3 N 5- x electrocatalyst toward superior room-temperature sodium-sulfur batteries

Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metal-sulfur batteries. Motivated by a theoretical prediction, herein, we strategically propose nitrogen-vacancy tantalum nitride (Ta 3 N 5-x ) impregnated inside the interconnected nanopores of nitrogen-decorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in room-temperature sodium-sulfur batteries. Through a pore-constriction mechanism, the nitrogen vacancies are controllably constructed during the nucleation of Ta 3 N 5-x . Further, the defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level, not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials, but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion. Moreover, the interconnected continuous Ta 3 N 5-x -in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior. Due to these attributes, the as-developed Ta 3 N 5-x -based electrode achieves superior rate capability of 730 mAh g -1 at 3.35 A g -1 , long-term cycling stability over 2000 cycles, and high areal capacity over 6 mAh cm -2 under high sulfur loading of 6.2mgcm -2 . This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries, but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.

25 ENERGY STORAGE↗
DOE OSTI2020

Synthesis and Characterization of Pd-based Nanomaterials

Bimetallic nanoparticles (BNPs) consist of two different types of metals or alloys that are bonded together. Unique properties such as optical, electronic, thermal, and catalytic effects differ for each type of BNP. Important BNPs range from Au-Pd, Ag- Pt, Au-Pt, and Ag-Ni. Pd bimetallic nanoparticles are of interest due to their many applications such as catalysis and sensing. Bimetallic catalysts have increase reaction rates and have improved catalyst stability through the geometry and ligand distribution. Pd nanoparticles are considered to be a strong catalyst due to their high activity at low temperatures and high tolerance to moisture. The catalytic properties of bimetallic nanoparticles depend on the structural properties such as size and shape. Core-shell, hollow structure, and multi-shell alloy are three possible structures nanoparticles can form as bimetallic catalysts. BNPs can be synthesized through different methods to control the size, shape, and structure. To obtain different morphologies, a variety of methods can be performed. Different methods can range from the usage of the glancing angle deposition (GLAD) to the galvanic replacement reaction, but the methods all depend on the properties of the metals. The galvanic displacement reaction was the method used to obtain Pd-based nanoparticles. This reaction is best know for obtaining hollow shaped NPs. To determine what redox process was preformed, the activity series of metals was used. From the activity series of metals, silver (Ag) was selected to preform Pd-based nanoparticles. Objectives: Synthesize Ag nanoparticles and Ag-Pd nanoparticles to understand the morphology. Characterize the synthesized nanoparticles using scanning electron microscopy (SEM), phase analysis light scattering (PALS), dynamic light scattering (DLS), energy dispersive X-ray spectroscopy (EDS), and UV-Vis spectroscopy. Results: In the UV-Vis spectrum, the Ag-Pd bimetallic NP's plasmon band decreased as the volume of palladium increased. The surface charge increases as the concentration of palladium increases. The Pd{sup 2+} ions interact with the sodium citrate surface, and decrease the negative charge. Conclusion: Ag-Pd nanoparticles were successfully created and stabilized with sodium citrate. The addition of Pd decreased the prominent plasmon band of the Ag nanoparticles. The SEM analysis showed that Ag nanoparticles had a well-defined structure, while the Ag-Pd nanoparticles showed hollow and rough structure. The EDX analysis confirmed the presence of silver and palladium. This material can be used in many industrial and research fields such as organic synthesis, fuel cells, and environmental sensing and remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Surface Immobilization of a Re(I) Tricarbonyl Phenanthroline Complex to Si(111) through Sonochemical Hydrosilylation

A sonochemical-based hydrosilylation method was employed to covalently attach a rhenium tricarbonyl phenanthroline complex to silicon(111). fac-Re(5-(p-Styrene)-phen)(CO) 3 Cl (5-(p-styrene)-phen = 5-(4-vinylphenyl)-1,10-phenanthroline) was reacted with hydrogen-terminated silicon(111) in an ultrasonic bath to generate a hybrid photoelectrode. Subsequent reaction with 1-hexene enabled functionalization of remaining atop Si sites. Attenuated total reflectance–Fourier transform infrared spectroscopy confirms attachment of the organometallic complex to silicon without degradation of the organometallic core, supporting hydrosilylation as a strategy for installing coordination complexes that retain their molecular integrity. Detection of Re(I) and nitrogen by X-ray photoelectron spectroscopy (XPS) further support immobilization of fac-Re(5-(p-styrene)-phen)(CO) 3 Cl. Cyclic voltammetry and electrochemical impedance spectroscopy under white light illumination indicate that fac-Re(5-(p-styrene)-phen)(CO) 3 Cl undergoes two electron reductions. Mott–Schottky analysis indicates that the flat band potential is 239 mV more positive for p-Si(111) co-functionalized with both fac-Re(5-(p-styrene)-phen)(CO) 3 Cl and 1-hexene than when functionalized with 1-hexene alone. XPS, ultraviolet photoelectron spectroscopy, and Mott–Schottky analysis show that functionalization with fac-Re(5-(p-styrene)-phen)(CO) 3 Cl and 1-hexene introduces a negative interfacial dipole, facilitating reductive photoelectrochemistry.

X-ray photoelectron spectroscopy↗
NASA NTRS1997

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗
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↗
DOE OSTI2022

Ga + -Chabazite Zeolite: A Highly Selective Catalyst for Nonoxidative Propane Dehydrogenation

Ga-chabazite zeolites (Ga-CHA) have been found to efficiently catalyze propane dehydrogenation with high propylene selectivity (96%). In situ FTIR spectroscopy and pulse titrations are employed to determine that upon reduction, surface Ga 2 O 3 is reduced and diffuses into the zeolite pores, displacing the Brønsted acid sites (BAS) and forming extra-framework Ga + sites. This isolated Ga + site reacts reversibly with H 2 to form GaHx (2034 cm -1 ) with an enthalpy of formation of ~ -51.2 kJ·mol -1 , a result supported by Density functional theory (DFT) calculations. The initial C 3 H 6 dehydrogenation rates decrease rapidly (40%) during the first 100 min and then decline slowly afterward, while the C 3 H 6 selectivity is stable at ~ 96%. The reduction in the reaction rate is correlated with the formation of polycyclic aromatics inside the zeolite (using UV-vis spectroscopy) indicating that the accumulation of polycyclic aromatics is the main cause of the deactivation. The carbon species formed can be easily oxidized at 600 °C with complete recovery of the PDH catalytic properties. The correlations between GaH x vs. Ga/Al ratio, and PDH rates vs. Ga/Al ratio show that extra-framework Ga + is the active center catalyzing propane dehydrogenation. The higher reaction rate on Ga + than In + in CHA zeolites, by a factor of 43, is the result of differences in the stabilization of the transition state due to the higher stability of Ga 3+ vs. In 3+ . The uniformity of the Ga + sites in this material makes it an excellent model for the molecular understanding of metal cation exchanged hydrocarbon interactions in zeolites.

10 SYNTHETIC FUELS↗
DOE OSTI2025

A comparison of ceramic and carbon-based reductants for vitrification of low-activity waste

Sucrose is the current baseline additive at the Hanford Waste Treatment and Immobilization Plant in Washington, USA to control foaming during waste feed to glass transitions and the redox state of the glass melt. Alternative reductants are being investigated to alleviate strain on effluent treatment from toxic acetonitrile production from incomplete combustion of sucrose. This study evaluates ceramic additive options including B4C, B6Si, SiC and VB2 in simulated low-activity waste feed, as well as coke dust, probing the feed volume expansion during melting as well as the gas evolution. All alternative reductant options examined significantly reduced acetonitrile production, however there was variability in their effectiveness as foam-reducing agents. VB2 and coke at the appropriate ratios were similarly effective as sucrose in controlling both foam volume and glass redox state, but with considerably less acetonitrile production. B4C, B6Si and SiC showed more promising foam control and very little acetonitrile production, however all of the final glasses were over reduced, i.e., Fe2+/FeT = 0.5. These alternative reductant studies provide operational flexibility to the operation of the vitrification plant, as well as options for alternative raw materials in industrial glass melting.

Rigby, Jessica C. (ORCID:0000000235719977)↗
DOE OSTI2025

Single-Determinant Ground State in Ce 4+ Imidophosphorane Complexes

X-ray spectroscopy techniques are critical in the electronic structure analysis of high-valent lanthanides. The interpretation of multipeaked features at the lanthanide L 3 -edge has remained a challenging question, as it is observed across a range of material classes. A series of structurally related Ce 4+ complexes were prepared to probe the potential ligand field perturbation of the ground state within the series. The tuning of relative 4f and ligand orbital energies in homoleptic and heteroleptic tetravalent Ce imidophosphorane complexes is achieved through ligand derivatization and is clearly demonstrated by UV−vis spectroscopy and electrochemically measured redox potentials. However, Ce L 3 - edge high-energy resolution fluorescence-detected (HERFD) X-ray absorption near-edge structure (XANES) spectra present features at consistent numbers and energies across the range of complexes. Resonant inelastic X-ray scattering (RIXS) is employed to visualize the observed features in the HERFD-XANES spectra. Large complete active space configuration interaction singles and doubles (CASCISD) calculations demonstrate that the ground-state wave function of all complexes can be described employing a single determinant. As a result, the multielectron feature at the L 3 -edge observed in this study for the Ce 4+ imidophosphorane complexes is described as excited-state multiconfigurational behavior that is independent of ligand variation, in systems where the ground state is described using the simple single determinant wave function.

Lanthanides↗
NASA NTRS1999

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗
DOE OSTI2021

Exsolution Synthesis of Nanocomposite Perovskites with Tunable Electrical and Magnetic Properties

Nanostructured functional oxides play an important role in enabling clean energy technologies and novel memory and processor devices. Using thin-film La 0.6 Sr 0.4 FeO 3 (LSF) as a model system, the novel utility of exsolution in fabricating self-assembled metal oxide nanocomposites with tunable functionalities is shown. Exsolution triggers the formation of metallic iron (Fe 0 ) nanoparticles, Ruddlesden–Popper domains, and nm-scale percolated Fe-deficient channels in LSF. Combining multimodal characterization with numerical modeling, the chemical, magnetic, and electrical properties of the exsolution-synthesized nanocomposite at different stages of Fe 0 exsolution as well as during redox cycling are assessed. After exsolution, the electronic conductivity of the nanocomposite LSF increased by more than two orders of magnitude. Based on numerical analysis representing all the constituents, it is expected that this increase in conductivity originates mainly from the Fe-deficient percolating channels formed during exsolution. Moreover, the exsolved nanocomposite is redox-active even at moderate temperatures. Such redox capabilities can enable dynamic control of the nanocomposite functionality by tailoring the oxygen non-stoichiometry. This concept is demonstrated with a continuous modulation of magnetization between 0 and 110 emu cm -3 . These findings point out that exsolution may serve as a platform for scalable fabrication of complex metal oxide nanocomposites for electrochemical and electronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Autonomous organic synthesis for redox flow batteries via flexible batch Bayesian optimization

Traditional trial-and-error methods for materials discovery are inefficient to meet the urgent demands posed by the rapid progression of climate change. This urgency has driven the increasing interest in integrating robotics and machine learning into materials research to accelerate experimental learning. However, idealized decision-making frameworks to achieve maximum sampling efficiency are not always compatible with high-throughput experimental workflows inside a laboratory. For multi-step chemical processes, differences in hardware capacities can complicate the digital framework by introducing constraints on the maximum number of samples in each step of the experiment, hence causing varying batch sizes in variable selection within the same batch. Therefore, designing flexible sampling algorithms is necessary to accommodate the multi-step synthesis with practical constraints unique to each high-throughput workflow. In this work, we designed and employed three strategies on a high-throughput robotic platform to optimize the sulfonation reaction of redox-active molecules used in flow batteries. Our strategies adapt to the multi-step experimental workflow, where their formulation and heating steps are separate, causing varying batch size requirements. By strategically sampling using clustering and mixed-variable batch Bayesian optimization, we were able to iteratively identify optimal conditions that maximize the yields. Our work presents a flexible approach that allows tailoring the machine learning decision-making to suit the practical constraints in individual high-throughput experimental platforms, followed by performing resource-efficient yield optimization using available open-source Python libraries.

Tamura, Clara [Univ. of Washington, Seattle, WA (U↗
DOE OSTI2022

The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

While Cr poisoning of the oxygen reduction reaction (ORR) at SOFC cathodes is widely agreed to involve deactivation of oxygen exchange sites, the degradation mechanism remains ambiguous. Here, we selected an alternative cathode material Pr 0.1 Ce 0.9 O 2− δ , free of Sr segregation, to systematically investigate the effect of Cr-induced degradation in ORR. We expand on our previous studies in which the acidity/basicity of binary additives was found to be a strong indicator of the rate of oxygen surface exchange, by electrochemically investigating the ORR activity of the PCO cathode by impedance spectroscopy. Serial infiltration with acidic Cr-based oxides was found to degrade ORR activity as reflected in a 20-fold increase in area specific resistance (ASR) without corresponding changes in activation energy, with the opposite trend obtained with Ca-based oxides. Detected changes in total capacitance, attributed to changes in surface capacitance, also suggest depressed/enhanced PCO surface redox behavior with Cr/Ca-based infiltrants. Taken together, these results point to a more universal source of ORR poisoning/activation, based on acidity/basicity, rather than physical blocking of active sites. With this improved understanding, one can expect progress to be made in the coming years in optimizing means for protecting catalytic surfaces from degradation and/or improving their performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Tunable angle-dependent electrochemistry at twisted bilayer graphene with moiré flat bands

Tailoring electron transfer dynamics across solid–liquid interfaces is fundamental to the interconversion of electrical and chemical energy. Stacking atomically thin layers with a small azimuthal misorientation to produce moiré superlattices enables the controlled engineering of electronic band structures and the formation of extremely flat electronic bands. Here, we report a strong twist-angle dependence of heterogeneous charge transfer kinetics at twisted bilayer graphene electrodes with the greatest enhancement observed near the ‘magic angle’ (~1.1°). Furthermore, this effect is driven by the angle-dependent tuning of moiré-derived flat bands that modulate electron transfer processes with the solution-phase redox couple. Combined experimental and computational analysis reveals that the variation in electrochemical activity with moiré angle is controlled by a structural relaxation of the moiré superlattice at twist angles of <2°, and ‘topological defect’ AA stacking regions, where flat bands are localized, produce a large anomalous local electrochemical enhancement that cannot be accounted for by the elevated local density of states alone.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Thermogravimetric Temperature-Programmed Thermal Redox Protocol for Rapid Screening of Metal Oxides for Solar Thermochemical Hydrogen Production

As combinatorial and computational methods accelerate the identification of potentially suitable thermochemically-active oxides for use in solar thermochemical hydrogen production (STCH), the onus shifts to quickly evaluating predicted performance. Traditionally, this has required an experimental setup capable of directly carrying out a two-stage thermochemical water-splitting process. But this can be a difficult endeavor, as most off-the-shelf equipment cannot adequately deal simultaneously with the high temperatures, varying oxygen partial pressures, and high H 2 O partial pressures required; achieving sufficient temporal sensitivity to accurately quantify the kinetics is also a major challenge. However, as proposed here, a less complicated experiment can be used as a first screening for thermochemical water splitting potential. Temperature-Programmed Thermal Redox (TPTR) using thermogravimetry evaluates the thermal reduction behavior of materials. This technique does not require water splitting or CO 2 -splitting analogs but can nonetheless predict water-splitting performance. Three figures of merit are obtained from the TPTR experiment: reduction onset temperature, extent of reduction, and extent of recovery upon reoxidation. These metrics can collectively be used to determine if a material is capable of thermochemical water-splitting, and, to good approximation, predict whether the thermodynamics are favorable for use under more challenging high-conversion conditions. This paper discusses the pros and cons of using TPTR and proposes a protocol for use within the STCH community.

08 HYDROGEN↗
DOE OSTI2024

Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis

Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.

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

Controlling Pt Crystal Defects on the Surface of Ni–Pt Core–Shell Nanoparticles for Active and Stable Electrocatalysts for Oxygen Reduction

A strategy of direct growth of Pt on Ni was used to create and control Pt crystal defects on the surface of Ni–Pt core–shell nanoparticles. The control over the types of defects was easily achieved by changing the surfactant system. Here, in this work, two types of crystal defects have been introduced into Ni–Pt core–shell nanoparticles: polycrystalline shells with multiple grain boundaries and step-edge shells with undercoordinated atoms at corners and steps. We show that the step-edge shell has a higher specific activity for the oxygen reduction reaction (ORR), while the thinner polycrystalline shell results in a higher activity per mass and stability. Our results suggest that Ni–Pt core–shell nanoparticles with a thin Pt shell that have high density of crystal defect should be targeted for high performance ORR catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Visible-Light Photoinitiation of (Meth)acrylate Polymerization with Autonomous Post-Conversion

Conversion plateaus rapidly in radical photopolymerizations (RPPs) following discontinuation of irradiation due to rapid termination of reactive radicals, which restricts the wider use of RPPs in applications that involve nonuniform light access including those with attenuated light transmission or irregular surfaces. Based on our recent report of a radical dark-curing photoinitiator (DCPI) that continues polymerization beyond the cessation of irradiation by enabling latent redox initiation with photo-released amine in the presence of a suitable oxidant, we developed a new DCPI with an absorption spectrum that extends well into the visible range. Our design process involved a series of computational investigations of candidate molecules, including a systematic study of substituents and their position-dependent effects on absorption characteristics, electronic transitions, and the photochemical mechanism and its associated energetics. Our quantum chemical computations identified the target compound 5,7-dimethoxy-6-bromo-3-aroylcoumarin-DMPT/BPh4 and predicted that it would facilitate the dark-curing mechanism by concurrent photo-radical generation and photo-induced release of an efficient redox reductant under visible irradiation. This reductant-tethered chromophore was then synthesized and optically characterized with UV–vis spectroscopy that revealed its strong visible-light absorption with a molar absorptivity of 5710 M–1 cm–1 at 405 nm and 50 M–1 cm–1 at 455 nm. We then demonstrated extensive dark-curing of >35% additional conversion over 25 min following brief activation of the shelf-stable one-part system by irradiation with a 455 nm LED that was ceased at 20% conversion. In contrast, shuttering irradiation of the control formulation at that same point resulted in immediate cessation of conversion, which plateaued at 20%. We determined a remarkable initiator efficiency of 2.82 that results from the additional redox-generated radicals with a 77% photo-reductant generation quantum yield. The combination of superior photo- and dark-curing efficiencies of this new visible DCPI is expected to open new application opportunities in RPP, especially those involving resins that are highly light attenuating, surfaces that possess irregular features that produce uneven irradiance, and production lines where continued dark-curing downstream of the light activation step enhances line efficiencies.

absorption spectrum↗
DOE OSTI2024

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH 2 -MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonance spectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min -1 . Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to the metal-organic framework surface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. In conclusion, the constructed photo-enzyme coupled system successfully combines enzyme catalysis’ selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

36 MATERIALS SCIENCE↗