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At least 631 records · Page 35

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration, (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control, and (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Ollis, David F.↗

Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

Ollis, David F.↗

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗

Overview of Propulsion Systems for a Mars Aircraft

The capabilities and performance of an aircraft depends greatly on the ability of the propulsion system to provide thrust. Since the beginning of powered flight, performance has increased in step with advancements in aircraft propulsion systems. These advances in technology from combustion engines to jets and rockets have enabled aircraft to exploit our atmospheric environment and fly at altitudes near the Earth's surface to near orbit at speeds ranging from hovering to several times the speed of sound. One of the main advantages of our atmosphere for these propulsion systems is the availability of oxygen. Getting oxygen basically "free" from the atmosphere dramatically increases the performance and capabilities of an aircraft. This is one of the reasons our present-day aircraft can perform such a wide range of tasks. But this advantage is limited to Earth; if we want to fly an aircraft on another planetary body, such as Mars, we will either have to carry our own source of oxygen or use a propulsion system that does not require it. The Mars atmosphere, composed mainly of carbon dioxide, is very thin. Because of this low atmospheric density, an aircraft flying on Mars will most likely be operating, in aerodynamical terms, within a very low Reynolds number regime. Also, the speed of sound within the Martian environment is approximately 20 percent less than it is on Earth. The reduction in the speed of sound plays an important role in the aerodynamic performance of both the aircraft itself and the components of the propulsion system, such as the propeller. This low Reynolds number-high Mach number flight regime is a unique flight environment that is very rarely encountered here on Earth.

Colozza, Anthony J.↗

Clostridium autoethanogenum alters cofactor synthesis, redox metabolism, and lysine-acetylation in response to elevated H 2 :CO feedstock ratios for enhancing carbon capture efficiency

Clostridium autoethanogenum is an acetogenic bacterium that autotrophically converts carbon monoxide (CO) and carbon dioxide (CO 2 ) gases into bioproducts and fuels via the Wood–Ljungdahl pathway (WLP). To facilitate overall carbon capture efficiency, the reaction stoichiometry requires supplementation of hydrogen at an increased ratio of H 2 :CO to maximize CO 2 utilization; however, the molecular details and thus the ability to understand the mechanism of this supplementation are largely unknown. In order to elucidate the microbial physiology and fermentation where at least 75% of the carbon in ethanol comes from CO 2 , we established controlled chemostats that facilitated a novel and high (11:1) H 2 :CO uptake ratio. We compared and contrasted proteomic and metabolomics profiles to replicate continuous stirred tank reactors (CSTRs) at the same growth rate from a lower (5:1) H 2 :CO condition where ~ 50% of the carbon in ethanol is derived from CO 2 . Our hypothesis was that major changes would be observed in the hydrogenases and/or redox-related proteins and the WLP to compensate for the elevated hydrogen feed gas. Our analyses did reveal protein abundance differences between the two conditions largely related to reduction–oxidation (redox) pathways and cofactor biosynthesis, but the changes were more minor than we would have expected. While the Wood–Ljungdahl pathway proteins remained consistent across the conditions, other post-translational regulatory processes, such as lysine-acetylation, were observed and appeared to be more important for fine-tuning this carbon metabolism pathway. Metabolomic analyses showed that the increase in H 2 :CO ratio drives the organism to higher carbon dioxide utilization resulting in lower carbon storages and accumulated fatty acid metabolite levels. This research delves into the intricate dynamics of carbon fixation in C. autoethanogenum, examining the influence of highly elevated H 2 :CO ratios on metabolic processes and product outcomes. The study underscores the significance of optimizing gas feed composition for enhanced industrial efficiency, shedding light on potential mechanisms, such as post-translational modifications (PTMs), to fine-tune enzymatic activities and improve desired product yields.

09 BIOMASS FUELS↗

The path to 2060: Saudi Arabia's long-term pathway for GHG emission reduction

Saudi Arabia, as part of its Saudi Green Initiative, has announced its goal to achieve net zero green-house gas emissions by 2060. This ambitious target underscores the nation's dedication to address-ing climate change. However, there is a significant gap in comprehensive analysis regarding the long-term effects of Saudi Arabia's climate policies and their collective contribution towards the net-zero objective. This study endeavors to bridge this gap through a detailed examination using the GCAM-KSA, a specialized version of the Global Change Analysis Model tailored for Saudi Arabia, employing a multi-sectoral methodology that integrates economic, energy, and land use systems within a coherent framework to assess the impact of climate policies on GHG emissions. Our anal-ysis reveals that reaching net-zero GHG emissions by 2060 is a complex challenge requiring con-certed efforts across all sectors of the economy. While transitioning to low-carbon electricity and improving energy efficiency offer considerable emission reductions, fully decarbonizing the indus-trial and transportation sectors poses a significant hurdle. Our findings suggest that Saudi Arabia must triple its emission reduction commitments in its next Nationally Determined Contributions (NDCs) update to align with its 2060 net-zero goal. Early action and increased ambition could avoid the chances of getting locked into the high emission assets and give enough time to transform the energy system. Furthermore, the adoption and integration of Carbon Dioxide Removal (CDR) tech-nologies are identified as crucial for offsetting residual emissions, especially in sectors that might continue to rely on fossil fuels.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Climate-induced shifts in sulfate dynamics regulate anaerobic methane oxidation in a coastal wetland

Anaerobic methane oxidation (AMO) is a key microbial pathway that mitigates methane emissions in coastal wetlands, but the response of AMO to changing global climate remains poorly understood. Here, we assessed the response of AMO to climate change in a brackish coastal wetland using a 5-year field manipulation of warming and elevated carbon dioxide ( e CO 2 ). Sulfate (SO 4 2− )–dependent AMO (S-DAMO) was the predominant AMO process at our study site due to tidal inputs of SO 4 2− . However, SO 4 2− dynamics responded differently to the treatments; warming reduced SO 4 2− concentration by enhancing SO 4 2− reduction, while eCO 2 increased SO 4 2− concentration by enhancing SO 4 2− regeneration. S-DAMO rates mirrored these trends, with warming decreasing S-DAMO rates and e CO 2 stimulating them. These findings underscore the potential of climate change to alter soil AMO activities through changing SO 4 2− dynamics, highlighting the need to incorporate these processes in predictive models for more accurate representations of coastal wetland methane dynamics.

54 ENVIRONMENTAL SCIENCES↗

Advanced Oxygen Recovery via Series-Bosch Technology

Oxygen recovery from metabolically-produced carbon dioxide (CO2) is of critical importance for long-duration manned space missions beyond low Earth orbit. On the International Space Station (ISS), oxygen is provided to the crew through electrolysis of water in the Oxygen Generation Assembly (OGA). Prior to 2011, this water was entirely resupplied from Earth. A CO2 Reduction Assembly based on the Sabatier reaction (1) was developed by Hamilton Sundstrand and delivered to ISS in 2010. The unit recovers oxygen by reducing metabolic CO2 with diatomic hydrogen (H2) to produce methane and product water. The water is cleaned by the Water Purification Assembly and recycled to the OGA for continued oxygen production. The methane product is vented overboard.

Abney, Morgan B.↗

Improving the performance for direct electrolysis of CO 2 in solid oxide electrolysis cells with a Sr 1.9 Fe 1.5 Mo 0.5 O 6– δ electrode via infiltration of Pr 6 O 11 nanoparticles

Direct CO 2 electrolysis using solid oxide electrolysis cells (CO 2 -SOECs) holds promise to efficiently convert carbon dioxide to carbon monoxide and oxygen. Cathodes with desirable catalytic activity and chemical stability play a critical role in the development of direct CO 2 -SOECs. Although Sr 2 Fe 1.5 Mo 0.5 O 6–δ (SFM) has exhibited promise for direct CO 2 -SOECs due to its redox stability, it suffers from insufficient activity for the CO 2 reduction reaction (CO 2 RR). Here we report interface engineering of nanosized Pr 6 O 11 on the SFM cathode obtained through infiltration to promote the CO 2 RR performance for direct CO 2 -SOECs. The effect of Pr 6 O 11 loading on the performance of the CO 2 RR is systematically investigated. At 800 °C, the current density of the Pr 6 O 11 infiltrated SFM cathode with an optimum Pr 6 O 11 loading of 14.8 wt% reaches 1.61 A cm –2 at 1.5 V, more than double that of the SFM cathode (0.76 A cm –2 ) under the same operating conditions. X-ray photoelectron spectroscopy (XPS) characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicate that the adsorption ability of CO 2 on the SFM cathode has been significantly improved by the formation of Pr 6 O 11 . Temperature-programmed desorption (TPD) of CO 2 measurements further manifest that a 14.8 wt% Pr 6 O 11 -SFM cathode has better CO desorption capacity. In addition, polarization resistance of the SFM cathode has significantly decreased with the addition of Pr 6 O 11 . Three-electrode measurement was used to analyze the improved electrode kinetics. Finally, these results demonstrate that the formation of Pr 6 O 11 in the SFM cathode through infiltration is a promising approach for increasing CO 2 RR activity for CO 2 -SOECs.

03 NATURAL GAS↗

Methanol from Integrated Direct Air Capture and Ceramic Electrolysis (MIDACE)

The Methanol from Integrated Direct Air Capture and Ceramic Electrolysis (MIDACE) project advanced a novel system concept for integrating pressurized co-electrolysis of steam and crude carbon dioxide captured directly from ambient air using a sorbent technology. The co-electrolysis produced syngas provides feedstock for a gas-to-liquid methanol synthesis reactor. The system recovers waste heat from the reactor and electrolyzer into regenerating the direct air capture sorbent. The purpose of the project was to demonstrate critical integration elements of the design and perform a technical study illustrating how a large-scale installation could achieve the $800/ton program target for green methanol production. The concept addresses the program objective to consolidate operations by combining crude CO 2 cleanup, hydrogen production, and partial CO 2 reduction steps within a carbon tolerant high temperature electrolyzer. The design lowers costs by simplifying the methanol recovery cycle, reducing carbon losses from venting, reducing sensitivity to catalyst selectivity, and avoiding syngas compression.

10 SYNTHETIC FUELS↗

Numerical Simulations of Geologic Storage Reservoir Management to Support Risk Mitigation Evaluation

This report provides a detailed description of a set of numerical simulations that represent reservoir behavior over time in response to different operational decision scenarios for detection of potential leakage and reduction or avoidance of leakage impact at a hypothetical geological carbon storage (GCS) site. These simulations serve as the basis for a series of GCS leakage risk forecasts that are to be developed using the National Risk Assessment Partnership’s Open-Source Integrated Assessment Model (NRAP-Open-IAM), and a demonstration of a simple decision support workflow for evaluation of mitigation strategies based on results of those system model forecasts. This risk assessment and decision support study is forthcoming. Four injection scenarios were considered: a constant rate carbon dioxide (CO 2 ) injection case (base case), a case with CO 2 injection rate adjustment, a case with early termination of injection operations, and a case with brine extraction. CO 2 injection operations were controlled to ensure that the pressure transient remains below the defined manageable reservoir fracture pressure, with consideration shown to hypothetical locations within the modeled spatial domain where the overburden was weaker and lower transient pressure increases were allowable. Additionally, a brine extraction alternative was considered as a reservoir management and risk mitigation option to reduce reservoir pressure, steer the plume away from any hypothetical geohazard such as fault as needed, and enhance storage capacity. Such operational actions contribute to risk management overtime. This study explores the potential utility of reservoir management for risk reduction at GCS sites. This study shows that the injection design may modify the time to CO 2 breakthrough at a legacy well; in particular, these results show that brine extraction can add value for mitigating risk both by delaying leakage and reducing pressure build-up. For the scenario considered, both pressure plots and pressure distributions demonstrate that pressure build-up was decreased by 3% with brine extraction. Additionally, extraction of brine afforded enhancement of CO 2 storage capacity by 5% compared to the base case. These findings suggest that brine extraction has substantial potential to steer the risk-related reservoir effects away from known geohazards (e.g., faults and legacy wells) by conducting pressure transient effects and CO 2 plume movement toward the production well. Injection rate adjustment scenarios considered in this study show potential value for managing both reservoir pressure transients and CO 2 plume behavior. Operational actions for reducing injection and/or early termination of injection (as compared to the base case), however, require careful design; tailoring both the extent and timing of injection rate adjustment over the injection and post-injection operational period must be thoroughly planned to balance maximizing storage and minimizing subsurface environmental risk. The study also gives preliminary consideration to the effectiveness that monitoring strategy may play in providing useful information to inform reservoir management decisions for risk reduction. Two types of monitoring were considered: 1) pressure build-up or pressure transient; and 2) potential leakage detection from a CO 2 mass or plume. Four hypothetical legacy wells, two plugged and two abandoned, were placed in the model domain. Monitoring along these wells was measured over time in individual stacked reservoir formations and shale formations to support risk mitigation decisions, especially operational decisions that assisted in risk reduction. These simulations will serve as the basis for a series of GCS leakage risk forecasts that are to be developed using NRAP’s Open-IAM, and demonstration of a simple decision support workflow for comparative assessment of mitigation alternatives based on results of those system model forecasts. This risk assessment and decision support study is forthcoming.

54 ENVIRONMENTAL SCIENCES↗

Abstract for CRADA between NETL and the AZ Board of Regents on behalf of Arizona State University

Arizona State University (ASU) and the National Energy Technology Laboratory (NETL) will collaborate on the development and scale up of sorbent composites that efficiently capture carbon dioxide (CO 2 ) directly from air under an awarded project from the Department of Energy’s Direct Air Capture (DAC) Pre-Commercialization Technology Prize. For DAC to be considered a viable technology for decarbonization, the cost of carbon removal needs to decrease below the proposed carbon tax incentive outlined in the recent Inflation Reduction Act (IRA) (Section 45 Q), which is set at $\$$180 per ton of CO 2 . Achieving this goal requires the development of a cost-effective, environmentally friendly sorbent with high CO 2 sorption capacity and efficient kinetics under DAC conditions as the overall cost of CO 2 captured is highly sensitive to factors such as sorbent cost and sorbent lifetime. ASU has developed a sorbent technology that can potentially reduce CO 2 removal costs by DAC. NETL has expertise in DAC TEA and LCA development and DAC sorbent testing. The collaboration between ASU and NETL aims to accelerate development and deployment of ASU’s technology by quantifying the performance, cost and lifecycle impacts of ASU’s technology and validating sorbent performance.

54 ENVIRONMENTAL SCIENCES↗

Effect of fuel zoning and fuel nozzle design on pollution emissions at ground idle conditions for a double-annular ram-induction combustor

An exhaust emission survey was conducted on a double-annular ram induction combustor at simulated ground idle conditions. The combustor was designed for a large augmented turbofan engine capable of sustained flight speeds up to Mach 3.0. The emission levels of total hydrocarbon (THC), carbon monoxide, carbon dioxide, and nitric oxide were measured. The effects of fuel zoning, fuel nozzle design, and operating conditions (inlet temperature and reference Mach number) on the level of these emissions were determined. At an overall combustor fuel/air ratio of 0.007, fuel zoning reduced THC emissions by a factor of 5 to 1. The reduction in THC emissions is attributed to the increase in local fuel/air ratio provided by the fuel zoning. An alternative method of increasing fuel/air ratio would be to operate with larger-than-normal compressor overboard bleed; however, analysis on this method indicated an increase in idle fuel consumption of 20 percent. The use of air-atomizing nozzles reduced the THC emissions by 2 to 1.

Clements, T. R.↗

NASA Tech Briefs, October 2013

Topics include: A Short-Range Distance Sensor with Exceptional Linearity; Miniature Trace Gas Detector Based on Microfabricated Optical Resonators; Commercial Non-Dispersive Infrared Spectroscopy Sensors for Sub-Ambient Carbon Dioxide Detection; Fast, Large-Area, Wide-Bandgap UV Photodetector for Cherenkov Light Detection; Mission Data System Java Edition Version 7; Adaptive Distributed Environment for Procedure Training (ADEPT); LEGEND, a LEO-to-GEO Environment Debris Model; Electronics/Computers; Millimeter-Wave Localizers for Aircraft-to-Aircraft Approach Navigation; Impedance Discontinuity Reduction Between High-Speed Differential Connectors and PCB Interfaces; SpaceCube Version 1.5; High-Pressure Lightweight Thrusters; Non-Magnetic, Tough, Corrosion- and Wear-Resistant Knives From Bulk Metallic Glasses and Composites; Ambient Dried Aerogels; Applications for Gradient Metal Alloys Fabricated Using Additive Manufacturing; Passivation of Flexible YBCO Superconducting Current Lead With Amorphous SiO2 Layer; Propellant-Flow-Actuated Rocket Engine Igniter; Lightweight Liquid Helium Dewar for High-Altitude Balloon Payloads; Method to Increase Performance of Foil Bearings Through Passive Thermal Management; Unibody Composite Pressurized Structure; JWST Integrated Science Instrument Module Alignment Optimization Tool; Radar Range Sidelobe Reduction Using Adaptive Pulse Compression Technique; Digitally Calibrated TR Modules Enabling Real-Time Beamforming SweepSAR Architectures; Electro-Optic Time-to-Space Converter for Optical Detector Jitter Mitigation; Partially Transparent Petaled Mask/Occulter for Visible-Range Spectrum; Educational NASA Computational and Scientific Studies (enCOMPASS); Coarse-Grain Bandwidth Estimation Scheme for Large-Scale Network; Detection of Moving Targets Using Soliton Resonance Effect; High-Efficiency Nested Hall Thrusters for Robotic Solar System Exploration; High-Voltage Clock Driver for Photon-Counting CCD Characterization; Development of the Code RITRACKS; and Enabling Microliquid Chromatography by Microbead Packing of Microchannels.

Source record↗

Status Report 2: Advanced Nuclear Reactors Utilized for Synthetic Fuel Creation

Synthetic fuels (synfuels) are hydrocarbon fuels that source energy from electricity. Synfuels have the potential to significantly reduce greenhouse gas emissions throughout the transportation sector. To achieve this substantial reduction in greenhouse gas emissions, the electricity must be sourced from zero- or near-zero-carbon fuel sources such as solar, wind, hydroelectricity, and nuclear power. Synfuels are produced from a combination of carbon and hydrogen sources. Hydrogen can be sourced from water electrolysis with near-zero-carbon electricity and heat (e.g., nuclear), while carbon dioxide can be sourced from ethanol and ammonia plants. In the hydrocarbon fuel synthesis process, hydrogen and carbon dioxide can be reacted to produce carbon monoxide and water, via the so-called reverse watergas shift reaction. Carbon monoxide can then react with additional hydrogen to form hydrocarbons, with carbon chains ranging from C1–C30 in the reaction known as the Fischer-Tropsch (F-T) synthesis reaction. The synthesized hydrocarbon molecules can then be hydro-processed with additional hydrogen and distilled into different carbon chain lengths so as to be compatible with existing conventional gasoline, jet, and diesel fuels. Carbon-free synfuel production comes with a “green premium” over the manufacture of identical products via conventional fossil fuels. Reports from Argonne National Laboratory (ANL) reveal that hydrogen costs dominate the cost of carbon-free synfuel production. This suggests that for the cost of green synfuel to approach that of conventional petroleum fuel, the cost of hydrogen must be approximately $\$1$/kg. Of the primary low-carbon energy sources, only nuclear carries the potential to produce hydrogen at below $\$2$/kg. (Still a bit above the lofty $\$1$/kg goal, but perhaps manageable). To further identify the potential for creating low-cost synfuels capable of competing with legacy technologies, the Department of Energy Office of Nuclear Energy has funded a multi-program, multi-lab effort among ANL, Idaho National Laboratory (INL), the Integrated Energy Systems (IES) program, and the Light Water Reactor Sustainability (LWRS) program. This collaboration effort will determine the possibility of using current and next generation nuclear reactors to create low-cost carbon-free synfuels for sale in the U.S. energy and commodities market.

10 SYNTHETIC FUELS↗

Reacting CO 2 with Light Alkanes to Value-Added Products

Catalytic conversion of anthropogenic carbon dioxide (CO 2 ) into value-added products is a promising strategy to mitigate global carbon emissions. Concurrently, the shale gas revolution has provided an abundant supply of light alkanes (methane, ethane, propane, and butane), presenting a unique opportunity to employ these underutilized hydrocarbons as an effective, low-cost hydrogen source for CO 2 reduction. In this Perspective, we summarize past efforts, current state, and future opportunities for reacting CO 2 with light alkanes to generate a diverse range of value-added products. Compared with direct alkane conversion, the introduction of CO 2 fundamentally alters reaction thermodynamics and kinetics, enabling selective C–H and C–C bond activation while suppressing catalyst deactivation from coke formation. Building on decades of research in dry reforming and CO 2 -assisted dehydrogenation, recent advances in catalyst design have enabled CO 2 -assisted dehydrogenation processes that approach chemical equilibrium for the selective production of olefins and syngas. Importantly, advances in catalyst design and reactor engineering have further expanded the product scope beyond gas-phase (syngas and olefins) to include liquid-phase (oxygenates and aromatics), and solid-phase products (carbon nanomaterials). We highlight key catalyst design principles for controlling reaction pathways and discuss major challenges and opportunities in developing selective and versatile platforms for the simultaneous upgrading of CO 2 and light alkanes.

CO2↗

A Review of the Use of Immobilized Ionic Liquids in the Electrochemical Conversion of CO2

This paper is a review on the application of imidazolium-based ionic liquids tethered to polymer backbones in the electrochemical conversion of CO2 to carbon monoxide and formic acid. These tethered ionic liquids have been incorporated into novel anion ion exchange membranes for CO2 electrolysis, as well as for ionomers that have been incorporated into the cathode catalyst layer, providing a co-catalyst for the reduction reaction. In using these tethered ionic liquids in the cathode catalyst composition, the cell operating current increased by a factor of two or more. The Faradaic efficiencies also increased by 20–30%. This paper provides a review of the literature, in addition to providing some new experimental results from Dioxide Materials, in the electrochemical conversion of CO2 to CO and formic acid.

09 BIOMASS FUELS↗

Mechanically-, Thermally, and Chemically-Robust High-Temperature Ceramic Composites

In an effort to lower the levelized cost of electricity generated by Concentrated Solar Power (CSP) plants, the heat-to-electricity conversion efficiency may be increased by operating such plants with higher turbine inlet temperatures using closed Brayton cycles with high-pressure, supercritical carbon dioxide (sCO 2 ) as the working fluid. For example, if the turbine inlet temperature is raised to ≥750°C, in combination with sCO2 closed Brayton cycles, the relative heat-to-electricity efficiency may be raised by more than 20% (compared to subcritical steam Rankine cycles operating with turbine inlet temperatures ≤550°C). The associated reduction in the cost of dispatchable electricity from such CSP plants (utilizing high-temperature thermal energy storage) would be an important breakthrough on the path towards direct competition with fossil-fuel-based plants. A key barrier to achieve such high-temperature efficient operation has been the limited thermomechanical performance of metal alloys used in compact, primary printed circuit- type heat exchangers (PCHEXs) for heat transfer to high-pressure sCO 2 . The maximum allowed stresses for the use of conventional stainless steels and nickel-based superalloys at high sCO 2 pressures (≥20 MPa) decline rapidly at temperatures ≥550°C. This project has been focused on demonstrating the desired high-temperature properties and attractive manufacturing characteristics of mechanically-, thermally-, and chemically-robust ceramic/metal composites (cermets), in order to allow for the use of such composites in primary PCHEXs for heat transfer to sCO 2 at ≥750°C and ≥20 MPa in CSP plants. Prior work with high-temperature, co-continuous carbide/refractory metal cermets, such as ZrC/W composites, has already demonstrated: i) the attractive combination of high-temperature properties exhibited by such materials (e.g., high values of stiffness, failure strength, and thermal conductivity at 800°C), and ii) cost-effective processes for manufacturing PCHEX plates comprised of such cermets with tailorable channel patterns. However, ZrC/W cermets were not found to be inherently corrosion resistant in sCO 2 at 750°C and 20 MPa. While the application of a Cu coating to ZrC/W surfaces, along with a modest addition (50 ppm) of CO to CO 2 , rendered such composites resistant to corrosion for 1000 h in such sCO 2 -based fluids at 750°C, such additional steps would increase the design complexity of such cermet-based components. An alternative approach (the focus of this project) is to develop mechanically-robust, cost- effective cermets that are inherently resistant to high-temperature oxidation in air and CO 2 . The overall goals of this project have been to demonstrate: i) the oxidation resistance of at least one cermet at 750°C in air and in CO 2 (i.e., with a projected annual corrosion ≤30 μm), ii) the mechanically robust nature of at least one cermet at 750°C (i.e., with an average failure strength ≥200 MPa), and iii) that the selected cermet can be manufactured via low-cost forming techniques.

14 SOLAR ENERGY↗