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DOE OSTI2024

BioRT‐HBV 1.0: A Biogeochemical Reactive Transport Model at the Watershed Scale

Abstract Reactive Transport Models (RTMs) are essential tools for understanding and predicting intertwined ecohydrological and biogeochemical processes on land and in rivers. While traditional RTMs have focused primarily on subsurface processes, recent watershed‐scale RTMs have integrated ecohydrological and biogeochemical interactions between surface and subsurface. These emergent, watershed‐scale RTMs are often spatially explicit and require extensive data, computational power, and computational expertise. There is however a pressing need to create parsimonious models that require minimal data and are accessible to scientists with limited computational background. To that end, we have developed BioRT‐HBV 1.0, a watershed‐scale, hydro‐biogeochemical RTM that builds upon the widely used, bucket‐type HBV model known for its simplicity and minimal data requirements. BioRT‐HBV uses the conceptual structure and hydrology output of HBV to simulate processes including advective solute transport and biogeochemical reactions that depend on reaction thermodynamics and kinetics. These reactions include, for example, chemical weathering, soil respiration, and nutrient transformation. The model uses time series of weather (air temperature, precipitation, and potential evapotranspiration) and initial biogeochemical conditions of subsurface water, soils, and rocks as input, and output times series of reaction rates and solute concentrations in subsurface waters and rivers. This paper presents the model structure and governing equations and demonstrates its utility with examples simulating carbon and nitrogen processes in a headwater catchment. As shown in the examples, BioRT‐HBV can be used to illuminate the dynamics of biogeochemical reactions in the invisible, arduous‐to‐measure subsurface, and their influence on the observed stream or river chemistry and solute export. With its parsimonious structure and easy‐to‐use graphical user interface, BioRT‐HBV can be a useful research tool for users without in‐depth computational training. It can additionally serve as an educational tool that promotes pollination of ideas across disciplines and foster a diverse, equal, and inclusive user community.

Sadayappan, Kayalvizhi↗
DOE OSTI2020

Impact of Biofuel Blends on Black Carbon Emissions from a Gas Turbine Engine

With a view towards renewable feedstock while decreasing the CO2 footprint associated with jet travel, biofuels are receiving increasing interest. Presented here is an overview of non-volatile particulate matter (nvPM) emissions, i.e. “soot” as gauged by varied TEM analyses for a J-85 turbojet fueled with Jet-A as well as with blends of Jet-A using Camelina biofuel. A unifying explanation is provided encompassing fuels and spanning length scales across three orders of magnitude. The variation of primary particle size, aggregate size and nanostructure are analyzed as a function of biofuel blend across range of engine thrust levels. The postulate is based on where fuels start along the soot formation pathway. Increasing biofuel content lowers aromatic concentration while placing increasing dependence upon fuel pyrolysis reactions to form the requisite concentration of aromatics for particle inception and growth. The required “kinetic” time for pyrolysis reactions to produce benzene and multi-ring PAHs allows increased fuel-air mixing by turbulence, diluting the fuel-rich soot-forming regions, effectively lowering their equivalence ratio. With a lower precursor concentration, particle inception is slowed, the resulting concentration of primary particles is lowered and smaller aggregates. The lower equivalence ratio also results in smaller primary particles given the lower concentration of growth species.

Kumal, Raju R.↗
DOE OSTI2024

Data Analytics for Catalysis Predictions: Are We Ready Yet?

Catalysis informatics has received tremendous attention in recent years as a tool to design catalysts and discover unique descriptors that capture the relationships between chemical properties and catalytic performance. One of the stop-gaps in understanding catalytic effects, which is often ignored and limits the deployment of data science tools, relates to the lack of uniform data. The catalytic cleavage of C–X (X= H, C, N, and O) bonds is relevant to many fundamental catalytic processes. In this Perspective, we performed data analytics on four groups of C–X cleavage reactions that are common in production, upcycling, or reactive separation: the C–C cleavage in cyclopropyl alcohol, the C–H cleavage in hydroacylation reactions, the C–O cleavage in β-O-4 linkages, and the C–N cleavage in amides, using experimental data collected from the literature to understand their underlying correlations. Experimental variables of high impact are identified for each reaction by dimensionality reduction methods. We highlight the urgent need for experimental data sets that include full details on the reaction conditions, such as reagent concentration, reaction temperature, or time in machine-readable forms. We discuss the potential improvement of the data of these reactions and promising approaches such as autonomous experiments to fill the gaps in unbiased experimental data. Finally, we also address the early stage consideration of separation aspects in the experimental design of efficient catalytic systems for these fundamental examples of chemical reactivity.

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

Shell effects in quasi-fission for calcium induced reactions forming thorium isotopes

Quantum shell effects induce an asymmetric fission mode in actinides, which disappears in neutron deficient isotopes. Quasi-fission, characterized by a significant mass transfer in heavy ion collisions at low-energies, is expected to be affected by similar shell effects. This is studied in 40−56 Ca+176 reactions with the time-dependent Hartree-Fock approach. All reactions exhibit a mass equilibration process that stops when a heavy fragment with 𝑍 ≃ 54 protons is formed. Unlike the fission of thorium compound nuclei, quasi-fission does not exhibit a transition to symmetric modes in neutron deficient systems. This observation is interpreted in terms of potential energy surfaces that show a persistence of an asymmetric valley with an increasing barrier preventing its population in fission of the most neutron deficient thorium isotopes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

mesoflow [SWR-22-56]

Mesoflow is a continuum scale simulation tool developed specifically for modeling transport and chemistry at the mesoscale. Our solver utilizes Cartesian block-structured adaptive mesh refinement to resolve complex surface morphologies (of catalysts/biomass particles among others) directly obtained from X-ray tomography data. An immersed boundary based formulation enables rapid representation of complex geometries prevalent in most mesoporous interfaces. The solver is developed on top of open-source performance portable library, AMReX, providing parallel execution capabilities on current and upcoming high-performance-computing (HPC) architectures. Our flexible software framework enables integration of complex chemical mechanisms at heterogenous interfaces and time-split algorithms for circumventing highly disparate reaction and flow time-scales. Our current studies indicate a ten-fold performance gain by using graphics-processing-units (GPU) compared to a single processor for representative problem sizes (2 million cell mesh).

Sitaraman, Hariswaran↗
DOE OSTI2022

Mesoflow: An Open-Source Reacting Flow Solver for Catalysis at Mesoscale

We present the capabilities and software performance metrics of our open-source continuum solver for catalysis, Mesoflow, developed specifically for modeling transport and chemistry at the mesoscale. Our solver utilizes Cartesian block-structured adaptive mesh refinement to resolve complex catalyst surface morphologies directly obtained from X-ray tomography data. An immersed boundary based formulation enables rapid representation of complex geometries prevalent in most mesoporous catalyst interfaces. The solver is developed on top of open-source performance portable library, AMReX, providing parallel execution capabilities on current and upcoming high-performance-computing (HPC) architectures. Our flexible software framework enables integration of complex chemical mechanisms at heterogenous interfaces and time-split algorithms for circumventing highly disparate reaction and flow time-scales. Our current studies indicate a ten-fold performance gain by using graphics-processing-units (GPUs) compared to a single processor for representative problem sizes (2 million cell mesh). We will also present a brief introduction on how to build and use this software for application problems pertaining to catalytic upgrading and gas transport within porous catalyst particles.

adaptive meshing↗
DOE OSTI2023

Charged particle reconstruction in CLAS12 using Machine Learning

In this work, we present studies of track parameter reconstruction from raw information in CLAS12 detector's Drift Chambers, using Machine Learning (ML). We study the resolution of tracks reconstructed with different types of ML models/algorithms, including Multi-Layer Perceptron (MLP), Extremely Randomized Trees (ERT) and Gradient Boosting Trees (GBT) using simulated data. We find that the resulting ML model is capable of reconstructing track parameters (particle momentum, and polar and azimuthal angles) with accuracy similar to Hit Based (HB) tracking code, but $150$ times faster. Moreover, physics reactions can be identified using the particles reconstructed by the neural network in real-time (with a rate of about $34~kHz$) during experimental data collection. The developed model can be used in numerous applications, such as triggering specific physics reactions in real-time, detector performance monitoring, and real-time detector calibration.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Constraining the destruction rate of K 40 in stellar nucleosynthesis through the study of the Ar 40 ( p , n ) K 40 reaction

Background: We present that K 40 plays a significant role in the radiogenic heating of Earth-like exoplanets, which can affect the development of a habitable environment on their surfaces. The initial amount of K 40 in the interior of these planets depends on the composition of the interstellar clouds from which they formed. Within this context, nuclear reactions that regulate the production of K 40 during stellar evolution can play a critical role. Purpose: In this study, we constrain for the first time the astrophysical reaction rate of K 40 ( n , p ) Ar 40 , which is responsible for the destruction of K 40 during stellar nucleosynthesis. We provide to the nuclear physics community high-resolution data on the cross section and angular distribution of the Ar 40 ( p , n ) K 40 reaction. These are important to various applications involving Ar 40 . The associated reaction rate of the Ar 40 ( p , n ) K 40 process addresses a reaction rate gap in the Joint Institute for Nuclear Astrophysics REACLIB database in the region of intermediate-mass isotopes. Methods: We performed differential cross-section measurements on the Ar 40 ( p , n ) K 40 reaction, for six energies in the center-of-mass system between 3.2 and 4.0 MeV and various angles between 0 ° and 135 ° . The experiment took place at the Edwards Accelerator Laboratory at Ohio University using the beam swinger target location and a standard neutron time-of-flight technique. We extracted total and partial cross sections by integrating the double differential cross sections we measured. Results: The total and partial cross sections varied with energy due to the contribution from isobaric analog states and Ericson type fluctuations. The energy-averaged neutron angular distributions were symmetrical relative to 90 ° . Based on the experimental data, local transmission coefficients were extracted and were used to calculate the astrophysical reaction rates of Ar 40 ( p , n ) K 40 and K 40 ( n , p ) Ar 40 reactions. The new rates were found to vary significantly from the theoretical rates in the REACLIB library. We implemented the new rates in network calculations to study nucleosynthesis via the slow neutron capture process, and we found that the produced abundance of K 40 is reduced by up to 10% compared to calculations with the library rates. At the same time, the above result removes a significant portion of the previous theoretical uncertainty on the K 40 yields from stellar evolution calculations. Conclusions: Our results support a destruction rate of K 40 in massive stars via the K 40 ( n , p ) Ar 40 reaction that is larger compared to previous estimates. The rate of K 40 destruction via the K 40 ( n , p ) Ar 40 reaction now has a dramatically reduced uncertainty based on our measurement. Lastly, this result directly affects the predicted stellar yields of K 40 from nucleosynthesis, which is a critical input parameter for the galactic chemical evolution models that are currently employed for the study of significant properties of exoplanets.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Kinetically Controlled Linker Binding in Rare Earth-2,5-Dihydroxyterepthalic Acid Metal–Organic Frameworks and Its Predicted Effects on Acid Gas Adsorption

In the pursuit of highly stable and selective metal–organic frameworks (MOFs) for the adsorption of caustic acid gas species, an entire series of rare earth MOFs have been explored. Each of the MOFs in this series (RE-DOBDC; RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; DOBDC = 2,5-dihydroxyterepthalic acid) was synthesized in the tetragonal space group I4/m. Crystallized MOF samples, specifically Eu-DOBDC, were seen to have a combination of monodentate and bidentate binding when synthesized under typical reaction conditions, resulting in a contortion of the structure. However, extended crystallization times determined that this binding is kinetically controlled and that the monodentate binding option was crystallographically eliminated by extended reaction times at higher temperatures. Furthermore, this series allows for the direct study of the effect of the metal center on the structure of the of the MOF; herein, the lanthanide metal ionic radii contraction across the periodic table results in a reduction of the MOF pore size and lattice parameters. Scanning electron microscopy–energy-dispersive spectroscopy was used to investigate the stages of crystal growth for these RE-DOBDC MOFs. All MOFs, except Er-DOBDC had a minimum of two stages of growth. These analogues were demonstrated by analysis of neutron diffraction (PND) to exhibit a cooperative rotational distortion of the secondary building unit, resulting in two crystallographically distinct linker sublattices. Computational modeling efforts were used to show distinct differences on acid gas (NO 2 and SO 2 ) binding energies for RE-DOBDC MOFs when comparing the monodentate/bidentate combined linker with the bidentate-only linker crystal structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Water film-driven Mn (oxy)(hydr)oxide nanocoating growth on rhodochrosite

Minerals exposed to moist air stabilize thin water films that drive a score of chemical reactions of great importance to water-unsaturated terrestrial environments. In this study, we identified Mn (oxy)(hydr)oxide nanocoatings formed by the dissolution, oxidation and precipitation of Mn in oxygenated water films grown on rhodochrosite (MnCO 3 ) microparticles. Nanocoatings that could be identified by vibrational spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and (scanning and transmission) electron microscopy formed in water films containing the equivalent of at least 7 monolayers (~84 H 2 O/nm 2 ). These films were formed by exposing microparticles to moist air with at least 50% relative humidity (RH). Films of neutral pH reacted up to 14% of the Mn II located in the topmost ~5 nm region of the microparticles in atmospheres of up to 90% RH for 7 d. These reactions produced MnOOH, birnessite (MnO 2 ) and hausmannite (Mn 3 O 4 ) nanoparticles of low crystallinity, while exposure to atmospheric air for 1 yr. converted only 2% of Mn II in this region to MnOOH. In contrast, reactions in alkaline water films converted up to ~75% of the Mn II but only after 16 d of reaction. These films produced MnOOH and MnO 2 of low crystallinity, as well as crystalline hausmannite. Kinetic modeling of the time-resolved growth of the Mnsingle bondO stretching vibrational bands of these nanocoatings revealed two concurrent reaction processes. A 1 rst -order process was assigned to nucleation events terminating only after a few hours, and a 0-order process was assigned to the sustained growth of nanocoatings from these nuclei over longer reaction time. By identifying nanocoatings formed by water film-driven reactions on rhodochrosite, our study adds new insight into mineralogical transformations relevant to anoxic–oxic boundaries in water-unsaturated environments.

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

Identification and time evolution of thionyl chloride (SOCl 2 ) radiolysis products

In this study, innovative solutions are needed to reduce the amount of high-level waste generated by used nuclear fuel recycling strategies to support the widespread adoption of sustainable nuclear fission energy technologies. To this end, a new sulfur chloride-based process has been developed to recycle zirconium alloy-based materials, which make up a significant fraction of high-level radioactive waste. To support the continued development of this process, we present new data on the potential reaction pathways over time of the products arising from the gamma and electron beam radiolysis of neat thionyl chloride (SOCl 2 ). Interrogation of the gamma irradiated liquid by Raman spectroscopy provided more conclusive identification of the SOCl 2 degradation products, specifically sulfur dichloride (SCl 2 ), molecular chlorine (Cl 2 ), sulfur dioxide (SO 2 ), and sulfuryl chloride (SO 2 Cl 2 ). In comparison, the high dose rate (~10 7 Gy s -1 ) electron beam irradiations formed significantly more degradation products. For both cobalt-60 gamma and electron beam irradiations, the observed degradation products were found to evolve as a function of time post-irradiation via the same reaction pathways, with indication of a solvent regeneration mechanism. These findings are fortuitous for process development, as such a mechanism would be beneficial for process longevity and cost effectiveness.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Impacts on mechanical strength of chemical reactions induced by hydrous supercritical CO2 in Boise Sandstone

Geomechanics experiments were used to assess mechanical alteration of Boise Sandstone promoted by reactions with supercritical carbon dioxide (scCO 2 ) and water vapor. During geologic carbon storage, scCO 2 is injected into subsurface reservoirs, forming buoyant plumes. At brine-plume interfaces, scCO 2 can dissolve into native brines, and water from brines can partition into scCO 2 , forming hydrous scCO 2 . This study investigates the effect of hydrous scCO 2 on the strength of Boise Sandstone. Samples are first exposed to recirculating hydrous scCO 2 for 24 h at 70 °C and 13.8 MPa scCO 2 pressure. Samples are reacted with scCO 2 with added water contents up to 500 mL. After scCO 2 exposure, samples are deformed at room temperature under confining pressures of 3.4, 6.9, and 10.3 MPa. The results demonstrate that hydrous scCO 2 induces chemical reactions in Boise Sandstone, with ions migrating from the solid into the hydrous scCO 2 phase. At the longer time-scales, these reactions could lead to mechanical weakening in the samples; however, on the scale of our experiments, the strength changes are within sample variability. Because the solubility of water in scCO 2 is extremely low (0.008 mol H 2 O per 1 mol CO 2 ), the mineral dissolution of Boise Sandstone was under 0.002 wt.%. Additionally, mineral grains and pore throats in Boise Sandstone are cemented with quartz, which is not susceptible to dissolution at these conditions. Our results indicate that humidity in scCO 2 plumes is unlikely to sustain chemical reactions and induce long term strength changes in quartz cemented sandstones due to resistant mineralogies and low water solubility.

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

Chemical Modeling of ATR Fuel in DOE Standard Canisters with Borated Stainless Steel Corrosion

Road-ready and final disposition packaging configurations for the ATR fuel dictates storage within helium backfilled sealed DOE standard canisters. The packaging configuration for the DOE canisters places 10 ATR elements within a Type 1a basket, and three baskets are loaded within each DOE canister. In order to provide a criticality control mechanism, these stainless baskets are proposed to be built with 1-2 weight percentage of boron. This report seeks to identify effects of corrosion of this basket material over time. The primary reaction found through surveying literature was the oxidation of the iron in steel by water to produce some hydrogen. This reaction was built into the previous chemical model of the DOE canister to assess additional hydrogen and pressure build up over time. Literature for non-borated stainless steel, and carbon steel has shown that irradiation increases the rate of corrosion, and it is assumed a similar effect would occur with borated stainless steel. Due to the wide range of results in literature, and the variation of the corrosion with boron content, a wide range of corrosion rates was tested in the model from 80 nm/yr up to 1800 nm/yr.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Discovering CO Adsorption and Desorption Pathways from Chemical Reaction Neural Network Modeling of Transient Kinetics Spectroscopy

Here, we demonstrate a data-driven approach to interpreting surface reactions by combining time-resolved gas pulsing infrared spectroscopy with chemical reaction neural networks (CRNNs). Using CO adsorption and desorption on Pd(111) at 460–490 K as a model system, we show how transient kinetic data can reveal detailed reaction mechanisms. Starting with a simple one-species model, we systematically evaluate increasingly complex mechanisms involving hollow and bridge site adsorption. Despite the similar goodness of fit to the same experimental absorbance data, our models predict distinct coverage dynamics for different adsorption sites. Through analysis of spectral peak stability and predicted dynamics, we identify a mechanism in which CO primarily adsorbs on bridge sites followed by rapid conversion to hollow sites as being the most physically consistent with experimental observations. This work provides a framework for extracting mechanistic insights from limited experimental data, demonstrating how machine learning can bridge the gap between transient kinetic measurements and a molecular-level understanding of surface reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Electrolyte-Dependent, “Microscopically Irreversible” H-Atom Transfer Kinetics of Ce-Based Metal–Organic Framework, Ce-MOF-808

Redox reactions at the interface of metal oxides and protic electrolytes almost always involve protons and electrons in equal amounts. Given the stoichiometry, these proton-coupled electron transfer (PCET) reactions are thermochemically equivalent to net H-atom transfer (HAT) reactions. The correlation between the chemical nature of solid catalysts and HAT kinetics has been employed for decades as the design principle for energy-relevant reactions (e.g., reactions of 2H + /H 2 ). More recently, chemists have experimentally determined that a change in liquid electrolytes that alters the microenvironment at the redox-active sites has an equally profound impact on electrocatalysis involving PCET/HAT. Yet, precise correlations between the chemical nature of electrolytes and the PCET kinetics are, to date, rare in the literature. Herein, we report our findings using the Ce-based metal−organic framework, Ce-MOF-808, as a model system. Each Ce 6 (μ 3 −O) 4 (μ 3 − OH) 4 (OH) 6 (H 2 O) 6 node of this MOF undergoes a 1H + /1e − redox reaction. Using chronoamperometry and the Cottrell analysis, we have determined that the PCET hopping kinetics within the pores of Ce-MOF-808 can change by orders of magnitude by altering the buffer species and the proton activity of the electrolyte. Furthermore, in all buffers, reductive reactions were ∼3−10 times faster in kinetics than the reverse oxidative reaction with the same electrochemical driving force, suggesting that the system, at first glance, violates the principle of microscopic reversibility. Isothermal titration calorimetry (ITC) and computational simulations corroborated that the buffer-node binding thermodynamics are quite distinct, depending on the chemical nature of the buffer and the oxidation state of the node. Together, these results suggest that the substrate and the product during the oxidative vs reductive reaction of Ce-MOF-808 are chemically different species, which explains the apparent ‘microscopic irreversibility.’ Thus, the rational modulation of electrolytes can dramatically enhance PCET kinetics, even though the solid electrodes remain identical. Implications of these findings are contrasted with the electrochemical/electrocatalytic behavior of other redox-active MOFs, heterogeneous catalysts, and enzymatic systems at the solid−liquid interface.

Ce-based MOF↗
DOE OSTI2024

Differential cross sections of the 16 O (𝑛,𝛼) reaction at neutron energies from 3.8 to 15 MeV

The importance of studying the 16 O (𝑛,𝛼) reaction is motivated by multiple nuclear applications which rely on an accurate nuclear reaction data library for oxygen. Discrepancies between past experimental data on the 16 O (𝑛,𝛼) 13 C reaction and its time-reverse 13 C ⁡(𝛼,𝑛) 16 O reaction have led to various different nuclear data evaluations. Here, we have measured 16 O (𝑛,𝛼) reaction cross sections using the LENZ instrument with the unmoderated white neutron source at LANSCE. Results from 2016/2017 data are discussed and used to benchmark the mcnp and geant simulations of the LENZ experimental setup. We report partial differential cross sections of 16 O (𝑛,𝛼 0 ) at 𝐸 𝑛 = 3.8–15 MeV and 16 O ⁡(𝑛,𝛼 1 +𝛼 2 +𝛼 3 ) at 𝐸 𝑛 =9–15 MeV, based on the new measurement in 2021. The resonances that we observed are in good agreement with the levels in 17 O that were previously measured. The LENZ cross sections are in better agreement with the ENDF/B-VIII.0 evaluation than the with reduced cross section found in ENDF/B-VII.1 up to 6 MeV. However, the current results for 16 O ⁡(𝑛,𝛼 0 ) 13 C g.s. appear to be in the best agreement over the entire energy range with that of JENDL/AN-2005 (ENDF/B-VI.0).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Determination of Phenolic Groups in Bio-Oils Using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022

Phenol components are ubiquitous in wood-derived bio-oils and biocrudes. Their reaction with other functional groups (e.g., aldehydes) may contribute to the formation of carbonaceous species and the expected thermal instability of pyrolysis oils. During hydrotreating, phenols can be recalcitrant species, requiring higher reaction temperatures than other oxygen-containing functional groups. Phenols are also present in upgraded products and have been shown to lead to catalyst deactivation during hydrotreating. They also are the first oxygenated functional group to re-appear in the upgraded product, signaling catalyst deactivation. This procedure covers the determination of phenolic compounds in fast pyrolysis oils. This Laboratory Analytical Procedure (LAP) includes two methods, the first allowing for shorter analysis time at increased reaction temperature, while the second employs a longer analysis time but at room temperature. Additionally, the use of both a single cuvette and of a plate reader are also presented.

09 BIOMASS FUELS↗
DOE OSTI2021

Understanding Reaction Networks through Controlled Approach to Equilibrium Experiments Using Transient Methods

We report a combined experimental/theoretical approach to studying heterogeneous gas/solid catalytic processes using low-pressure pulse response experiments achieving a controlled approach to equilibrium that combined with quantum mechanics (QM)-based computational analysis provides information needed to reconstruct the role of the different surface reaction steps. We demonstrate this approach using model catalysts for ammonia synthesis/decomposition. Polycrystalline iron and cobalt are studied via low-pressure TAP (temporal analysis of products) pulse response, with the results interpreted through reaction free energies calculated using QM on Fe-BCC(110), Fe-BCC(111), and Co-FCC(111) facets. In TAP experiments, simultaneous pulsing of ammonia and deuterium creates a condition where the participation of reactants and products can be distinguished in both forward and reverse reaction steps. This establishes a balance between competitive reactions for D* surface species that is used to observe the influence of steps leading to nitrogen formation as the nitrogen product remains far from equilibrium. Here, the approach to equilibrium is further controlled by introducing delay timing between NH 3 and D 2 which allows time for surface reactions to evolve before being driven in the reverse direction from the gas phase. The resulting isotopic product distributions for NH 2 D, NHD 2 , and HD at different temperatures and delay times and NH 3 /D 2 pulsing order reveal the role of the N 2 formation barrier in controlling the surface concentration of NH x * species, as well as providing information on the surface lifetimes of key reaction intermediates. Conclusions derived for monometallic materials are used to interpret experimental results on a more complex and active CoFe bimetallic catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗