Search NASA⌕ Search

SEARCH · Search NASA

Results for “reactive potentials”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Molecular dynamics simulations of reflection and sputtering behavior of boron under deuterium ion irradiation

Boronization is a commonly used method of wall conditioning in fusion reactors. The application of boron films to the plasma-facing materials results in enhanced plasma performance due to the reduction of intrinsic impurities. This is primarily driven by a reduction in oxygen content that is chemically trapped in the boron film. The reactive nature of these boron films also raises questions concerning interactions with hydrogen isotopes. In this work, boron-deuterium interactions were studied using molecular dynamics (MD). Reactive force field potentials were used to model the chemical interactions between B and D. An amorphous boron substrate was irradiated by D atoms at varying incident energies, 10 eV < E i < 150 eV and angles, 0° < α < 85°. The reflection probability was calculated and compared to results from the commonly-used binary collision approximation (BCA) method. This comparison found that the BCA underestimated the reflection probability at E i < 35 eV and α > 45 ∘ . The source of this discrepancy was found to be the surface binding energy model. The BCA calculation with an isotropic surface binding energy model was more closely aligned to the MD result. This, in combination with a correction function based on the MD results allows for corrections to the reflection probability of deuterium impinging on boron surfaces. The sputtering of the substrate material was also studied. While this study did not contain sufficient events to quantitatively describe the sputtering behavior, some qualitative results emerged: namely, chemical sputtering of B and D-containing molecules (BD, BD 2 , BD 3 ) at low ( < 20 eV) incident deuterium energies. This result suggests that chemical sputtering could be a significant factor in limiting boron coating lifetime when exposed to lower ion energies, such as those in detached plasmas. The results show that chemical interactions should be taken into account when modeling the interactions between D ions and B surfaces.

Boron↗
DOE OSTI2025

Carbon Mineralization of Sulfate Wastes Containing Pb: Synchrotron Pb M3-Edge XANES Analysis of Simultaneous Heavy Metal and Carbon Sequestration

Sulfate wastes are produced in large quantities and contain toxic heavy metals such as lead (Pb), posing environmental risks. Because of favorable solubility differences, these wastes can be repurposed for engineered carbon dioxide (CO 2 ) sequestration. Understanding the fate and mobility of heavy metals during this process is important. This study focuses on Pb and the effect of zinc (Zn) on Pb in carbon mineralization. Synthesized gypsum was treated with a carbonate-rich solution at pH 11.5 to convert the sulfates to carbonates. Aqueous solutions and mineral solids were analyzed. Synchrotron-based micro-X-ray fluorescence and a novel application of Pb M3-edge X-ray absorption near-edge structure provided detailed insights into Pb distribution and mineral forms. Results showed significant reductions in aqueous Pb and Zn concentrations, indicating effective metal sequestration. Carbon mineralization transformed Pb from soluble anglesite (PbSO 4 ) into insoluble cerussite (PbCO 3 ) and hydrocerussite (Pb 3 (CO 3 ) 2 (OH) 2 ). Pb primarily precipitated onto calcium carbonate surfaces through surface-mediated precipitation reactions. While the presence of Zn modified crystallization dynamics, it did not impede Pb sequestration and potentially enhanced surface reactivity, facilitating greater Pb immobilization. These findings highlight carbon mineralization as a sustainable approach to immobilize toxic metals in sulfate wastes while advancing CO 2 sequestration efforts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Vanadium Substitution Dictates H Atom Uptake at Lindqvist-type Polyoxotungstates

Understanding how modification of molecular structures changes the thermochemistry of H atom uptake can provide design criteria for the formation of highly active catalysts for reductive transformations. Herein, we describe the effect of doping an atomically precise polyoxotungstate with vanadium on proton-coupled electron transfer (PCET) reactivity. The Lindqvist-type polyoxotungstate [W 6 O 19 ] 2– displays reversible redox chemistry, which was found to be unchanged in the presence of acid, indicating an inability to couple reduction with protonation. However, the incorporation of a single vanadium center into the structure significantly changes the reactivity, and the potential required for one-electron reduction of [VW 5 O 19 ] 3– was shown to vary with the strength of the acid added. Construction of a potential-pK a diagram allowed assessment of the thermodynamics of H atom uptake, indicating BDFE(O–H) ≈ 64 kcal/mol, while chemical synthesis of the reduced/protonated derivative (TBA) 3 [VW 5 O 19 H] was used to probe the position of protonation.

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

Lignin valorization reshapes sustainable biomass refining

As the largest natural reservoir of aromatics, lignin offers significant potential for bioproduct manufacturing through advances in valorization technologies. However, the intrinsically complex structures of lignin pose significant challenges for its fractionization and downstream valorization. Overcoming challenges in lignin chemistry modification is crucial for achieving effective lignin valorization and establishing sustainable biorefinery industries. This review explores the potential of tailoring lignin reactivity to enable functional bioproduct manufacturing thereby contributing to profitable biorefining. The intrinsic characteristics of lignin are first summarized, highlighting their roles in both fractionization and valorization. The latest progress in lignin fractionation is then presented, emphasizing their potential to tailor lignin chemistry, reactivity, and processibility. Furthermore, advancements in lignin valorization are covered, recognizing that tailored lignin reactivity is key to defining bioproduct functionality. By examining these chemical mechanisms, this review sheds on the structure-function relationships between lignin and its derived products. To address the dilemma of lignin valorization and biorefineries, a promising synergistic biorefinery is proposed. This involves redesigning biomass fractionation strategies, tailoring lignin chemistry, and upgrading both carbohydrate and lignin streams across the entire biorefinery chain—from feedstock to application. Altogether, a deeper understanding of tailored lignin chemistry is crucial for decoding the reaction mechanisms in biomass processing. A synergistic biorefinery could harness lignin's intrinsic properties to improve product functionality and address key challenges, paving the way for cost-effective, sustainable biorefinery solutions.

09 BIOMASS FUELS↗
DOE OSTI2026

Mechanochemical synthesis of hydraulically reactive calcium silicate minerals via thermally-assisted mechanical grinding

This study explores a thermally assisted mechanochemical approach alternative to conventional cement synthesis as a potential to produce hydraulically reactive calcium silicate phases. Ball milling of mixed CaO/SiO 2 feedstocks at temperature ranges 100-300 °C increases the formation of the Ca-O-Si bonds and precursor reactivity. Spectroscopic analyses (FTIR, MAS-NMR, UV-Vis DRS) indicate increasing amorphization with milling temperature, attributed to improved mixing and thermally assisted diffusion. Upon hydration, all treated samples exhibit exothermic heat release, with the sample prepared at 300 °C showing the most pronounced reactivity. Thermal analysis reveals weight loss consistent with C-S-H formation, confirming cement-like behavior. In summary, moderate thermal input during milling promotes structural activation and enhances downstream hydraulic reactivity, providing a proof-of-concept for energy-reduced cement precursor processing.

Alite↗
DOE OSTI2025

Including Physics-Informed Atomization Constraints in Neural Networks for Reactive Chemistry

Machine learning interatomic potentials (MLIPs) have emerged as powerful tools for investigating atomistic systems with high accuracy and a relatively low computational cost. However, a common and unaddressed challenge with many current neural network (NN) MLIP models is their limited ability to accurately predict the relative energies of systems containing isolated or nearly isolated atoms, which appear in various reactive processes. To address this limitation, we present a mathematical technique for modifying any existing atom-centered NN architecture to account for the energies of isolated atoms. The result produces a consistent prediction of the atomization energy (AE) of a system using minimal constraints on the model. Using this technique, we build a model architecture that we call hierarchically interacting particle neural network (HIP-NN)-AE, an AE-constrained version of the HIP-NN, as well as ANI-AE, the AE-constrained version of the accurate NN engine for molecular energies (ANI). Our results demonstrate AE consistency of AE-constrained models, which drastically improves the AE predictions for the models. We compare the AE-constrained approach to unconstrained models as well as models from the literature in other scenarios, such as bond dissociation energies, bond dissociation pathways, and extensibility tests. These results show that the constraints improve the model performance in some of these tasks and do not negatively affect the performance on any tasks. The AE constraint approach thus offers a robust solution to the challenges posed by isolated atoms in energy prediction tasks.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Rotating cylinder electrode in reactive CO 2 capture: Identifying active C species via transport, VLE models and kinetics

Here, this article explores technical challenges and potential methodologies for understanding electrochemical Reactive CO 2 Capture (RCC) mechanisms. RCC offers potential energy cost advantages by directly converting captured CO 2 into fuels and chemicals, unlike traditional carbon capture and utilization (CCU) processes that require sequential capture, concentration, and compression. However, direct conversion of captured CO 2 introduces complexity due to additional equilibrium buffer reactions, making it challenging to identify active species for reduction in electrochemical studies. This article discusses methods to integrate transport, thermodynamics, and kinetics concepts to identify active carbon sources in RCC. Vapor‐Liquid Equilibrium (VLE) and transport models are validated against experimental results obtained in a gastight rotating cylinder electrode reactor and are shown as useful tools for studying RCC in heterogeneous electrocatalysts across different capture agents, solvents, and temperatures. This article establishes an experimental framework for advancing research in electrochemical RCC.

Electrocatalysis↗
DOE OSTI2024

Vivianite oxidation is not photocatalyzed

Vivianite is a hydrous Fe2+ phosphate mineral found in anoxic environments that plays an integral role in P cycling and environmental biogeochemistry. Imbued in the vivianite literature dating as far back as 1918 is the notion that vivianite is light-sensitive and susceptible to rapid photooxidation induced entirely by solar light. However, despite an exhaustive search, to our knowledge this conventionally accepted assumption has never been directly tested, nor has the band gap ever been measured. Resolving this question of photochemical control of vivianite redox chemistry is important for performing and interpreting experiments involving vivianite reactivity with contaminants, and potentially iron and phosphate cycling in the photic zone of aquatic systems. The present study was specifically designed to add¬ress this question. Pure synthetic vivianite samples were irradiated in aqueous suspensions with a Xe lamp at conditions mimicking the solar spectrum and compared to dark controls. Particles stirred in anoxic suspensions for up to 66 days showed no detectable oxidation irrespective of light exposure, according to colorimetric Fe2+/Fe3+ assays, micro X-ray diffraction, and Raman spectroscopy. In contrast, the same experiment performed using air-equilibrated suspensions showed systematic oxidation of up to ~80% mol% Fe(II) at 66 days, but again with no detectable light exposure effect. To test for UV reactivity, further experiments on vivianite powders under air versus N2 atmosphere were performed using a Hg lamp with a longpass filter. In contrast to oxidation in air where no effect of light was detected, after 24 hrs irradiation anoxically, 0.78% Fe was oxidized compared to dark controls, and after 13 days only an additional 0.3% Fe was oxidized. The band gap of pure vivianite was measured by the Tauc method to be 3.5 eV. Contrary to previous reports, solar light has minimal impact on the oxidation of pure vivianite, insignificant in particular when compared to its relatively fast oxidation by oxygen exposure. As such, light does not need to be excluded when running typical vivianite laboratory experiments. Long-term storage of natural vivianite in museums or private collections should continue protective measures given that a possible photocatalytic role of impurities cannot yet be ruled out. Nonetheless, at all depths in natural aquatic systems it appears that the primary abiotic control on the reactivity and half-life of vivianite particles should be the dissolved oxygen concentration, not light exposure.

Vivianite, photochemistry, oxidation↗
DOE OSTI2025

Mo Atom Rearrangement Drives Layer-Dependent Reactivity in Two-Dimensional MoS 2

Two-dimensional (2D) materials offer a valuable platform for manipulating and studying chemical reactions at the atomic level, owing to the ease of controlling their microscopic structure at the nanometer scale. While extensive research has been conducted on the structure-dependent chemical activity of 2D materials, the influence of structural transformation during the reaction has remained largely unexplored. In this work, we report the layer-dependent chemical reactivity of MoS 2 during a nitridation atomic substitution reaction and attribute it to the rearrangement of Mo atoms. Our results show that the chemical reactivity of MoS 2 decreases as the number of layers is reduced in the few-layer regime. In particular, monolayer MoS 2 exhibits significantly lower reactivity compared with its few-layer and multilayer counterparts. Atomic-resolution transmission electron microscopy (TEM) reveals that MoN nanonetworks form as reaction products from monolayer and bilayer MoS 2 , with the continuity of the MoN crystals increasing with layer number, consistent with the local conductivity mapping data. The layer-dependent reactivity is attributed to the relative stability of the hypothetically formed MoN phase, which retains the number of Mo atomic layers present in the precursor. Specifically, the low chemical reactivity of monolayer MoS 2 is attributed to the high energy cost associated with Mo atom diffusion and migration necessary to form multilayer Mo lattices in the thermodynamically stable MoN phase. In conclusion, this study underscores the critical role of lattice rearrangement in governing chemical reactivity and highlights the potential of 2D materials as versatile platforms for advancing the understanding of materials chemistry at the atomic scale.

Chemical reactivity↗
DOE OSTI2026

Vibrational Quantum-State-Controlled Reactivity in the O 2 + + C 3 H 4 Reaction

Quantum-state-controlled reactivity is a long-standing goal in the field of physical chemistry. In this work, we explore the vibrational-state-dependent behavior of the ion–molecule reaction between O 2 + in distinct vibrational states and two isomers of C 3 H 4 , allene (H 2 C 3 H 2 ) and propyne (H 3 C 3 H). While most products are formed regardless of the vibrational state of O 2 + , the branching ratios are influenced by vibrational excitation, and a new product, C 2 O + , appears exclusively in the excited-state reactions. This selective formation of C 2 O + demonstrates that vibrational excitation can effectively activate a reaction pathway, providing direct evidence of quantum-state control in the reactivity. These results represent an important step toward the goal of quantum-state-controlled chemistry in molecular systems.

Chemical reactions↗
DOE OSTI2024

Preparation of Neptunyl and Plutonyl Acetates To Access Nonaqueous Transuranium Coordination Chemistry

Uranyl diacetate dihydrate is a useful reagent for the preparation of uranyl (UO 2 2+ ) coordination complexes, as it is a well-defined stoichiometric compound featuring moderately basic acetates that can facilitate protonolysis reactivity, unlike other anions commonly used in synthetic actinide chemistry such as halides or nitrate. Despite these attractive features, analogous neptunium (Np) and plutonium (Pu) compounds are unknown to date. Here, in this study, a modular synthetic route is reported for accessing stoichiometric neptunyl(VI) and plutonyl(VI) diacetate compounds that can serve as starting materials for transuranic coordination chemistry. The new NpO 2 2+ and PuO 2 2+ complexes, as well as a corresponding molecular UO 2 2+ complex, are isomorphous in the solid state, and in solution show similar solubility properties that facilitate their use in synthesis. In both solid and solution state, the +VI oxidation state (O.S.) is maintained, as demonstrated by vibrational and optical spectroscopy, confirming that acetate anions stabilize the oxidizing, high-valent +VI states of Np and Pu as they do for the more stable U(VI). All three acetate salts readily react with a model diprotic ligand, affording incorporation of U(VI), Np(VI), and Pu(VI) cores into molecular coordination compounds that occurs concomitantly with elimination of acetic acid; the new complexes are high-valent, yet overall charge neutral, facilitating entry into nonaqueous chemistry by rational synthesis. Computational studies reveal that the dianionic ligand framework assists in stabilizing the +VI O.S. via donation to the 5f shells of the actinides, highlighting the potential usefulness of protonolysis reactivity toward preparation of stabilized high-valent transuranic species.

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

Trends and limits of CO 2 capture in solid and liquid sorbents at standard conditions

Carbon capture and storage (CCS) plays a critical role in achieving climate change mitigation targets, offering a pathway to decarbonize power generation, industrial processes, and heat production while addressing atmospheric CO 2 removal. While CCS technologies are technically advanced, the widespread adoption of 100 % CO 2 capture capacities such as 1 mol of CO 2 /mol of material and 1 g CO 2 /g storage (targeted by the DARPA, Defense Sciences Office, USA Govt.) has raised questions about the feasibility of achieving higher capture capacities. In the context of limiting global warming to 1.5°C, reaching 100 % CO 2 capture capacity is increasingly necessary, with residual emissions requiring complementary carbon dioxide removal (CDR) technologies. This review exclusively focuses on the CO 2 capture capacities of various sorbents under standard conditions, using different evaluation metrics. This study explores the performance of solid and liquid sorbents under standard conditions, analyzing factors including surface area, pore structure, solvent type, and functionalization to identify materials optimized for industrial-scale CCS applications. Emerging sorbents, including ILs, MOFs, COFs, POPs, DES, RCC, hybrid materials, and reactive sorbents, offer significant potential for enhanced selectivity and energy-efficient regeneration. Through a systematic assessment of gravimetric, volumetric, and molar capacities, the study provides insights into material efficiencies and trade-offs, offering guidance on optimizing sorbent selection for specific applications. The research advances understanding of scalable CCS technologies, contributing to global efforts to achieve net-zero emissions and address the pressing challenge of climate change.

Absorption↗
DOE OSTI2024

Atomic scale etching of diamond: insights from molecular dynamics simulations

Diamond is a promising material for multiple applications in quantum information processing and sensing as well as applications in microelectronics. However, diamond devices can be limited by surface defects that compromise charge stability and spin coherence, among others. Improved strategies in plasma etching of diamond could play an important role in minimizing or eliminating these defects. In this work, we explore plasma-assisted atomic scale etching of diamond using argon ions (Ar + ), hydrogen ions (H + ) and hydrogen atoms (H). We employ classical molecular dynamics (MD) simulations and test several interatomic potentials based on the Reactive Empirical Bond Order (REBO) form with comparisons to a variety of published experimental results. We performed MD simulations of low-energy hydrogen ($\leqslant$50 eV) and argon ( $\leqslant$200 eV) ion bombardment of diamond surfaces. Ar + bombardment can be used to locally smooth initially rough diamond surfaces via the formation of an amorphous C layer, the thickness of which increases with argon ion energy. Subsequent exposure with hydrogen ions (or fast neutrals) will selectively etch this amorphous C layer, leaving the underlying diamond layer mostly intact if the H energy is maintained below about 10 eV. The simulations suggest that combining Ar + smoothing with selective, near threshold energy H removal of amorphous C can be an effective strategy for diamond surface engineering, leading to more reliable and sensitive diamond color center devices.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

INFLUENCE OF SUPPLEMENTARY ARGON GAS SHIELDING ON THE MICROSTRUCTURE AND MECHANICAL BEHAVIOR OF SS316L ADDITIVELY MANUFACTURED BY DIRECTED ENERGY DEPOSITION

The dissolution of atmospheric gases into parts additively manufactured by directed energy deposition (DED) has long been of concern, and stock shielding solutions have usually proven inadequate at fully removing atmospheric gases from weld beads. The objective of this work was to design a new supplementary argon gas shroud for a specific DED printer and evaluate its effect on microstructure and macroscopic properties of SS316L and the potential for printing more reactive metals such as Ti-6Al-4V. This was investigated by printing four SS316L sample blocks, two with and two without the shroud, each printed in two different orientations. These samples were subsequently evaluated with inert gas fusion (IGF), SEM/EDS imaging, and tensile tests. The shroud reduced oxygen content by 0.019-0.031%, and SEM imaging revealed fewer oxide inclusions. A more dramatic reduction of 0.13% oxygen and 0.171% nitrogen was observed by the inert gas fusion of Ti-6Al-4V samples. Overall, the results indicated the shroud was successful at reducing atmospheric gas uptake within the print region and may enable the printing of reactive metal powders in DED systems.

Helvie, Kyle↗
DOE OSTI2025

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

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

Challenges in Product Selectivity for Electrocatalytic Reduction of Amine-Captured CO 2 : Implications for Reactive Carbon Capture

CO 2 is a potential feedstock for carbon-based fuels or materials, but is only available in dilute streams. Integrated processes for CO 2 capture and conversion directly valorize the CO 2 captured by sorbent materials, skipping the energetically expensive sorbent regeneration step. Amines are the most heavily studied liquid-phase sorbent materials for CO 2 capture from dilute streams. Amines react with CO 2 in a 2:1 ratio to form the corresponding ammonium carbamate. Ammonium carbamate [NH 4 ][H 2 NCO 2 ] was tested as the substrate using the highly selective and robust CO 2 -to-formate reduction electrocatalyst [( tBu POCOP)Ir(H)(NCCH 3 ) 2 ], where ( tBu POCOP) is the tridentate pincer ligand 2,6-bis(di tert -butyl-phosphonito). When ammonium carbamate was used as the substrate instead of CO 2 , only hydrogen was produced. An equivalent electrolysis with ammonium hexafluorophosphate with CO 2 also resulted in primarily hydrogen. Methyl carbamate and urea were also tested as substrates as proxies for carbamate that do not contain an equivalent of ammonium, and there was also negligible reduction to carbon-based products. These results indicate that the loss of selectivity observed for aminecaptured CO 2 , or ammonium carbamate, is likely due to the generation of the acidic ammonium equivalent as well as the greater challenge of reducing carbamate compared to CO 2 . This study illustrates that catalysts with high selectivity for concentrated CO 2 can favor hydrogen evolution and loss of carbon-based products when amine-captured CO 2 is used instead.

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

Surface chlorination of IrO2(110) by HCl

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.

Chemistry↗
DOE OSTI2025

Interfacial dynamics and catalytic behavior of single Ni atom site

Single-atom catalysts (SACs) have garnered significant interest due to their ability to reduce metal particles to the atomic scale, enabling finely tunable local environments and enhanced catalytic properties in terms of reactivity and selectivity. Despite this potential, their application has largely been confined to small-molecule transformations as metal-catalyzed reaction. Here, in this study, we present a diverse single-atom nickel (Ni) catalyst established via a nanoporous carbon (NPC) supported practice. This catalyst represents a breakthrough by achieving the bond formation between carbon and nitrogen and interfacial dynamics in the SAC. The present first principle-based density functional simulations establish the reaction dynamics and catalytic behaviour of such SAC. This dynamic nature comprises an exclusive nitrogen intercalated site showing excellent base effects. This base quickly tunes the interfacial atmosphere, enabling dynamic movement of adatoms into the NPC species, significantly changing the reaction path in Ni SACs due to superior steric effects. The research demonstrates that SACs can extend the capabilities of catalytic systems to include a wider range of complex reactions, offering substantial promise for the development of new, efficient synthetic methods for creating value-added molecular products.

36 MATERIALS SCIENCE↗