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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Catalytic Mechanism of Interfacial Water in the Cycloaddition of Quadricyclane and Diethyl Azodicarboxylate

"On-water" catalysis, the unusual activity of water molecules at the organic solvent-water interface, has been demonstrated in many organic reactions. However, the catalytic mechanism has remained unclear, largely because of the irreproducibility of the organic-water interface under the common stirring condition. In this work, the interfacial area was controlled by employing adsorbed water on mesoporous silica nanoparticles as the catalyst. Reliable kinetics of the cycloaddition reaction of quadricyclane and diethyl azodicarboxylate (DEAD) at the toluene-water interface within the nanoparticle pores were measured. Data reveal an Eley-Rideal mechanism, wherein DEAD adsorbs at the toluene-water interface via hydrogen bonds formed with interfacial water, which lower the activation energy of the cycloaddition reaction. The mechanistic insights gained and preparation of surface water in silica pores described herein may facilitate the future design of improved "on-water" catalysts.

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

A chemical kinetics theory for interpreting the non-monotonic temperature dependence of enzymatic reactions

Abstract. One notable observation of enzymatic chemical reactions is that, for a given abundance of enzymes and substrates, temperature increases cause reaction rates to first increase consistent with the Arrhenius relationship, then plateau, and finally fall off quickly to zero at high temperatures. While many mathematical functions have been used to describe this pattern, we here propose a chemical kinetics theory which successfully replicates this observation and provides insights into the processes responsible for these dynamics. The chemical kinetics theory combines the law of mass action, von Smoluchowski's diffusion-limited chemical reaction theory, and Eyring's transition state theory. This new theory reveals that the thermally reversible enzyme denaturation ensured by the ceaseless thermal motion of molecules and ions in an enzyme solution explains the plateau and subsequent decrease in chemical reaction rates with increasing temperature. The temperature-dependent affinity parameter (K) that relates enzymes and substrates through their binding also affects the shape of the emergent temperature response. We demonstrate that with an increase in substrate availability, K shifts the optimal temperature, where reaction rates plateau, towards higher values. Further, we show that the chemical kinetics theory accurately represents 12 sets of published enzyme assay data and includes the popular mechanistic model by Ratkowsky et al. (2005) as a special case. Given its good performance and solid theoretical underpinning, we believe this new theory will facilitate the construction of more mechanistic-based environmental biogeochemical models.

Tang, Jinyun↗
DOE OSTI2022

Effect of Intermediate Semiconducting TiOx Thin Films on Nanoparticle-Mediated Electron Transfer: Electrooxidation of CO

The concept of nanoparticle-mediated electron transfer (eT) across insulating thin films was elucidated theoretically by Allongue and Chazalviel in 2011. In their model, metal nanoparticles (NPs) are immobilized atop passivating, self-assembled monolayers (SAMs). They found that under certain conditions, related to the thickness of the SAM and the size of the NPs, efficient faradaic oxidation and reduction reactions could proceed at the NP surface. In the absence of NPs, however, eT was suppressed by the insulating SAM thin films. Allongue and Chazalviel concluded that, within certain bounds, eT is mediated by fast tunneling between the conductive electrode and the metal NPs, while the kinetics of the redox reaction are controlled by the NPs. This understanding has been confirmed using a variety of experimental models. The theory is based on electron tunneling; therefore, the nature of the intervening medium (the insulator in prior studies) should not affect the eT rate. In the present manuscript, however, we show that the theory breaks down under certain electrochemical conditions when the medium between conductors is an n-type semiconductor. Specifically, we find that in the presence of either Au or Pt NPs immobilized on a thin film of TiOx, CO electrooxidation does not proceed. In contrast, the exact same systems lead to the efficient reduction of oxygen. At present, we are unable to explain this finding within the context of the model of Allongue and Chazalviel.

Galyamova, Aigerim↗
DOE OSTI2021

Moisture-induced autonomous surface potential oscillations for energy harvesting

A variety of autonomous oscillations in nature such as heartbeats and some biochemical reactions have been widely studied and utilized for applications in the fields of bioscience and engineering. Here, we report a unique phenomenon of moisture-induced electrical potential oscillations on polymers, poly([2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide-co-acrylic acid), during the diffusion of water molecules. Chemical reactions are modeled by kinetic simulations while system dynamic equations and the stability matrix are analyzed to show the chaotic nature of the system which oscillates with hidden attractors to induce the autonomous surface potential oscillation. Using moisture in the ambient environment as the activation source, this self-excited chemoelectrical reaction could have broad influences and usages in surface-reaction based devices and systems. As a proof-of-concept demonstration, an energy harvester is constructed and achieved the continuous energy production for more than 15,000 seconds with an energy density of 16.8 mJ/cm 2 . A 2-Volts output voltage has been produced to power a liquid crystal display toward practical applications with five energy harvesters connected in series.

42 ENGINEERING↗
DOE OSTI2026

Excitation energy of fission fragments within nuclear time-dependent density functional theory

The number and properties of the neutrons and photons emitted in nuclear fission are directly related to the excitation energy of the fission fragments when they are formed at scission. Though not observable experimentally because of the extremely short timescales, the excitation energy of fission fragments can be predicted by microscopic theory based on time-dependent density functional theory (TDDFT). Initial results on the value of the total kinetic energy of fission reactions were very promising, but could not probe all possible fragmentations. Here, in this work, we perform large-scale TDDFT calculations in 240 Pu enabled by the development of a new TDDFT solver. We obtain TDDFT trajectories covering nearly all possible fragmentations. We find that the total kinetic energy is close to experimental values only for the most likely fission while it is severely underestimated at both small and large asymmetries. This conclusion seems rather independent of the parametrization of the energy functional, both in its particle-hole and particle-particle channels.

Physics - Nuclear physics and radiation physics↗
DOE OSTI2026

The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO

The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Multiscale Reactive Model for 1,3,5-Triamino-2,4,6-trinitrobenzene Inferred by Reactive MD Simulations and Unsupervised Learning

When high-energy-density materials are subjected to thermal or mechanical insults at extreme conditions (shock loading), a coupled response between the thermo-mechanical and chemical behaviors is systematically induced. Herein we develop a reaction model for the fast chemistry of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) at the mesoscopic scale, where the chemical behavior is determined by underlying microscopic reactive simulations. The slow carbon cluster formation is not discussed in the present work. All-atom reactive molecular dynamics (MD) simulations are performed with the ReaxFF potential, and a reduced-order chemical kinetics model for TATB is fitted to isothermal and adiabatic simulations of single crystal chemical decomposition. Unsupervised machine learning techniques based on non-negative matrix factorization are applied to MD trajectories to model the decomposition kinetics of TATB in terms of a four-component model. The associated heats of reaction are fit to the temperature evolution from adiabatic decomposition trajectories. Using a chemical species analysis, we show that non-negative matrix factorization captures the main chemical decomposition steps of TATB and provides an accurate estimation of their evolution with temperature. The final analytical formulation, coupled to a diffusion term, is incorporated into a continuum formalism, and simulation results are compared one-to-one against MD simulations of 1D reaction propagation along different crystallographic directions and with different initial temperatures. A good agreement is found for both the temporal and spatial evolution of the temperature field.

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

Best of both worlds: Enforcing detailed balance in machine learning models of transition rates

The slow microstructural evolution of materials often plays a key role in determining material properties. When the unit steps of the evolution process are slow, direct simulation approaches such as molecular dynamics become prohibitive and Kinetic Monte-Carlo (kMC) algorithms, where the state-to-state evolution of the system is represented in terms of a continuous-time Markov chain, are instead frequently relied upon to efficiently predict long-time evolution. The accuracy of kMC simulations however relies on the complete and accurate knowledge of reaction pathways and corresponding kinetics. This requirement becomes extremely stringent in complex systems such as concentrated alloys where the astronomical number of local atomic configurations makes the a priori tabulation of all possible transitions impractical. Machine learning models of transition kinetics have been used to mitigate this problem by enabling the efficient on-the-fly prediction of kinetic parameters. While conventional KMC methods based on transition state theory naturally yield reversible dynamics that exactly obey the detailed balance criterion, providing strong guarantees on the properties of the stationary distribution, many recently-proposed ML-based approaches to barrier predictions provide no such guarantees. In this study, we derive conditions under which physics-informed ML architectures exactly enforce the detailed balance condition by construction, even when relying on non-extensive descriptions of states in terms of local environments around mobile defects. In conclusion, using the diffusion of a vacancy in a concentrated alloy as an example, we show that such ML architectures also exhibit superior performance in terms of prediction accuracy, demonstrating that the imposition of physical constraints can facilitate the accurate learning of barriers at no increase in computational cost.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Curvature effects in the reaction-diffusion system governing frontal polymerization

Frontal polymerization is a fast and energy-efficient curing process of thermoset polymers involving the self-sustained propagation of a sharp front that transforms a liquid monomer or gel into a polymer. The temperature, speed, and geometry of the polymerization front are closely intertwined quantities that can affect the curing process and the mechanical properties of the polymer. This work investigates the effect of the front curvature on the front propagation speed based on a reaction-diffusion model. The proposed analytical relations between front speed and curvature are verified by finite element simulations and validated through experiments. The models show that a concave front has a higher front temperature and speed than its convex counterpart. When the curvature of a convex front reaches a critical value, the reaction can no longer be sustained, and the front is quenched. The relation between the speed of a steadily propagating front and its geometry is derived, showing good agreement with experimental observations. This study also provides analytical estimates of the thickness of the polymerization front and insight into the relationship between the front curvature and the kinetics of the exothermic reaction.

42 ENGINEERING↗
DOE OSTI2022

Controlling Structural, Electronic, and Energy Flow Dynamics of Catalytic Processes through Tailored Nanostructures

MoS 2 (molybdenum disulfide) is a highly-versatile catalyst material for support of numerous reactions from hydrodesulfurization and denitrogenation to the focus of this renewal proposal: hydrogenation of CO/CO 2 towards (higher) alcohols. At the same time, MoS 2 is a non-toxic, environmentally-benign and rather inert material- which under ambient conditions for some time has served as a lubricant and, more recently, as next-generation electronic material. The apparent contrast between inertness and stability in ambient, and catalytic activity under reactive conditions is puzzling and calls for a synergistic theoretical and experimental investigation with the long-term objective of enabling the rational design of MoS 2 -based catalysts for alcohol-formation reactions by providing a microscopic understanding of the environmental factors that determines site activity and selectivity. Our research project seeks answers to the questions (a) what conformation does MoS 2 adopt under reaction conditions (as opposed to that under ultrahigh vacuum and low temperatures)?; (b) what reaction pathways exist on such a material?; (c) how can the local environment of the active sites be manipulated so as to make MoS 2 an efficient catalyst for production of higher alcohol from syngas? In particular, research strategies will explore how the basal plane composed of sulfur atoms can be activated so as to exhibit a reactivity of its own, by addressing three research targets and building on extensive preliminary and enabling work: (1) vacancies and vacancy aggregates on the basal plane; (2) non-local catalyst transformation through alkali doping, hydrogenation and phase transition; (3) fabrication of a metal-nanoparticle-activated MoS 2 system, in which particle anchoring, reactive sites and pathways as well as selectivity are controlled by design, as an example of predictive development of a catalyst material,. All strategies are directed to improve the efficacy of the key reactive sites and selectivity of chemical pathways by design, to replace the inefficient methodology of trial and error in catalyst development. This research project represents a synergistic combination of computational guidance, foundational surface-science-based experiments and validation under reactive conditions that aims at transformative new insights into the working of MoS 2 -based hydrogenation-catalysts, a topic squarely at the center of the interest of DOE BES. Guided and led by Talat Rahman, a computational physicist, this project will apply density functional theory to understand structure, reaction pathways and chemical potentials associated with MoS 2 -based CO/CO 2 hydrogenation, augmented by kinetic Monte Carlo methods for reaction rates and prefactors as well as ab-initio molecular dynamics for evaluation of thermal stability. Complementary experimental input and validation will originate from co-PI Ludwig Bartels, a physical chemist and materials scientist, whose group focuses on local imaging and preparation of MoS 2 materials, from co-PI Peter Dowben, an experimental physicist, whose group is expert in the spectroscopy of occupied and unoccupied electronic states, and from senior collaborator Michael White of Brookhaven National Laboratory, whose group generates high-resolution electronic and activity information on size-selected well-defined metal chalcogenide clusters. This collaborative effort will enable a comprehensive understanding of the correlation of structural integrity and catalytic activity of MoS 2 in forms ranging from extended films to individual particles with known geometries and binding sites. Alcohol formation from syngas is a rapidly emerging application that has great potential through facile, economic, and decentralized biomass gasification. CO 2 activation is one of the most pressing concerns of our time: increasing CO 2 levels in the atmosphere change the climate and expose the globe to environmental transformations with the potential for enormous economic and societal impact. We will investigate CO/CO 2 hydrogenation via an interdisciplinary research collaboration with established synergy – one that, in accordance with the mission of the DOE, involves accredited Hispanic-Serving Institutions and that, through student exchange with international collaborators and National Labs, will directly benefit a broad spectrum of communities and generate human resources in sciences essential to their future.

2D materials↗
DOE OSTI2021

Unimolecular and bimolecular formic acid decomposition routes on dispersed Cu nanoparticles

The elementary steps and site requirements in formic acid (HCOOH) dehydrogenation on Cu surfaces remain of keen interest because formate species act as intermediates or spectators in methanol synthesis and water–gas shift reactions. Steady-state and transient kinetic data, isotopic effects, infrared spectra during catalytic and stoichiometric reactions, and theoretical treatments based on density functional theory (DFT) provide evidence for bimolecular reactions, in which saturated bidentate formate (*HCOO*) adlayers, present at 0.25 ML (0.25 *HCOO* per surface Cu atom), react with undissociated species (HCOOH$^\square$) bound at interstices within formate adlayers ($^\square$) to form H-bonded bimolecular HCOOH$^\square$-*HCOO* adducts. The co-existence of vicinal HCOOH$^\square$ and *HCOO* moieties is evident from antisymmetric infrared bands for *HCOO* that become stronger as a result of their H-bonding that perturbs the induced dipole moment of *HCOO* upon vibration, consistent with DFT-derived vibrational frequencies and intensities for such perturbed species. The *HCOO* moiety in this complex undergoes C-H activation via a transition state that is preferentially stabilized through H-bonding with the vicinal HCOOH$^\square$ relative to its *HCOO* precursor. DFT-derived HCOOH dehydrogenation activation barriers and those determined from the evolution of CO 2 from pre-adsorbed *HCOO* species are about 10 kJ mol -1 smaller in the presence of gaseous HCOOH reactants (because of HCOOH$^\square$-*HCOO* interactions) than those for the unimolecular decomposition of bound *HCOO* species. Such bimolecular routes are consistent with measured effects of HCOOH, H 2 , and CO pressures and of H/D isotopic substitution on dehydrogenation turnover rates and represent the predominant channel for the formation of CO 2 and H 2 during catalytic HCOOH dehydrogenation on Cu nanoparticles. A saturated *HCOO* adlayer that retains binding interstices and the presence of HCOOH(g) enable a sequence of elementary steps unavailable for *HCOO* species, thus circumventing unassisted unimolecular routes that exhibit higher activation barriers.

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

Kinetic modeling of microbial growth, enzyme activity, and gene deletions: An integrated model of β-glucosidase function in Cellvibrio japonicus

Understanding the complex growth and metabolic dynamics in microorganisms requires advanced kinetic models containing both metabolic reactions and enzymatic regulation to predict phenotypic behaviors under different conditions and perturbations. Most current kinetic models lack gene expression dynamics and are separately calibrated to distinct media, which consequently makes them unable to account for genetic perturbations or multiple substrates. This challenge limits our ability to gain a comprehensive understanding of microbial processes towards advanced metabolic optimizations that are desired for many biotechnology applications. Here, we present an integrated computational and experimental approach for the development and optimization of mechanistic kinetic models for microbial growth and metabolic and enzymatic dynamics. Our approach integrates growth dynamics, gene expression, protein secretion, and gene-deletion phenotypes. We applied this methodology to build a dynamic model of the growth kinetics in batch culture of the bacterium Cellvibrio japonicus grown using either cellobiose or glucose media. The model parameters were inferred from an experimental data set using an evolutionary computation method. The resulting model was able to explain the growth dynamics of C. japonicus using either cellobiose or glucose media and was also able to accurately predict the metabolite concentrations in the wild-type strain as well as in β-glucosidase gene deletion mutant strains. We validated the model by correctly predicting the non-diauxic growth and metabolite consumptions of the wild-type strain in a mixed medium containing both cellobiose and glucose, made further predictions of mutant strains growth phenotypes when using cellobiose and glucose media, and demonstrated the utility of the model for designing industrially-useful strains. Importantly, the model is able to explain the role of the different β-glucosidases and their behavior under genetic perturbations. Here, this integrated approach can be extended to other metabolic pathways to produce mechanistic models for the comprehensive understanding of enzymatic functions in multiple substrates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

Metal oxides have been actively explored as promising conversion-type electrode materials for lithium ion batteries due to high deliverable capacity but still notorious for poor cyclability, capacity fading, voltage hysteresis, etc. Yet, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. Difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li-Metal (M)-O, suggesting lithium removal accompanies with the Li/M ionic exchange and rearrangement of oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by remaining Li-M-O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. Furthermore, this work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Restructuring of the Lewis Acid Sites in Y-Modified Dealuminated Beta-Zeolite by Hydrothermal Treatment

Yttrium-modified dealuminated Betazeolite (Y-BEA) represents a type of Lewis acid zeolite that has gained attention for its potential to efficiently catalyze the conversion of biomass-derived oxygenates. The structure of the Y active sites and their dynamics during biomass conversion reactions, which normally involve substantial amounts of water, necessitate thorough investigation for the rational design of more active and stable catalysts. Here, we conducted a study where a series of Y-BEA catalysts with different yttrium loadings (1–7 wt.%) were subjected to hydrothermal treatment (450 °C, 20% water) and investigated for their structural and catalytic activity changes through a combination of multiple characterizations and kinetic measurements. The number of acid sites of Y-BEA decreased without a change in acid strength following the hydrothermal treatment, which was confirmed by the results of acid site titration, infrared spectroscopy of probe molecules, and kinetic measurements for probe reactions (acetone aldol condensation). Structural analysis using X-ray diffraction (XRD), specific surface area measurement, X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS) demonstrated that both the zeolite structure and the isolation status of the Y site remain intact after hydrothermal treatment. Further, the Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) spectra, thermogravimetric analysis (TGA), and operando 1 H and 29 Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) revealed the dehydroxylation of Y-BEA induced by hydration-rearrangement-condensation restructuring during the high-temperature steam treatment. Dehydroxylation affects the structure of Y sites by reducing their vicinal silanol sites. In conclusion, this conversion of Lewis acidic Y sites into nonacidic sites is the primary factor behind the change in acid site quantity and catalytic activity on Y-BEA.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A high-temperature sample changer for parallelized in situ X-ray studies to efficiently explore reaction space

A sample environment for high-throughput X-ray scattering studies in transmission geometry to probe the mechanism and kinetics of moderate-temperature reactions in solution, molten fluxes and solids is described. This high-temperature sample changer enables efficient studies of reactions that are slow relative to the timescale of the X-ray scattering measurements by allowing up to 18 samples to be probed at the same temperature in parallel. This significantly enhances the throughput ofin situX-ray scattering studies as the sample changer effectively facilitates systematic studies that compare different reaction parameters (e.g.concentration, precursor, composition, additives), reference samples (e.g.background, pure precursors) and replicates (to demonstrate reproducibility) with enhanced consistency afforded by the quasi-simultaneous nature of the measurements. The large sample volumes, compared with those typically used for X-ray scattering measurements, are on a similar scale to those in the laboratory, making the results more directly comparable.

Chemistry↗
DOE OSTI2024

Accelerated Steam Methane Reforming by Dynamically Applied Charges

Catalyst design has traditionally focused on tuning active site properties to optimally bind reaction intermediates and balance the kinetic requirements of multiple competing chemical processes, as necessitated by the Sabatier principle. It has recently been proposed that for reactions following certain potential energy landscapes, the activity limit imposed by the Sabatier principle may be overcome by using programmed oscillations of surface electron density at the timescales of surface reactions (i.e., “catalytic resonance”). Here, we use a combination of density functional theory (DFT) simulations and transient kinetic models (TKMs) to simulate the kinetics of steam methane reforming (SMR) on Ru(211) surfaces under statically and dynamically applied charges. DFT-calculated binding energies of SMR intermediates and transition states exhibit strong sensitivity to positively applied charges and follow unique scaling relationships that deviate from linear periodic trends across transition metals. Our simulations demonstrate that applying a small positive charge to Ru dramatically enhances the steady-state turnover frequency (TOF) of SMR by up to 5 orders of magnitude above the TOF observed over neutral Ru. Thus, statically charging Ru catalysts may be an effective strategy to lower the temperature requirements for SMR. Dynamic square-wave oscillations in charge resulted in SMR catalytic resonance with an onset frequency f ∼ 106 Hz and the corresponding average TOFs exceeding the statically charged Ru surface by an additional 15%. Here, based on sensitivity analyses performed for the two end points of oscillation, we propose that dynamic TOF improvement beyond the Sabatier maximum can be expected when the system oscillates between two kinetic regimes that are uniquely controlled by distinct elementary steps.

Catalysts↗
DOE OSTI2026

Distinct Kinetic Signatures of Photodesorption from Metal Nanoparticles

Visible photon fluxes can influence the rate and selectivity of heterogeneously catalyzed reactions on metal nanoparticle surfaces. Models describing the influence of photon fluxes have typically introduced photon flux dependent apparent thermal kinetic parameters (reaction orders, activation energies, binding energies, etc.). This has relied on empirical fitting of reaction rate data, making mechanistic interpretations of how photon fluxes influence elementary step rates challenging and inconsistent with fundamental descriptions of photochemistry on metal surfaces developed from surface science studies. Using the CO adsorption–desorption quasi-equilibrium reaction on Pt/Al 2 O 3 catalysts as a model system, we measured steady state adsorbed CO (CO*) coverages under isothermal and isobaric (1 mbar CO) conditions as a function of temperature (473–573 K) and of 440 nm photon flux ((0.1–5.2) × 10 3 # hv Pt site –1 s –1 ) using in situ IR spectroscopy. Steady state CO* coverage on Pt was photon flux dependent with increasing photon flux causing decreasing coverage, consistent with photons driving CO* desorption rates faster than thermal CO* desorption rates. However, photon flux dependent CO* coverages were essentially temperature independent, inconsistent with models that describe photon effects using perturbations to apparent thermal kinetic parameters. Instead, 120 steady state CO* coverages as a function of temperature and photon flux are quantitatively described by a kinetic model in which the overall desorption rate is a summation of independent thermal and photon induced CO* desorption rates. Site-resolved analysis reveals distinct kinetic parameters for photon driven desorption of CO* from well-coordinated, under-coordinated, and highly under-coordinated Pt sites, with temperature-dependent apparent quantum efficiencies (AQE) consistent with temperature dependence of vibrational quanta distribution of adsorbed CO. The rigorous kinetic rate laws for independent photon and thermal driven pathways allow for predictive modeling of the influence of photon fluxes on the rates of CO* desorption under catalytic conditions. Further, the analysis provides evidence that steady state continuous wave photon fluxes can drive desorption/adsorption reactions on metal surfaces out of thermal equilibrium, reconciling surface science observations of molecular photodesorption with applied catalysis. The work establishes a general kinetic framework to be considered for photon driven processes on metals, and defines catalyst, reaction, and photon flux characteristic design principles for breaking Sabatier limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗