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DOE OSTI2025

AUTOIGNITION DELAY TIMES FOR REFORMATE GAS MIXTURES FROM METHANE GAS ENGINES

Methane slip is a prominent issue in natural gas reciprocating engines that are used in transportation and marine applications. The incomplete combustion that results in methane slip can be resolved with the introduction of hydrogen within the combustion mixture to improve methane oxidation and further enable combustion within the engine crevices where methane has previously remained unreacted. Steam methane reforming (SMR) is a common method used to produce hydrogen and can be used to design an onboard device to reduce methane slip from reciprocating engines. The development of this reformer device requires the validation of high-fidelity chemical kinetic models at the low temperatures of the crevice volumes of these engines. In this work, auto-ignition data is obtained using a shock tube at lean (φ—0.714 or λ—1.4) and stoichiometric (φ, λ = 1) equivalence ratios spanning a temperature range of 1042–1234 K at the 80-bar operating pressure of the test engine. Blends of methane, hydrogen, and reformate products from the SMR reaction are shock-heated in synthetic air, with the ignition delay time measured using an OH* chemiluminescence detector at 310 nm and a CH* detector at 430 nm. The experimental results are compared to several state-of-the-art chemical kinetic mechanisms from the literature. In general, most of the mechanisms show very good agreement with experiments at higher temperatures, with simulation results showing little deviation from experiments at lower temperatures. A sensitivity analysis was conducted, and the results reveal that the reaction H2 + CH3O2 = H + CH3O2H has a very significant role in determining low-temperature ignition delay times (IDTs) of SMR mixtures. These findings provide valuable insights into the chemical kinetics governing methane reformate combustion and contribute to the optimization of onboard reformer designs aimed at mitigating methane slip in natural gas-fueled engines.

Fraze, Matthew↗
DOE OSTI2022

Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials

Since their introduction in 1929, Pauling’s five rules have been used by scientists from many disciplines to rationalize and predict stable arrangements of atoms and coordination polyhedra in crystalline solids; amorphous materials such as silicate glasses and melts; nanomaterials, poorly crystalline solids; aqueous cation and anion complexes; and sorption complexes at mineral-aqueous solution interfaces. The predictive power of these simple yet powerful rules was challenged recently by George et al. (2020), who performed a statistical analysis of the performance of Pauling’s five rules for about 5000 oxide crystal structures. They concluded that only 13% of the oxides satisfy the last four rules simultaneously and that the second rule has the most exceptions. They also found that Pauling’s first rule is satisfied for only 66% of the coordination environments tested and concluded that no simple rule linking ionic radius to coordination environment will be predictive due to the variable quality of univalent radii. We address these concerns and discuss quantum mechanical calculations that complement Pauling’s rules, particularly his first (radius sum and radius ratio rule) and second (electrostatic valence rule) rules. We also present a more realistic view of the bonded radii of atoms, derived by determining the local minimum in the electron density distribution measured along trajectories between bonded atoms known as bond paths, i.e., the bond critical point (rc). Electron density at the bond critical point is a quantum mechanical observable that correlates well with Pauling bond strength. Moreover, a metal atom in a polyhedron has as many bonded radii as it has bonded interactions, resulting in metal and O atoms that may not be spherical. O atoms, for example, are not spherical in many oxide-based crystal structures. Instead, the electron density of a bonded oxygen is often highly distorted or polarized, with its bonded radius decreasing systematically from ~1.38 Å when bonded to highly electropositive atoms like sodium to 0.64 Å when bonded to highly electronegative atoms like nitrogen. Bonded radii determined for metal atoms match the Shannon (1976) radii for more electropositive atoms, but the match decreases systematically as the electronegativities of the M atoms increase. As a result, significant departures from the radius ratio rule in the analysis by George et al. (2020) is not surprising. We offer a modified, more fundamental version of Pauling’s first rule and demonstrate that the second rule has a one-to-one connection between the electron density accumulated between the bonded atoms at the bond critical point and the Pauling bond strength of the bonded interaction. Pauling’s second rule implicitly assumes that bond strength is invariant with bond length for a given pair of bonded atoms. Many studies have since shown that this is not the case, and Brown and Shannon (1973) developed an equation and a set of parameters to describe the relation between bond length and bond strength, now redefined as bond valence to avoid confusion with Pauling bond-strength. Brown (1980) used the valence-sum rule, together with the path rule and the valence-matching principle, as the three axioms of bond-valence theory (BVT), a powerful method for understanding many otherwise elusive aspects of crystals and also their participation in dynamic processes. We show how a priori bond-valence calculations can predict unstrained bond-lengths and how bond-valence mapping can locate low-Z atoms in a crystal structure (e.g., Li) or examine possible diffusion pathways for atoms through crystal structures. In addition, we briefly discuss Pauling’s third, fourth, and fifth rules, the first two of which concern the sharing of polyhedron elements (edges and faces) and the common instability associated with structures in which a polyhedron shares an edge or face with another polyhedron and contains high-valence cations. The olivine [α-(MgxFe1–x)2SiO4] crystal structure is used to illustrate the distortions from hexagonal close-packing of O atoms caused by metal-metal repulsion across shared polyhedron edges. We conclude by discussing several applications of BVT to Earth materials, including the use of BVT to: (1) locate H+ ions in crystal structures, including the location of protons in the crystal structures of nominally anhydrous minerals in Earth’s mantle; (2) determine how strongly bonded (usually anionic) structural units interact with weakly bonded (usually cationic) interstitial complexes in complex uranyl-oxide and uranyl-oxysalt minerals using the valence-matching principle; (3) calculate Lewis acid strengths of cations and Lewis base strengths of anions; (4) determine how (H2O) groups can function as bond-valence transformers by dividing one bond into two bonds of half the bond valence; (5) help characterize products of sorption reactions of aqueous cations (e.g., Co2+ and Pb2+) and oxyanions [e.g., selenate (Se6+O4)2- and selenite (Se4+O3)2-] at mineral-aqueous solution interfaces and the important role of protons in these reactions; and (6) help characterize the local coordination environments of highly charged cations (e.g., Zr4+, Ti4+, U4+, U5+, and U6+) in silicate glasses and melts.

Geochemistry & Geophysics↗
DOE OSTI2023

High-pressure behavior of 3.65 Å phase: Insights from Raman spectroscopy

Abstract The 3.65 Å phase [MgSi(OH)6] is a hydrous phase that is predicted to be stable in a simplified MgO-SiO2-H2O (MSH) ternary system at pressures exceeding 9 GPa. Along cold subduction zones, it is likely to transport water, bound in its crystalline lattice, into the Earth’s interior. The 3.65 Å phase consists of Mg and Si octahedral sites attached to the hydroxyl group that forms a hydrogen bond and is predicted to undergo pressure-induced symmetrization of the hydrogen bond. Therefore, in this study, we investigate the high-pressure behavior of the 3.65 Å phase using Raman spectroscopy. We have conducted five distinct compressions up to ~60 GPa using two different pressure-transmitting media—alcohol mixture and neon. At ambient conditions, we identified vibrational modes using complementary first-principles simulations based on density functional perturbation theory. Upon compression, we note that the first derivative of the vibrational modes in the lattice region stiffens, i.e., b1lattice > 0. In contrast, the hydroxyl region softens, i.e., b1OH > 0. This is indicative of the strengthening of hydrogen bonding upon compression. We noticed a significant broadening of vibrational modes related to hydroxyl groups that are indicative of proton disorder. However, within the maximum pressures explored in this study, we did not find evidence for pressure-induced symmetrization of the hydrogen bonds. We used the pressure derivative of the vibrational modes to determine the ratio of the bulk moduli and their pressure derivative. We note that the smaller bulk moduli of hydrous phases compared to the major mantle phases are compensated by significantly larger pressure derivatives of the bulk moduli for the hydrous phases. This leads to a significant reduction in the elasticity contrast between hydrous and major mantle phases. Consequently, the detection of the degree of mantle hydration is likely to be challenging at greater depths.

Geochemistry & Geophysics↗
DOE OSTI2023

Thermal equation of state of ice-VII revisited by single-crystal X-ray diffraction

Abstract Ice-VII is a high-pressure polymorph of H2O ice and an important mineral widely present in many planetary environments, such as in the interiors of large icy planetary bodies, within some cold subducted slabs, and in diamonds of deep origin as mineral inclusions. However, its stability at high pressures and high temperatures and thermoelastic properties are still under debate. In this study, we synthesized ice-VII single crystals in externally heated diamond-anvil cells and conducted single-crystal X-ray diffraction experiments up to 78 GPa and 1000 K to revisit the high-pressure and high-temperature phase stability and thermoelastic properties of ice-VII. No obvious unit-cell volume discontinuity or strain anomaly of the high-pressure ice was observed up to the highest achieved pressures and temperatures. The volume-pressure-temperature data were fitted to a high-temperature Birch-Murnaghan equation of state formalism, yielding bulk modulus KT0 = 21.0(4) GPa, its first pressure derivative KT0′ = 4.45(6), dK/dT = –0.009(4) GPa/K, and thermal expansion relation αT = 15(5) × 10–5 + 15(8) × 10–8 × (T – 300) K–1. The determined phase stability and thermoelastic properties of ice-VII can be used to model the inner structure of icy cosmic bodies. Combined with the thermoelastic properties of diamonds, we can reconstruct the isomeke P-T paths of ice-VII inclusions in diamond from depth, offering clues on the water-rich regions in Earth’s deep mantle and the formation environments of those diamonds.

Geochemistry & Geophysics↗
DOE OSTI2024

Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K -edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems

Abstract The synchrotron technique of micro X-ray absorption near-edge structure spectroscopy at the sulfur K-edge (S-XANES) provides a unique opportunity to measure the proportion of different oxidation states of sulfur (S) in silicate glasses. Although applied extensively in the analysis of basaltic silicate glasses, few S-XANES studies have investigated variations in S oxidation states with fO2 in felsic silicate glasses. In addition, no study has systematically compared the S-XANES results obtained from the same samples at different photon flux densities to quantify the relationship between exposure time and changes in S speciation in silicate glass, as has been done for Fe and V. This study evaluates observed differences in S speciation measured in experimentally produced H2O-saturated dacitic glasses over a range of reducing to oxidizing conditions (from log fO2 = ΔFMQ-0.7 to ΔFMQ+3.3; FMQ is the fayalite-magnetite-quartz mineral redox buffer) and equilibrated at 1000 °C and 300 MPa. S-XANES spectra were collected at three different photon flux densities using three microspectroscopy beamlines. As is observed in S-XANES analyses of basaltic silicate glasses, beam-induced changes to the S6+/ΣS are observed as a function of photon flux density and beam exposure time. Our results demonstrate that silicate glasses of dacitic composition undergo beam-induced photo-reduction in samples equilibrated at ΔFMQ > +1.75 and photo-oxidation if equilibrated at ΔFMQ < +1. The time required to observe beam-induced changes in the spectra varies as a function of flux density, and our study establishes an upper photon density limit at ~1.0 × 1012 photons/µm2. The S6+/ΣS calculated from spectra collected below this absorbed photon limit at intermediate flux densities (~1–4 × 109 photons/s per µm2) are affected by beam damage, as no conditions were found to be completely free of beam-induced changes. However, the S6+/ΣS ratios calculated below the limit at intermediate flux densities are consistent with thermodynamic constraints, demonstrating that S6+/ΣS ratios calculated from S-XANES spectra can be considered reliable for estimating the oxygen fugacity. Our results carry important implications for the S budget of felsic magmas and dissolution mechanisms in evolved melts. While our results from all three flux densities show the presence of S4+ dissolved in relatively oxidized (ΔFMQ > +1.75) dacitic glass, even in the spectra exposed to the lowest photon densities, we are unable to rule out the possibility that the S4+ signal is the result of instantaneous X-ray irradiation induced beam damage using S-XANES alone. When our spectra are compared to S-XANES spectra from basaltic silicate glasses, important differences exist in the solubility of S2– and S6+ between dacitic silicate melts, pointing to differences in solubility mechanisms as melt composition changes. This study highlights the need for further investigation into beam damage systematics, presence of S4+, and the solubility mechanisms of different oxidation states of S as silicate melt composition changes.

Geochemistry & Geophysics↗
DOE OSTI2024

Bobfinchite, Na[(UO2)8O3(OH)11]·10H2O, a new Na-bearing member of the schoepite family

Abstract The new mineral bobfinchite (IMA2020-082), Na[(UO2)8O3(OH)11]·10H2O, was found in the Burro mine, Slick Rock district, San Miguel County, Colorado, U.S.A., where it occurs as an oxidation product of uraninite on asphaltite matrix in intimate association with gypsum, natrozippeite, metaschoepite, and uranopilite. Bobfinchite crystals are transparent to translucent, yellow, lozenge-shaped disks up to 0.3 mm wide. Crystals are flattened on [100] and exhibit the forms {100}, {011}, {021}, {021}, and {011}. Bobfinchite has a pale-yellow streak and emits very dim yellow fluorescence under 365 nm ultraviolet illumination. The crystals are brittle with very good {100} cleavage and irregular, stepped fracture. The Mohs hardness is ca. 2 based on scratch tests. The calculated density is 5.044 g/cm3 based on the empirical formula and 5.036 g/cm3 for the ideal formula. Bobfinchite is optically biaxial (–), with α = 1.690(5), β = 1.7205(5), and γ = 1.730(5) (white light). The measured 2V, estimated from the interference figure, is 55(5)° and the calculated value is 59.1°. Dispersion is moderate, r > v; orientation: X = a, Y = b, Z = c; pleochroism: X nearly colorless, Y yellow, Z yellow; X < Y ≈Z. Electron microprobe analysis provided the empirical formula (Na0.99Pb0.02)[(UO2)7.99O3(OH)11]·10H2O. The five strongest X-ray powder diffraction lines are [dobs in Å(I)(hkl)]: 7.34(100)(200), 3.59(50)(024), 3.23(60)(224), 3.18(36)(240), and 2.01(23)(624,551,208,640,346). Bobfinchite is orthorhombic, Pbcn, a = 14.6249(9), b = 14.0389(10), c = 16.6923(10) Å, V = 3427.2(4) Å3, and Z = 4. The structure of bobfinchite (R1 = 0.0330 for 3770 I > 4σI) is built from uranyl oxide-hydroxide sheets that adopt the fourmarierite topology, with interlayer Na+ and H2O groups. Both the sheet and interlayer topology mimic those observed in natural and synthetic Na-metaschoepites studied previously, and as seen in other uranyl oxide hydrate minerals, charge balance is achieved at specific sites in the sheet through the substitution O2– ↔ (OH)–.

Geochemistry & Geophysics↗
DOE OSTI2024

Atmospheric Observation System for Greenhouse Gases (GHG) Instrument Handbook

The Greenhouse Gas (GhG) Measurement system is a combination of two systems in series: (1) the Tower Gas Processing (TGP) System, an instrument rack which pulls, pressurizes, and dries air streams from an atmospheric sampling tower through a series of control and monitoring components, and (2) the Picarro model G2301 cavity ringdown spectrometer (CRDS), which measures CO2, CH4, and H2O vapor; the primary measurements of the GhG system.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrochemical Behaviors of Bilayer Oxygen Electrode for Reversible Solid Oxide Cells

Reducing the resistances of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) while retaining the stability of an oxygen electrode, even in the presence of air contaminants such as Cr, H2O and CO2, is of paramount importance to the current commercial development of intermediate-temperature reversible solid oxide cells (IT-RSOCs). In this presentation, a multifunctional, coarsening-resistant, air-contaminants-tolerant and yet ORR/OER-active oxygen electrode (OE) for IT-RSOCs is described. The testing results show that new bilayer OE exhibits a much better ORR/OER activity and stability than the single-layer benchmark LSCF-GDC OE. Remarkably, the new bilayer OE also demonstrates an exceptionally high resistance to Cr-attack, a critical issue to the development of commercial meal-interconnect loaded SOFC/SOEC stacks/systems. Theoretical analysis is also presented to understand the fundamental reasons for the improved ORR/OER activity and stability observed under real-world operating conditions.

Huang, Kevin↗
DOE OSTI2022

Establishing Validation Sites for Field-Level Emissions Quantification from Grain Sorghum in Southern Great Plains

Establish publicly available open-source, high-resolution datasets of greenhouse gas (GHG) emissions, meteorology, soil, and vegetation to support testing and validation of emerging biofuel production monitoring technologies. The project team deployed latest technologies to collect “Gold Standard” data for field- level fluxes of CO 2 , N 2 O, CH 4 and H 2 O in grain sorghum production systems in Texas, Oklahoma, and Kansas. The Oklahoma State University led SMARTFARM was initiated on Oct 1, 2020, due to COVID-19 pandemic delay. We installed closed-path dual laser Eddy Covariance (EC) flux measurement system along with a well-established open-path EC system for simultaneously measuring field-level fluxes of CO 2 , N 2 O, CH 4 , and H2O. The eddy flux data are combined with sub-acre soil moisture and temperature measurements, plant and soil analysis data (nutrient, composition, carbon, growth, and phenology), spatial surveys of soil EC, and pH. Grain sorghum crop was managed including planting and harvesting by producers. All teams recruited postdocs and students for the project and submitted purchase orders for field equipment. The team has developed a draft impact sheet and finalized the advisory board for the project.

09 BIOMASS FUELS↗
DOE OSTI2024

Microwave Absorbing Perovskite Catalysts for Efficient Electrification of Syngas Production from CO2 and Methane

Microwave absorbing catalysts have the potential to make thermal reactions such as methane reforming (CH4 + CO2 + H2O → H2 + CO) into carbon negative processes when coupled with decarbonized electricity. Due to microwaves directly heating the catalyst rather than heating the reactor and gases, even high temperature reactions such as dry reforming methane (DRM, CH4 + CO2 → H2 + CO) can be achieved rapidly, efficiently, and on-demand, ideal for coupling with intermittent renewable electricity. However, microwave catalysts present unique design challenges due to the same material needing to both efficiently absorb microwaves in oxidative and reductive reaction conditions and be an efficient and stable catalyst in inherently non-isothermal reactors. We screened from over 28 catalysts in the La0.8Sr0.2(Co-Ni-Mn)O3 perovskite solid-solution family to determine promising microwave reforming catalysts and identify design principles for effective materials. The best performing catalyst candidate was able to produce syngas ratios (H2:CO) from 1-3, and scale up testing showed CO and H2 production efficiencies rivaling conventional carbon intensive steam reforming efficiencies at the liters per minute level of production.

Marin, Christopher↗
DOE OSTI2024

High-Temperature Oxidation Behavior of Wrought and Additive Manufactured H282 in Direct-Fired Supercritical CO2 Power Cycle Environments

Materials selection is a key concern for corrosion resistance in high temperature and pressure direct-fired supercritical CO2 power cycles. The effect of elevated pressure on corrosion resistance can be critical, as impurities within the supercritical fluid such as H2O and O2 can result in additional corrosion behaviors. Utilizing additive manufacturing (AM) methods for construction of power cycle components requiring both compact and complex designs could be advantageous. AM H282 produced by laser powder bed fusion was exposed to direct-fired conditions (95CO2 – 4H2O – 1 O2) at 750 °C at both atmospheric pressure and supercritical conditions (20 MPa) for up to 4,000 hours. Oxidation behavior, sub-surface carbide formation, and chromia scale volatilization was dependent upon AM preparation techniques and surface modifications. These results are discussed in terms of the potential compatibility issues that may arise when using AM alloys in high temperature regions of direct-fired sCO2 power cycles, particularly for thin-walled components.

Carney, Casey↗
DOE OSTI2024

A Solar Fuels Nexus: Molecules and Materials for Light-Driven Catalysis

The American Chemical Society (ACS) selects two groups of graduate students each year to plan and host a one-day symposium at each national meeting (both fall and spring).This year our Graduate Student Symposium Planning Committee (GSSPC), composed of seven students from four universities, proposal entitled “A Solar Fuels Nexus: Molecules and Materials for Light-Driven Catalysis” was selected for the “Crossroads in Chemistry” ACS Meeting that will take place March 23-26, 2023 in Indianapolis, IN. All members of our GSSPC are affiliated with the DOE Fuels from Sunlight Energy Innovation Hub, with two from the Liquid Sunlight Alliance (LiSA) and five from the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE). Here we request funds to support this symposium. This symposium will highlight research progress and perspectives in the solar fuels generation field and seeks to advance the four priority research objectives (PROs) established by the Department of Energy’s Office of Basic Energy Sciences (DOE-BES) Roundtable Report that are also central to many research goals within LiSA and CHASE. The symposium will consist of research presentations from 10 invited senior researcher speakers on topics such as molecular catalyst design, computational modeling of electron transfer systems, microenvironmental effects on CO2 reduction and H2O oxidation catalysis, and intelligent design of semiconductor interfaces with ample time for discussions. These research topics fit very well with the Solar Photochemistry supported research areas of “light-driven electron and energy transfer in condensed phase and interfacial molecular systems,” “electrocatalysis and photocatalysis of solar fuels reactions,” and “semiconductor photoelectrochemistry.” More broadly, this symposium seeks to advance the DOE-BES’s mission to: “support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules” by providing a diverse atmosphere where such research will be disseminated, discussed, and debated. There will be a strong focus on Diversity, Equity, and Inclusivity (DEI) in our symposium. Of our 10 speakers, 7 will be from underrepresented demographics in STEM, including 5 who identify as women. Furthermore, we have representatives from academia accompanied by one national lab scientist and one officer from the Office of Fossil Energy and Carbon Management at the DOE. All speakers will be holding a short DEI moment ahead of their talks. In order to support the career development of attending early career scientists, we will also be hosting a luncheon specifically for graduate students and postdocs to provide them opportunities to network with the distinguished speakers and other attendees. DOE funds for this symposium will be used to support the attendance and participation of 15 graduate students from US institutions by defraying travel and registration costs. These funds will promote engagement and conversation between early career scientists in the solar fuels field, while disseminating solar fuels research funded by and relevant to the DOE.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Multi-Parameter Optical Fiber for Distributed Sensing of Humidity, CH4, CO2, and Corrosion

This work describes the use of the optical fiber sensor (OFS) for successful monitoring of humidity, CH4, and CO2 based on the strain produced along the single-mode fiber (SMF) sensor. This is enabled by absorption of H2O/gases onto the commercially available polyacrylate coated jacketed portion of the fiber resulting in a change in strain. Under equilibrium, a differential microstrain was observed along the jacketed portion of the SMF with N2, CH4, and CO2 at different relative humidity (RH) conditions. The strain response of the SMF under various mixed gas composition and different RH conditions were also measured and made calibration curves accordingly. Linear regression and principal component analysis of the strain datasets provided deconvolution of the impact of strain from H2O, N2, CH4, and CO2. Additionally, modified OFS comprised of the Fe coated fiber section was employed to monitor corrosion based on the increase in backscattered intensity amplitude of the light being passed once corrosion of Fe occurs. Also, corrosion of Fe was studied under soil by installing the fiber in soil with protective measures which would prevent the sensor being mechanically disturbed or broken during installation. The corrosion rates were studied by monitoring the rate at which the intensity of backscattered light amplitude attains a steady state value when complete corrosion of Fe with a specific coating thickness occurs.

Mainali, Badri↗
DOE OSTI2025

Combined TDLAS and chemiluminescence imaging in a flat flame burner operated with NH3/H2 blends

Ammonia is viewed as a viable hydrogen carrier due to favorable storage and transport characteristics. While it can be re-converted to hydrogen at point-of-use via thermal catalytic cracking, direct utilization in combustion systems can result in reduced costs and improved efficiency. A major barrier to this approach is the low flammability and potential for high nitrogen oxide emissions, driven by fuel-bound nitrogen and complex kinetic pathways. While a number of kinetic mechanisms currently exist for simulating ammonia combustion, a major need continues to be direct information about species profiles in easy-to-model systems capable of isolating chemical kinetics from multi-dimensional fluid dynamic effects. This paper reports on recent species measurements made in a flat flame burner using a combined tunable-diode-laser-absorption-spectroscopy (TDLAS) and chemiluminescence imaging approach. Three flame conditions were included representative of NH3/H2 blends, partially cracked NH3 (inc. N2), and 100% NH3 with enhanced air (30% oxygen). Two NIR distributed feedback (DFB) laser diodes were used to determine H2O concentration and temperature (via ratio thermometry) at various radial and axial positions, after which an inverse Abel transform was used to infer centerline values. Companion images were collected using a Princeton Instrument PI-MAX intensified camera equipped with a 105mm UV lens and multiple filter sets targeting OH*, NH*, and NH2* emission. Results were compared to companion Cantera burner-stabilized flame simulations using various kinetic mechanisms. A recent mechanism including excited species chemistry was also included, to investigate whether excited and ground state profiles exhibit significant differences.

ammonia combustion↗
DOE OSTI2025

The Effect of Flow on CO2 Corrosion of Self-Healing Metallic Coatings

Internal corrosion is an issue that affects natural gas pipelines, a significant part of the United States’ energy infrastructure. Over time, this corrosion has worn away longstanding pipelines due to the original construction materials used for the lines and impurities in the gas and liquid streams flowing through them. The main impurities in natural gas are H2O, CO2, H2S, and O2. One of the leading causes of corrosion is the CO2 dissolved in water, giving rise to carbonic acid formation, which can further dissolve the steel pipe. The National Energy Technology Laboratory (NETL) has been studying different solutions to this problem. One potential answer is a self-healing sacrificial metallic coating applied by a novel cold spray technique. This study explored the impact of flow on corrosion with this coating and carbon steel when exposed to a saturated CO2 environment by simulating the pipeline flow profile in a small-scale lab setting. The samples were evaluated using multiple electrochemical techniques that found corrosion rates and were backed up with surface analysis to conclude the behavior of the corrosion mechanisms. The cold spray coating exhibited steel corrosion protection under flow conditions. This study has significantly advanced our understanding of CO2 corrosion, particularly in the context of natural gas pipelines and coating design.

carbon steel↗
DOE OSTI2025

Theoretical study of CO2 capture mechanisms of SrO and Sr(OH)2.nH2O (n=0,1,8)

This presentation encapsulated the use of density functional theory (DFT) to investigate the mechanism of CO2 conversion on various crystal surfaces, including SrO, Sr(OH)2, Sr(OH)2·H2O, and Sr(OH)2·8H2O. The study provides unique insights into the fundamental mechanism for CO2 capture using SrO and its hydrated forms.

catalyst performance↗