Results for “Hydrocarbon trap” — Page 2

DOE OSTI2022

Fetch-trap Pairs: Exploring definition of carbon storage prospects to increase capacity and flexibility in areas with competing uses

As CCS grows beyond isolated first-mover projects, the question of how to identify potential storage sites (prospects) is key to siting projects amidst the constraints of neighboring storage projects, hydrocarbon fields and other considerations. To date, prospects have been defined either by the extent of a buoyant trap or by the predicted maximum extent of the CO 2 or pressure plume. Both approaches have worked, but they may struggle in places like the Gulf of Mexico where complex geologic structure can invalidate simple assumptions of radial plume spread and buoyant traps are commonly unattractive due to numerous legacy well penetrations. Here, we propose identifying prospective storage sites by fetch area (drainage cell) rather than by buoyant closure alone. Doing so offers 1) greater freedom in siting injectors to avoid surface and subsurface constraints, including legacy wells that tend to cluster on structural high; and 2) a coherent flow regime in which buoyancy drives all injected CO 2 toward a common high. This strategy gives space to dissipate injection pressure and minimize the number of legacy wells needing review. It may also offer 1) better injectivity by bringing synclines and associated channel axes into play; and 2) potentially improved capacity by tapping a larger rock volume and taking advantage of migration losses.

58 GEOSCIENCES↗

DOE OSTI2020

Reduced methane recovery at high pressure due to methane trapping in shale nanopores

By 2050, shale gas production is expected to exceed three-quarters of total US natural gas production. However, current unconventional hydrocarbon gas recovery rates are only around 20%. Maximizing production of this natural resource thus necessitates improved understanding of the fundamental mechanisms underlying hydrocarbon retention within the nanoporous shale matrix. In this study, we integrated molecular simulation with high-pressure small-angle neutron scattering (SANS), an experimental technique uniquely capable of characterizing methane behavior in situ within shale nanopores at elevated pressures. Samples were created using Marcellus shale, a gas-generative formation comprising the largest natural gas field in the United States. Our results demonstrate that, contrary to the conventional wisdom that elevated drawdown pressure increases methane recovery, a higher peak pressure led to the trapping of dense, liquid-like methane in sub-2 nm radius nanopores, which comprise more than 90% of the measured nanopore volume, due to irreversible deformation of the kerogen matrix. These findings have critical implications for pressure management strategies to maximize hydrocarbon recovery, as well as broad implications for fluid behavior under confinement.

58 GEOSCIENCES↗

DOE OSTI2025

High-Resolution Simulations of Geological CO 2 Injection: Application to the SPE11 Benchmark

Geological carbon sequestration (GCS) will play a critical role in decarbonization and in facilitating the transition to clean energy systems. Because CO 2 is highly mobile, ensuring its safe and permanent injection into subsurface geological formations involves monitoring over larger spatial domains and longer time periods than is typical for hydrocarbon reservoirs. This can benefit from simulation tools capable of modeling key CO 2 trapping mechanisms, particularly those optimized for speed and scalability on high-performance computing systems. Using isothermal versions of the SPE11B and SPE11C benchmark cases, we conduct a mesh refinement study simulating CO 2 injection into kilometer-scale rock formations at centimeter resolution with the GEOS open-source simulation framework. We focus on how mesh refinement improves the accuracy of convective mixing in both 2D and 3D simulations. The computational costs associated with achieving a converged solution highlight the need for predictive upscaling techniques. A systematic performance scaling analysis—including both central processing unit (CPU) and graphics processing unit (GPU) architectures—complements the “Results” section.

Geosciences↗

DOE OSTI2022

Iraq/Afghanistan war lung injury reflects burn pits exposure

This descriptive case series retrospectively reviewed medical records from thirty-one previously healthy, war-fighting veterans who self-reported exposure to airborne hazards while serving in Iraq and Afghanistan between 2003 and the present. They all noted new-onset dyspnea, which began during deployment or as a military contractor. Twenty-one subjects underwent non-invasive pulmonary diagnostic testing, including maximum expiratory pressure (MEP) and impulse oscillometry (IOS). In addition, five soldiers received a lung biopsy; tissue results were compared to a previously published sample from a soldier in our Iraq Afghanistan War Lung Injury database and others in our database with similar exposures, including burn pits. We also reviewed civilian control samples (5) from the Stony Brook University database. Military personnel were referred to our International Center of Excellence in Deployment Health and Medical Geosciences, Donald and Barbara Zucker School of Medicine at Hofstra/Northwell under the auspices of Northwell IRB: 17-0140-FIMR Feinstein Institution for Medical Research “Clinicopathologic characteristics of Iraq Afghanistan War Lung Injury.” We retrospectively examined medical records, including exposure data, radiologic imaging, and non-invasive pulmonary function testing (MGC Diagnostic Platinum Elite Plethysmograph) using the American Thoracic Society (ATS) standard interpretation based on Morgan et al., and for a limited cohort, biopsy data. Lung tissue, when available, was examined for carbonaceous particles, polycyclic aromatic hydrocarbons (Raman spectroscopy), metals, titanium connected to iron (Brookhaven National Laboratory, National Synchrotron Light Source II, Beamline 5-ID), oxidized metals, combustion temperature, inflammatory cell accumulation and fibrosis, neutrophil extracellular traps, Sirius red, Prussian Blue, as well as polarizable crystals/particulate matter/dust. Among twenty-one previously healthy, deployable soldiers with non-invasive pulmonary diagnostic tests, post-deployment, all had severely decreased MEP values, averaging 42% predicted. These same patients concurrently demonstrated abnormal airways reactance (X5Hz) and peripheral/distal airways resistance (D5–D20%) via IOS, averaging – 1369% and 23% predicted, respectively. These tests support the concept of airways hyperresponsiveness and distal airways narrowing, respectively. Among the five soldiers biopsied, all had constrictive bronchiolitis. We detected the presence of polycyclic aromatic hydrocarbons (PAH)—which are products of incomplete combustion—in the lung tissue of all five warfighters. All also had detectable titanium and iron in the lungs. Metals were all oxidized, supporting the concept of inhaling burned metals. Combustion temperature was consistent with that of burned petrol rather than higher temperatures noted with cigarettes. All were nonsmokers. Neutrophil extracellular traps were reported in two biopsies. Compared to our prior biopsies in our Middle East deployment database, these histopathologic results are similar, since all database biopsies have constrictive bronchiolitis, one has lung fibrosis with titanium bound to iron in fixed mathematical ratios of 1:7 and demonstrated polarizable crystals. These results, particularly constrictive bronchiolitis and polarizable crystals, support the prior data of King et al. (N. Engl. J. Med. 365:222–230, 2011) Soldiers in this cohort deployed to Iraq and Afghanistan since 2003, with exposure to airborne hazards, including sandstorms, burn pits, and improvised explosive devices, are at high risk for developing chronic clinical respiratory problems, including: (1) reduction in respiratory muscle strength; (2) airways hyperresponsiveness; and (3) distal airway narrowing, which may be associated with histopathologic evidence of lung damage, reflecting inhalation of burned particles from burn pits along with particulate matter/dust. Non-invasive pulmonary diagnostic tests are a predictor of burn pit-induced lung injury

36 MATERIALS SCIENCE↗

DOE OSTI2020

Noncontact catalysis: Initiation of selective ethylbenzene oxidation by Au cluster-facilitated cyclooctene epoxidation

Traditionally, a catalyst functions by direct interaction with reactants. In a new noncontact catalytic system (NCCS), an intermediate produced by one catalytic reaction serves as an intermediary to enable an independent reaction to proceed. An example is the selective oxidation of ethylbenzene, which could not occur in the presence of either solubilized Au nanoclusters or cyclooctene, but proceeded readily when both were present simultaneously. The Au-initiated selective epoxidation of cyclooctene generated cyclooctenyl peroxy and oxy radicals that served as intermediaries to initiate the ethylbenzene oxidation. This combined system effectively extended the catalytic effect of Au. The reaction mechanism was supported by reaction kinetics and spin trap experiments. NCCS enables parallel reactions to proceed without the constraints of stoichiometric relationships, offering new degrees of freedom in industrial hydrocarbon co-oxidation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Inorganometallic Catalyst Design Center (ICDC) EFRC Accomplishments

The ICDC focused largely on heterogeneous catalysis of oxidative chemical transformations, especially those that came to prominence as natural gas (wet shale gas) supplanted crude oil as the primary feedstock in North America for carbon-based manufacturing of commodity chemicals. Driven by fracking-enabled access to enormous stores of shale-trapped wet gas, the feedstock change from oil to gas enabled a shift away from high-temperature catalytic breakdown of large hydrocarbons to catalytic build-up of C4, C3, C2, and C1 into desired intermediates, but now at much more modest temperatures. In turn, the much lower thermal force accompanying these kinds of reactions facilitates catalyst stabilization and characterization, including operando characterization, while slowing on-stream catalyst evolution (i.e., preserving catalyst structure), accommodating catalyst complexity, and enabling creation of uniform arrays of heterogeneous catalysts with single-atom or near-single-atom precision—at least for model systems. Together these features have proven to be a boon to hypothesis-driven catalysis science and to experimentally testable computation-based design advances and mechanism explication. The ICDC has greatly facilitated the integration of catalyst synthesis, advanced characterization, performance assessment, and computational elucidation—with advances in each of these realms spurring achievements in catalysis science and complementary realms.

03 NATURAL GAS↗

DOE OSTI2025

Radiation-Induced Chemical Yields of Carbon-Centered Radicals and Hydrogen Atoms from the Gamma Irradiation of n -Dodecane

Here, this study investigates the radiolytic yields of carbon-centered radicals and hydrogen atoms in n-dodecane under gamma irradiation. Utilizing molecular iodine (I 2 ) and 2,4,6-tri-tert-butylnitrosobenzene (3tBNB) as radical scavengers, we quantified the yields of molecular hydrogen and various carbon-centered radicals formed from bond scission of the solvent excited states. The yield of primary alkyl radicals was significantly lower than that of the secondary radicals, aligning with expected stabilities and bond dissociation energies. For the overall loss of n-dodecane, total yields of 0.598 ± 0.004 species/100 eV for C–C bond scission, 1.648 ± 0.012 species/100 eV for C–H bond scission, and 3.20 ± 0.10 species/100 eV for unimolecular H 2 elimination were determined. Notably, the I 2 scavenging data provided robust estimates, while the 3tBNB displayed lower efficiency in radical trapping. This research enhances our understanding of radiolytic processes in n-dodecane and offers insights for future studies on the behavior of hydrocarbons under ionizing radiation, with implications for improving UNF reprocessing strategies.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

DOE OSTI2021

Alkyl decorated metal–organic frameworks for selective trapping of ethane from ethylene above ambient pressures

Here the trapping of paraffins is beneficial compared to selective olefin adsorption for adsorptive olefin purification from a process engineering point of view. Here we demonstrate the use of a series of Zn 2 (X-bdc) 2 (dabco) (where X-bdc 2- is bdc 2- = 1,4-benzenedicarboxylate with substituting groups X, DM-bdc 2- = 2,5-dimethyl-1,4-benzenedicarboxylate or TM-bdc 2- = 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate and dabco = diazabicyclo[2.2.2.]octane) metal-organic frameworks (MOFs) for the adsorptive removal of ethane from ethylene streams. The best performing material from this series is Zn2(TM-bdc)2(dabco) (DMOF-TM), which shows a high ethane uptake of 5.31 mmol g -1 at 110 kPa, with a good IAST selectivity of 1.88 towards ethane over ethylene. Through breakthrough measurements a high productivity of 13.1 L/kg per breakthrough is revealed with good reproducibility over five consecutive cycles. Molecular simulations show that the methyl groups of DMOF-TM are forming a van der Waals trap with the methylene groups from dabco, snuggly fitting the ethane. Further, rarely used high pressure coadsorption measurements, in pressure regimes that most scientific studies on hydrocarbon separation on MOFs ignore, reveal an increase in ethane capacity and selectivity for binary mixtures with increased pressures. The coadsorption measurements reveal good selectivity of 1.96 at 1000 kPa, which is verified also through IAST calculations up to 3000 kPa. This study overall showcases the opportunities that pore engineering by alkyl group incorporation and pressure increase offer to improve hydrocarbon separation in reticular materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Tandem Electrocatalytic–Thermocatalytic Conversion of CO 2 to Aromatic Hydrocarbons

The reaction of CO 2 with H 2 O to produce aromatic hydrocarbons (benzene, toluene, ethylbenzene, and xylene isomers) (BTEX) represents a promising pathway for converting CO 2 to value-added liquid products. However, this reaction cannot be achieved in a single electrochemical or thermochemical process. This work utilizes tandem electrochemical-thermochemical reactors as a new paradigm by starting with CO 2 and H 2 O as the feed in a membrane electrode assembly (MEA) to produce C 2 H 4 , which subsequently undergoes thermochemical aromatization using a Gallium- and Phosphorus-modified zeolite ZSM-5 catalyst (Ga/ZSM-5/P) at ambient pressure to produce BTEX. The current study also demonstrates the potential advantage of the tandem strategy in mitigating negative effects of water by testing the tandem reactor system under different hydration conditions and by performing in-situ X-ray diffraction (XRD) and X-ray absorption (XAS) characterization of the aromatization catalysts. Finally, these results highlight the advantage of using the tandem process with the use of a water trap before the thermochemical reactor.

10 SYNTHETIC FUELS↗

DOE OSTI2025

Implementing Large-Scale CCS in Complex Geologic Reservoirs: Insights from Three Appalachian Basin Case Studies

This paper presents three design case studies for implementing large-scale geologic carbon storage in the Appalachian Basin region of the midwestern United States. While the Appalachian Basin has a challenging setting for carbon storage, the three case studies detailed in this article demonstrate that there are realistic options for implementing carbon storage in the basin. Carbonate rock formations, depleted hydrocarbon reservoirs, and moderate-porosity sandstones can be utilized as carbon-storage reservoirs in the Appalachian Basin. While these are not typical concepts for CO2 storage, the storage zones have advantages such as defined trapping mechanisms, multiple caprocks, and defined boundaries that are not always present in thick, permeable sandstones being targeted for many carbon-storage projects. The geologic setting, geotechnical parameters, and hydrologic setting for the three case studies are provided, along with the results of reservoir simulations of the CO2 injection-deployment strategies. The geological rock formations available for CO2 storage in the Appalachian Basin are more localized reservoirs with defined boundaries and finite storage capacities. Simulation results showed that accessing carbon-storage resources in these fields may require wellfields with 2–10 injection wells. However, these fields would have the capacity to inject 1–3 million metric tons of CO2 per year and up to 90 million metric tons of CO2 in total. The CO2 storage resources would fulfill decarbonization goals for many of the natural-gas power plants, cement plants, hydrogen plants, and refineries in the Appalachian Basin region.

Sminchak, Joel↗

DOE OSTI2020

Experimental evaluation of the role of redox during glauconite-CO 2 -brine interactions

Greensands formations are globally abundant sedimentary rocks rich in Fe clays (typically glauconite) that commonly contain natural hydrocarbon accumulations and may be important reservoirs for geologic storage of anthropogenic CO 2 . Diagenesis in greensands is commonly accompanied by the conversion of primary glauconite to siderite (FeCO 3 ), a process that could be exploited for the permanent trapping of CO 2 . Importantly, siderite formation after glauconite requires that the mostly oxidized Fe in the primary Fe clay minerals is reduced during diagenetic interactions. Here, we explore the effect of solution redox state on the stability of glauconite in sandstones with implications for the diagenetic and/or engineered formation of siderite. We performed two flow-through experiments on intact, glauconite-rich sandstone cores at 150 °C and 150 bar. Both experiments employed a 1 mol NaCl/kg, 0.1 mol NaHCO 3 /kg solution charged with ~0.58 mol CO 2 /kg solution, but the redox state of the injected fluid was manipulated between experiments in order to compare glauconite reactivity and siderite saturation state at oxidizing and reducing end-member conditions. After reaction with the oxidizing (O 2 (aq) ≈ 6 μmol/kg) fluid, chemical and Mӧssbauer spectroscopic analyses indicate the production of Fe(III)-oxy/hydroxide minerals from glauconite, whereas, in the reducing (H 2 (aq) ≈ 5–40 mmol/kg) experiment, thermodynamic calculations and coupled chemical, mineralogical, and Mӧssbauer analyses suggest glauconite dissolution and precipitation of an Fe(II) mineral, likely siderite, and minor magnetite formation. These experimental results, along with thermodynamic calculations, confirm that solution redox state is the master variable dictating siderite formation in greensands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Exploring Masses and Internal Mass Distributions of Single Carboxysomes in Free Solution Using Fluorescence and Interferometric Scattering in an Anti-Brownian Trap

Not Available

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Carbon-efficient conversion of natural gas and natural-gas condensates to chemical products and intermediate feedstocks via catalytic metal–organic framework (MOF) chemistry

The net-zero carbon emission scenario of stopping hydrocarbon use as fuel is unlikely to end the extraction of fossil hydrocarbons. Remaining will be a sizable need for hydrocarbons as feedstocks for commodity chemicals destined for transformation into polymers, manufacturing-relevant intermediates, and value-added chemicals. Historically, the primary feedstock source has been oil. Over the past dozen years, however, fracking-based extraction of shale-trapped natural gas from known enormous reserves, in North America, has resulted in feedstock sourcing instead from wet shale gas. This shift has transformed the catalytic chemistry of commodity chemical manufacturing. In this paper, following a brief discussion of the merits and limitations of crystallographically well-defined metal–organic frameworks (MOFs) as model catalysts and catalyst-supports, we examined their applications for understanding and potentially enabling carbon-economical, catalytic transformation of C 1 , C 2 , C 3 , and C 4 components of natural gas to desirable commodity chemicals, intermediates, or model compounds.

03 NATURAL GAS↗

DOE OSTI2021

Ultra-clean condensing gas furnace enabled with acidic gas reduction

Natural gas furnaces are the most common space heating equipment in the U.S. residential and commercial building markets. However, current residential natural gas condensing furnaces generate substantial acidic condensate as well as significant emissions of sulfur oxides (SOx), nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbons (HC), and methane (CH 4 ) contributing to environmental degradation of air, water, and soil. This paper describes a novel solution to reduce the environmental impact of natural gas condensing furnaces based on the technology of monolithic acidic gas reduction (AGR) catalyst for SOx trapping, NOx redox to nitrogen, and oxidation of formic acid, CO, HC, and CH 4 . This technology offers a new condensing natural gas furnace with both ultra-clean flue gas and neutral condensate. Here, a prototype of the condensing gas furnace with the AGR component is demonstrated to have condensate with pH = 7, NOx emissions of 1–2 ng/J, and an annual fuel utilization efficiency (AFUE) of 96%. The AGR component and the AGR-enabled furnace were tested for long-term reliability and durability, as well as for SOx storage and regeneration activity. In addition, this paper provides new data on measurements of the specific acidic gas content in natural gas condensing furnaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Clean Condensing Gas Furnace

Natural gas furnaces are the most common space heating equipment in the U.S. residential and commercial building markets. However, current residential natural gas condensing furnaces generate substantial acidic condensate as well as significant emissions of sulfur oxides (SOx), nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbons (HC), and methane (CH 4 ) contributing to environmental degradation of air, water, and soil. This report describes a novel solution to reduce the environmental impact of natural gas condensing furnaces based on the technology of a monolithic acidic gas reduction (AGR) catalyst for SOx trapping, NOx redox to nitrogen, and oxidation of formic acid, CO, HC, and CH 4 . The AGR technology offers the following benefits: (1) a neutral furnace condensate with a pH of ~7, allowing its safe release into the sewer system thus eliminating a second drainage system; (2) trapping and removing nearly all SOx emissions; (3) NOx emissions nearly at nearly 1-2 ng/J, more than 95% lower than new emissions standards in California; (4) the use of a low-cost heat exchanger as a condensing heat exchanger (HX) since the condensate is not acidic, avoiding the need for expensive stainless steel alloys; and (5) unburnt fuel energy recovery to boost efficiency.The AGR component and AGR-enabled furnace performance were broadly tested to determine their effects on long-term reliability and durability, as well as SOx storage and regeneration activity. The AGR regeneration does not impair the performance in achieving neutral condensate and ultra-low NOx emissions, and the AGR catalyst subjected to regeneration activities continued to function well and achieved slightly better annual fuel utilization efficiency (AFUE). The 400-hour reliability and durability test of the retrofitted condensing furnace with the AGR component shows that the furnace unit still achieves a neutral furnace condensate with a pH of ~7 and enables 0~3 ng/J of NOx emissions. However, the 400-hour operation slightly degraded the AFUE because of soot particle accumulation caused by frequent incomplete combustion owing to inappropriate condensate drainage during testing. Thus, proper condensate drainage is critical for AGR-enabled furnaces. Furthermore, neutron computed tomography was employed to survey the aged AGR component and demonstrate high-resolution 2D and 3D representations for the nondestructive diagnosis of the AGR component. The tomography showed that the AGR component did not deform or suffer broken AGR channels. A new AGR catalyst with low precious metal loading was preliminarily explored to identify a pathway of optimizing AGR material loading and maximizing acidic gas reduction at low cost. The new AGR component can reduce precious metal loading by 38% and still achieve neutral condensate and ultralow NOx emissions. The furnace with the AGR component of low Pt/Rh loading enables a maximum AFUE of 97%, which is meaningfully higher than the original furnace. Long-duration testing for the furnace enabled with the low precious metal loading AGR component will be vital in future research. Although the current work demonstrates a proof of concept for the AGR-enabled furnace, the AGR assembly needs to be optimized and integrated into the design of new OEM furnace products. Furthermore, the AGR technology can be applied not only for residential gas furnaces, but also for commercial rooftop units, gas heat pumps, gas-fired water heaters, combustion boilers, and other systems.

03 NATURAL GAS↗

DOE OSTI2024

Investigation of Ammonia Carrier Materials for Next Generation Ammonia Dosing System - CRADA 334 (Abstract)

Lean-burn gasoline and diesel engines can offer substantially higher fuel efficiency, good driving performance, and reduced carbon dioxide emission compared to stoichiometric gasoline engines. Various catalyst technologies have been developed to remove the pollutants from these engines. For example, a three-way catalyst (TWC) is used to remove hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) from gasoline engines during the stoichiometric conditions. During the lean-burn conditions, a TWC or a diesel oxidation catalyst (DOC) is used to control HC and CO emissions. NOx is removed by either lean NOx trap catalyst (LNT) that can store NOx under lean conditions and reduce NOx under rich conditions, or selective catalytic reduction catalyst (SCR) that can selectively remove NOx with a reducing agent. Among the NOx reduction catalyst technologies, SCR offers a number of advantages, including excellent NOx reduction efficiency over a wide range of temperatures and overall lower system cost. In fact, the SCR technology using ammonia (NH3) as reductant has been proven effective and used commercially for the removal of NOx emissions from stationary sources since the 1970s. Currently, SCR is being used to meet the NOx emission standards for diesel engines in Europe and North America, and also being considered for meeting the future NOx emission standards for lean-burn gasoline engines. Because of the challenges associated with storage, handling and transportation of ammonia on a vehicle, aqueous urea solution (e.g., Diesel Exhaust Fluid, AdBlue) has been developed as ammonia storage compound for mobile applications. When the aqueous urea solution is sprayed into exhaust gas stream, urea is decomposed to release ammonia, which then reduces NOx over the downstream SCR catalyst. Although aqueous urea solution technology has enabled automakers and engine manufacturers to meet the current NOx emission standards, this process of releasing ammonia requires a hot exhaust gas and sufficient mixing, creating challenges for low temperature NOx emission control and aftertreatment system packaging. For these reasons, alternative technologies have been developed as ammonia sources (e.g., solid urea, ammonium carbamate, metal ammine chloride) during the past few years. These technologies promise more convenient handling and distribution of ammonia sources, and help maximize the low-temperature performance of SCR catalysts and reduce the overall system volume and weight. However, none of these alternative technologies can be successfully implemented without the industry consensus. Therefore, the USCAR SCR work group, which is comprised of representatives from GM, Ford, and Chrysler, has decided to investigate the potential alternative ammonia carriers, define common standard vehicle interfaces, and address personal and environmental safety concerns with part suppliers and chemical companies. Under this CRADA Project, USCAR and Battelle will investigate alternative ammonia carrier materials that are currently under development. Based on the data and information derived under the CRADA project, the USCAR SCR work group plans to build the consensus and make recommendations for the industry.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Investigation of Ammonia Carrier Materials for Next Generation Ammonia Dosing System - CRADA 334 (Abstract)

Lean-burn gasoline and diesel engines can offer substantially higher fuel efficiency, good driving performance, and reduced carbon dioxide emission compared to stoichiometric gasoline engines. Various catalyst technologies have been developed to remove the pollutants from these engines. For example, a three-way catalyst (TWC) is used to remove hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) from gasoline engines during the stoichiometric conditions. During the lean-burn conditions, a TWC or a diesel oxidation catalyst (DOC) is used to control HC and CO emissions. NOx is removed by either lean NOx trap catalyst (LNT) that can store NOx under lean conditions and reduce NOx under rich conditions, or selective catalytic reduction catalyst (SCR) that can selectively remove NOx with a reducing agent. Among the NOx reduction catalyst technologies, SCR offers a number of advantages, including excellent NOx reduction efficiency over a wide range of temperatures and overall lower system cost. In fact, the SCR technology using ammonia (NH3) as reductant has been proven effective and used commercially for the removal of NOx emissions from stationary sources since the 1970s. Currently, SCR is being used to meet the NOx emission standards for diesel engines in Europe and North America, and also being considered for meeting the future NOx emission standards for lean-burn gasoline engines. Because of the challenges associated with storage, handling and transportation of ammonia on a vehicle, aqueous urea solution (e.g., Diesel Exhaust Fluid, AdBlue) has been developed as ammonia storage compound for mobile applications. When the aqueous urea solution is sprayed into exhaust gas stream, urea is decomposed to release ammonia, which then reduces NOx over the downstream SCR catalyst. Although aqueous urea solution technology has enabled automakers and engine manufacturers to meet the current NOx emission standards, this process of releasing ammonia requires a hot exhaust gas and sufficient mixing, creating challenges for low temperature NOx emission control and aftertreatment system packaging. For these reasons, alternative technologies have been developed as ammonia sources (e.g., solid urea, ammonium carbamate, metal ammine chloride) during the past few years. These technologies promise more convenient handling and distribution of ammonia sources, and help maximize the low-temperature performance of SCR catalysts and reduce the overall system volume and weight. However, none of these alternative technologies can be successfully implemented without the industry consensus. Therefore, the USCAR SCR work group, which is comprised of representatives from GM, Ford, and Chrysler, has decided to investigate the potential alternative ammonia carriers, define common standard vehicle interfaces, and address personal and environmental safety concerns with part suppliers and chemical companies. Under this CRADA Project, USCAR and Battelle will investigate alternative ammonia carrier materials that are currently under development. Based on the data and information derived under the CRADA project, the USCAR SCR work group plans to build the consensus and make recommendations for the industry.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

Role of Polycyclic Aromatic Alkylammonium Cations in Tuning the Electronic Properties and Band Alignment of Two-Dimensional Hybrid Perovskite Semiconductors

Two-dimensional hybrid organic–inorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However, n = 1 two-dimensional (2D) HOIPs face the challenge of low conductivity between the inorganic layers, leading to unsatisfactory device performance. Interestingly, 2D HOIPs employing π-conjugated molecules as organic moieties show energy and charge transfers between organic and inorganic layers, indicating potentially efficient carrier transport for photovoltaic applications. Nevertheless, the development of 2D HOIP-based solar cells especially utilizing polycyclic aromatic alkylammonium as cations is in its infancy. Herein, we investigated the electronic structure and band alignment of a series of n = 1 2D Ruddlesden–Popper (RP) phase HOIPs containing different polycyclic aromatic groups and alkyl chains, based on density functional theory calculations. We find that the polycyclic aromatic group plays an important role in controlling the functionality of 2D HOIPs by directly modifying band-edge states, and the band alignment at the organic–inorganic interface can be designed to promote either exciton trapping or dissociation for light-emitting or photovoltaic applications, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗