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Balancing volumetric and gravimetric uptake in highly porous materials for clean energy

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for the onboard storage of hydrogen and methane gas—alternatives to conventional fossil fuels. Here we report the simulation-motivated synthesis of ultraporous metal–organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative to other ultraporous MOFs, NU-1501-Al exhibits concurrently a high gravimetric Brunauer–Emmett–Teller (BET) area of 7310 m 2 g -1 and a volumetric BET area of 2060 m 2 cm -3 while satisfying the four BET consistency criteria. The high porosity and surface area of this MOF yielded impressive gravimetric and volumetric storage performances for hydrogen and methane: NU-1501-Al surpasses the gravimetric methane storage U.S. Department of Energy target (0.5 g g -1 ) with an uptake of 0.66 g g -1 [262 cm 3 (standard temperature and pressure, STP) cm -3 ] at 100 bar/270 K and a 5- to 100-bar working capacity of 0.60 g g -1 [238 cm 3 (STP) cm -3 ] at 270 K; it also shows one of the best deliverable hydrogen capacities (14.0 weight %, 46.2 g liter -1 ) under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar).

Science & Technology - Other Topics↗

Annual Technology Baseline: The 2020 Electricity Update

Consistent cost and performance data for various electricity generation technologies can be difficult to find and may change frequently for certain technologies. With the Annual Technology Baseline (ATB), the National Renewable Energy Laboratory annually provides an organized and centralized set of such cost and performance data. The ATB uses the best information from the Department of Energy national laboratories' renewable energy analysts. The ATB has been reviewed by experts and it includes the following electricity generation technologies: land-based wind, offshore wind, utility-scale solar photovoltaics (PV), commercial-scale solar PV, residential-scale solar PV, concentrating solar power, geothermal power, hydropower, utility-scale battery storage. EIA data for coal, natural gas, nuclear, and conventional biopower are included for reference. This webinar presentation introduces the 2020 update to the ATB Electricity data and documentation.

capacity factor↗

Mono-Ether and Alcohol Bioblendstocks to Reduce the Fuel Penalty of Mixing Controlled Compression Ignition (MCCI) Engine Aftertreatment

An integrated approach utilizing catalysis experiments, process systems engineering, fuel property modeling, and engine testing was utilized in this project to optimize the production process and composition of a #2 diesel bioblendstock produced from ethanol consisting primarily of long-chain mono-ethers. The primary objective of the project was to determine the composition and to design the production process for a bioblendstock for #2 diesel fuel with > 50% reduction in greenhouse gas emissions relative to conventional diesel fuel. The desired bioblendstock needed to be blendable with #2 diesel fuel at > 5 vol. % while still meeting ASTM D975 diesel fuel specification properties and achieving improvements in fuel properties: increased cetane number, decreased sooting, and reduced pour point and cloud point temperatures. At the same time, it needed to reduce the fuel energy penalty associated with MCCI engine aftertreatment resulting in improved system efficiency. The findings of the current project demonstrate that primary objective of the work has been met, i.e., to determine the composition and to design the production process for a bioblendstock for #2 diesel fuel with > 50% reduction in greenhouse gas emissions relative to conventional diesel fuel. Additionally, the results indicate that the property objectives (increased cetane number, reduced pour and cloud points, and reduced sooting propensity) for the designed bioblendstock composition have also been met. Engine testing performed has also confirmed that the increased reactivity of the bioblendstock can be used to improve catalyst heating operation and to reduce the fuel penalty associated with this operation mode. The fuel property results demonstrate that >5 vol.% blending is easily achieved while meeting the ASTM D975 #2 diesel fuel property specifications tested in this work, as this was achieved for a blend with 43 vol. % of the bioblendstock. The results provide a foundation for future work to scaleup the catalytic production process designed in this work, with many of the challenges and areas for improvement being identified in this work to enable economic production with low GHG lifecycle emissions.

09 BIOMASS FUELS↗

Baseline Airfoil Cooling Designs For 5-10MW Gas Turbines

This paper describes conventional cooling technologies that have been identified after a thorough review of public literature as a baseline for more detailed analysis and future testing. This effort is unique because the cooling features (i.e., leading edge, mid-chord, and trailing edge) are integrated together within an airfoil of realistic scale. The engineering models that have been developed to characterize the cooling performance for these baseline configurations will be described. It is believed that the cooling designs described in this paper are representative of gas turbines in the 5-10 MWe size range, but not identical to any commercial product. The present effort to establish a state-of-the-art cooling scheme is a first, and necessary, step in an on-going project to identify and test more advanced cooling concepts for CHP systems that are enabled by additive manufacturing.

Straub, Douglas↗

Colloidal Three-Dimensional Covalent Organic Frameworks and Their Application as Porous Liquids

Developing solid porous materials into free-flowing liquids with permanent porosity is a promising strategy for overcoming certain limitations of conventional sorbent materials employed in gas storage and separation applications. The ability to control the pore size and chemical functionalities of organic frameworks gives these particular nanoporous materials distinct advantages over other small cage-like molecules or hollow particles that have been developed into porous liquids. Here, we describe the synthesis of a 3D imine-linked colloidal covalent organic framework (COF)-based porous liquid, designed for efficient size-exclusion of solvent, as well as for long-term stability. By tethering ionic liquids to the colloid surface, the colloids can be dried, purified, and resuspended in a variety of solvents without irreversible aggregation typically observed of COF colloids. Colloid size could be controlled between 50 and 400 nm, with surface areas as high as 800 m2/g. The 3D intertwining morphology of the colloids had pore sizes ranging from 5 to 14 Å, allowing them to efficiently sizeexclude bulky ionic liquids. The COF colloids were stable towards flocculation in an ionic liquid for > 1 year. Permanent porosity was confirmed with a combination of 19F NMR measurements and gas sorption techniques. CO2 and CH4 uptake in these porous liquids increased more than 10 and 20-fold, respectively, over non-porous, neat ionic liquid control samples. The work not only advances the state of COF-based colloid science but also represents a practical advance towards developing more robust, tunable framework-based porous liquid materials for a host of gas storage and separation applications.

Mow, Rachel E.↗

First-Order Individual Gas Sensors as Next Generation Reliable Analytical Instruments

It is conventionally expected that the performance of existing gas sensors may degrade in the field compared to laboratory conditions because (i) a sensor may lose its accuracy in the presence of chemical interferences and (ii) variations of ambient conditions over time may induce sensor-response fluctuations (i.e., drift). Breaking this status quo in poor sensor performance requires understanding the origins of design principles of existing sensors and bringing new principles to sensor designs. Existing gas sensors are single-output (e.g., resistance, electrical current, light intensity, etc.) sensors, also known as zero-order sensors (Karl Booksh and Bruce R. Kowalski, Analytical Chemistry, DOI: 10.1021/ac00087a718). Any zero-order sensor is undesirably affected by variable chemical background and sensor drift that cannot be distinguished from the response to an analyte. To address these limitations, we are developing multivariable gas sensors with independent responses, which are first-order analytical instruments. Here, we demonstrate self-correction against drift in two types of first-order gas sensors that operate in different portions of the electromagnetic spectrum. Our radiofrequency sensors utilize dielectric excitation of semiconducting metal oxide materials on the shoulder of their dielectric relaxation peak and achieve self-correction of the baseline drift by operation at several frequencies. Our photonic sensors utilize nanostructured sensing materials inspired by Morpho butterflies and achieve self-correction of the baseline drift by operation at several wavelengths. These principles of self-correction for drift effects in first-order sensors open opportunities for diverse emerging monitoring applications that cannot afford frequent periodic maintenance that is typical of traditional analytical instruments.

Potyrailo, Radislav A.↗

Life cycle energy use and greenhouse gas emissions of ammonia production from renewable resources and industrial by-products

Conventionally, ammonia is produced from natural gas via steam methane reforming (SMR), water-gas shift reaction, and the Haber–Bosch process. The process uses fossil natural gas, which leads to 2.6 metric tons of life cycle greenhouse gas (GHG) emissions per metric ton of ammonia produced. With ammonia being the second most produced chemical in the world, its production accounts for approximately 2% of worldwide fossil energy use and generates over 420 million tons of CO 2 annually. To reduce its carbon intensity, ammonia synthesis relying on renewable energy or utilizing by-products from industrial processes is of interest. In this work, we conduct a life cycle analysis of conventional and alternative ammonia production pathways by tracking energy use and emissions in all conversion stages, from the primary material and energy resources to the ammonia plant gates. Of all the alternative pathways, obtaining N 2 from cryogenic distillation and H 2 from low-temperature electrolysis using renewable electricity has the lowest cradle-to-plant-gate GHG emissions, representing a 91% decrease from the conventional SMR pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Magnesium Borane Containing Solutions of Furans and Pyrroles as Reversible Liquid Hydrogen Carriers (Final Technical Report)

The objective of this project was the development of a two-way liquid hydrogen carrier having a greater energy efficiency and lower delivery costs than either existing hydrogen carriers or conventional compressed H 2 gas transport technology. It was hypothesized that a hydrogen carrier consisting of solutions of furans and pyrroles containing Mg(BH 4 ) 2 and pincer complex catalyst, would have more than twice the volumetric available hydrogen density of the conventional two-way liquid hydrogen carrier, methylcyclohexane. Most notably the envisioned liquid hydrogen carrier would: 1) maintain high product selectivity through multiple cycles of dehydrogenation and hydrogenation; and 2) undergo rapid dehydrogenation and re-hydrogenation. The project was specifically aimed at the demonstration of at least one LOHC solution of Mg(BH 4 ) 2 and pincer catalyst that releases ≥ 50 g H 2 /L at ≤ 200 °C upon dehydrogenation and undergoes ≥ 25% rehydrogenation under 100 atm of H 2 at ≤ 200 °C.

08 HYDROGEN↗

Microalgae Biomass Production for Utilization of CO2 and Mitigation of Greenhouse Gas Emissions

Microalgal cultivation processes for production of foods, feeds, fuels, fertilizers and other bioproducts and wastewater treatment are being considered for reducing CO2 and other greenhouse gas emissions. Major differences between microalgae and higher plant biomass cultivation are include their potential for much higher productivities, their higher content of major (N-P-K) and minor nutrients, and the challenge of harvesting such microscopic plants. Most critical, microalgal mass cultures, unlike higher plants, currently require fertilization with concentrated sources of CO2. As practically all of the C fixed into algal biomass will be re-emitted into the atmosphere in short order, algae processes do not sequester carbon. Their potential for CO2 emissions reductions must thus be based on comparisons with current technologies for the production of competing products, such as biofuels or animal feeds, or in wastewater treatment. Further, due to economic limitations to flue gas transport (3 to 12 % CO2), as well as highly variable diurnal and seasonal CO2 utilization and limited land and water availability near most CO2 sources, only a small fraction of waste CO2 emissions will be directly utilizeable for microalgae biomass production. However, for long-distance transport, flue gas CO2 capture by chemical processes would greatly increase the costs of flue gas utilization. More concentrated, sources of CO2 from refineries, fertilizer, chemical plants, and fermentations are available, but are also very limited relative to the quantities required for commodity production. Microalgae can also be cultivated on organic wastes, which provide both nutrients (N, P, K, etc.) and organic and inorganic carbon for algal growth, reducing greenhouse gas emissions compared to conventional treatment processes. To maximize the potential for algae biomass production and CO2 utilization, direct capture of CO2 from air will be required. This could be accomplished with the algal cultivation process itself in large open-raceway ponds, through chemical and biological enhancements of CO2 transfer into algal cutures. The relative productivities, economics, greenhouse gas balances, and resource potentials of these alternative CO2 sources for large-scale production of microalgae will be reviewed.

09 BIOMASS FUELS↗

Managing Solar Photovoltaic Integration in the Western United States: Power System Flexibility Requirements and Supply

As penetrations of variable renewable energy generation technologies such as wind and solar photovoltaics (PV) continue to increase across the United States, greater uncertainty and variability in the net load often lead to a concern about how power systems may adapt. Managing the system net load (i.e., load minus contribution from variable generation technologies) may become more challenging with increasing variable generation, as the magnitude and frequency of net ramps increase. However, there is inherent flexibility in power systems through the conventional generator fleet (under least-cost unit commitment and economic dispatch), less-conventional generation sources (e.g., storage, demand response, concentrating solar power with thermal energy storage), and imports and exports with neighbors. In this analysis, we create an open-source tool to analyze the flexibility of the results of a specific commercial unit commitment and economic dispatch tool (PLEXOS), but the code can be applied generically as well. The tool assesses the flexibility requirements (or demand) of a system through a net load analysis. The constraints and limitations of each generator are then considered to determine the availability (or supply) of flexibility. Then, the supply and demand of flexibility are compared to gain a more complete picture of potential flexibility concerns. We apply this open-source tool to high-penetration PV scenarios constructed for three focus regions in the western United States defined using the Resource Planning Model (RPM) capacity expansion modeling tool: RPM-OR, RPM-CO, and RPM-AZ. Generally, we find few flexibility concerns, as the western United States represents a large and interconnected power system with significant inherent flexibility. In addition, the PV scenarios we analyzed are overbuilt on capacity, leaving plenty of ramping ability on the system. We do find that for each focus region, the impact of imports on meeting ramping needs is essential. This means the PV integration in each focus region impacts the entire rest of the system. Each system has different dominant sources of flexibility. The conventional generator fleet (especially coal and gas combined-cycle technologies) as well as less-conventional sources such as storage are all shown to be important sources of flexibility. The scenarios evaluated here were designed to study the planning and operations impact of high solar penetration in each of three focus regions. However, none of the three focus regions likely will deploy PV in isolation, meaning the ability of imports and exports to provide flexibility may be considerably different in scenarios with strong PV deployment in every region. Overall, we intend that the framework we present here will be useful in future analysis of other system evolutions to identify whether and how flexibility may constrain the successful deployment of variable generation technologies.

14 SOLAR ENERGY↗

Current challenges in hydrate‐based desalination: Kinetic and thermodynamic perspective

Abstract Water scarcity is becoming a severe problem worldwide due to inadequate freshwater resources and swift population growth. Seawater desalination is one of the vital approaches to meet the demand for freshwater. However, energy and associated costs with conventional seawater desalination techniques are incentivizing non‐conventional water desalination processes. Water desalination using gas hydrates formation is one of the emerging non‐conventional processes. In this perspective article, recent advances in hydrate‐based seawater desalination (HBSD) have been critically analyzed to outline a future path towards a clean and efficient hydrate‐based desalination process. It provides a detailed comparison of various processes developed over decades, and measured desalination efficiencies with their process details. Moreover, the current challenges, limitations, and future perspectives of hydrate‐based desalination are also discussed. The study also recapitulates the thermodynamics and kinetics aspects of the hydrate‐based desalination process. In addition, various factors controlling the desalination efficiencies, such as control of the separation of hydrate crystals, salt deposition on hydrate particles, and hydrate morphology, were thoroughly investigated with their proposed process designs. The kinetics of hydrate formation is also assessed, with the possibility of a zero‐induction regime and its consequent impact on hydrate morphology. The current capabilities of the thermodynamics models (Gibbs energy minimization + electrolyte equation of state) were discussed using various commercially available software. Additionally, the role of hydrate promotors is also discussed, which can reduce the higher cost associated with the hydrate‐based desalination process.

Khan, Muhammad Naveed↗

Invited Review Paper in Commemoration of Over 50 Years of Oxidation of Metals: Addressing the Role of Water Vapor on Long-Term Stainless Steel Oxidation Behavior

In the past 20 years, it has become clear that the long-term exposure of chromia-forming austenitic stainless steels to air containing ~ 10 vol% water vapor at 650–800 °C significantly increases the Cr consumption rate compared to laboratory air. However, a similar acceleration does not occur in 100% steam because O 2 is not available to form volatile CrO 2 (OH) 2 . As the research has shown, this accelerated Cr loss is particularly important for thin-walled components like gas turbine recuperators. Typically, conventional austenitic stainless steels exhibit accelerated attack (i.e., rapid formation of Fe-rich oxide nodules), while higher alloyed steels resist this type of degradation until the alloy surface becomes Cr depleted. The development of strategies and solutions for this issue are reviewed. Model Fe–Cr–Ni alloys have been used to study composition effects on this behavior. For example, increasing the Mn content up to ~ 4 wt% was not beneficial, but increasing the Ni content improved oxidation resistance in this environment. However, at 650–700 °C even highly alloyed steels showed surface Cr depletion at alloy grain boundaries resulting in Fe-rich oxide nodule formation. The path forward for this issue will require more refined mechanistic understanding and increased used of modeling to develop better application-specific lifetime models to identify the most cost-effective alloy solutions.

36 MATERIALS SCIENCE↗

Comparative techno-economic and environmental analysis of using nuclear energy and fossil energy with carbon sequestration in U.S. Gulf Coast petroleum refineries

U.S. Gulf Coast refineries have processing capacity of approximately 9.4 million barrels of crude oil per day—about 50% of U.S. national capacity—while consuming natural gas, electricity, and hydrogen, resulting in approximately 100 million metric tonnes (MMT) of onsite CO₂ emissions in 2022. This study evaluates two alternative refinery energy supply pathways: nuclear energy (NE) and fossil energy-derived hydrogen with carbon capture and sequestration (FE-CCS; autothermal reforming), intermittent renewable sources are not considered as they cannot reliably meet continuous industrial heat and hydrogen demands. Using publicly available data for refineries, we conducted a bottom-up, facility-level assessment to estimate energy use by type, well-to-gate refinery emissions, and associated costs of integration. Compared to current refinery operations using natural gas energy supply and conventional hydrogen production (steam methane reforming without sequestration), NE and FE-CCS could produce, respectively, average emissions reductions of 37% and 42%, total abatement costs of $\$$52–$\$$221 and $\$$211–$\$$612/MT CO₂, and additional costs of about $\$$0.2–$\$$6 and $\$$3–$\$$11 per barrel of crude, respectively. Our analysis indicates that 25 out of 27 refineries have lower total additional cost ($\$$/bbl.) for the NE scenario than the FE-CCS scenario, making a strong case for NE integration with petroleum refineries. This work's main contribution is a detailed bottom-up refinery-level analysis method that can be utilized by the worldwide refining industry and stakeholders as they assess different technological options, along with their costs and environmental impacts for a specific refinery operation.

Carbon capture and sequestration↗

Decarbonizing nitrogen fertilizer production via the electrochemical nitrogen oxidation reaction

Nitric acid is an important commodity chemical with extensive applications in both agricultural and industrial sectors. However, current production methods involve a combination of the Haber–Bosch and Ostwald processes, which are both energy and carbon emission intensive. The electrochemical nitrogen oxidation reaction (NOR) to produce nitric acid or nitrates shows great potential as an environmentally friendly method for producing fertilizers under mild conditions. The key to progress in this field lies in understanding the fundamental mechanistic insights and establishing robust experimental methods, which is essential for the efficient design and synthesis of electrocatalysts for NOR. Additionally, poor gas mass transport in conventional electrochemical reactors at present lead to lower NOR activity, thereby limiting the progress in this field. In this work, we present a synergistic computational and experimental approach to map out the potential chemical and electrochemical steps and determine the energetics on PtO 2 catalyst to gain mechanistic insights into NOR. Here, this study marks the first attempt to perform NOR in a vapor-fed reactor designed using advanced (additive) manufacturing. The vapor-fed reactor significantly improved the N 2 mass transport to the catalyst, allowing us to report the highest rate for nitrate production to date at 3.3 μmol cm -2 h -1 at 2.01 V vs RHE.

30 DIRECT ENERGY CONVERSION↗

Techno-economic analysis and life cycle assessment for the catalytic hydrogenolysis and hydrocracking of polyethylene

Catalytic hydrogenolysis and hydrocracking are promising technologies for the conversion of polyolefin waste into hydrocarbons. Here, to explore the economic and environmental viability of these approaches, we conducted techno-economic analysis and life cycle assessment of polyethylene hydrogenolysis and hydrocracking processes that produce fuel-range products or olefins, respectively. Relative to primary production, the minimum selling price (MSP) of alkanes for linear-chain naphtha was estimated to be 1.8-fold higher, whereas branched-chain naphtha and propylene were shown to be cost competitive. Environmental impacts showed similar trends across scenarios, with propylene production by hydrocracking exhibiting greenhouse gas emissions comparable with conventional propylene due to relatively low hydrogen demand and high yield. Together, these results suggest that innovations in catalysis and reaction engineering will be required to make viable products that are scale matched with today's plastics, such as light olefins for closed-loop recycling.

09 BIOMASS FUELS↗

Enhanced power density in zero-vacuum-gap thermophotovoltaic devices

Thermophotovoltaic (TPV) devices, which convert infrared thermal radiation from a hot emitter into electricity, hold great promise for applications in energy storage and waste heat recovery. While recent advancements have developed TPV devices with high efficiency, much less attention has been focused on improving the power density. Current TPV methods face challenges in significantly boosting the power density using emitters at very high temperatures (>2000 °C) or using complex, costly architectures such as near-field TPV. Here, we present the first experimental demonstration of a novel far-field TPV concept called “zero-vacuum-gap TPV” that eliminates the vacuum or gas-filled gap in conventional designs. By incorporating a high-index, infrared-transparent, and thermally insulating fused quartz spacer, we achieved a two-fold increase in power density compared to the far-field counterpart under identical conditions. Notably, in our experiment, the zero-vacuum-gap far-field design transforms a less-optimized, low-power-density far-field device into one with one of the highest power densities reported at moderate temperatures (700–1100 °C). Moreover, our measurements using a graphite emitter surpass the blackbody limit for gap-integrated far-field devices and match the performance of near-field TPV devices with an ultrathin 200-nm gap. Our findings suggest that zero-vacuum-gap TPV offers potential for cost-effective, scalable manufacturing using current technologies. Additionally, our modelling predicts that further power enhancements over one order of magnitude are possible with other spacer materials.

14 SOLAR ENERGY↗

Application of motional Stark effect in situ background correction to a superconducting tokamak

A polychrometer-type motional Stark effect (MSE) diagnostic technique, originally developed for the Alcator C-Mod tokamak, has been extended and applied to the Korea Superconducting Advanced Tokamak Research (KSTAR) device, the long-pulse superconducting tokamak, for the first time. It demonstrates a successful in situ subtraction of the polarized reflections off the vacuum vessel wall, sometimes up to half the total signal in some sightlines. To avoid the secondary neutral beam emission that may contaminate conventional beam-into-gas calibrations, a new approach, where the beam-into-gas measurements are made at various torus pressures with fixed vacuum fields, has been devised, which is possible with the stable superconducting coil systems of KSTAR. The validity of this new calibration scheme has been checked via plasma jog experiments. The experimental evidence of the polarized background light and the necessity of its correction in the MSE measurements made in KSTAR are presented as well.

47 OTHER INSTRUMENTATION↗

The Challenge Ahead: A Critical Perspective on Meeting U.S. Growth Targets for Sustainable Aviation Fuel

With demand for jet fuel expected to more than double by 2050 and triple by 2070, continued and accelerated efforts to decarbonize the global aviation sector are needed to curtail rising emissions and avert the worst outcomes of climate change. In response to this call-to-action, the United States has unveiled the Sustainable Aviation Fuel (SAF) Grand Challenge, which seeks to expedite the development of alternative fuel pathways that offer a minimum of a 50% reduction in life cycle greenhouse gas emissions compared to conventional jet fuel. However, there is growing concern on whether sufficient biomass will be readily available to satisfy the projected sharp rise in demand for SAF. Carbon dioxide point-source emissions combined with rising supply from direct air capture efforts have the potential to complement and offset any supply gaps for biomass-derived SAF and other use cases. Independent of the chosen feedstock and conversion technology, numerous challenges persist across SAF production in seeking to drive down fuel cost and carbon intensity. To hit the 2030 target of 3 billion gal/yr, this means about a 100% compound annual growth rate in volumetric SAF production (about 130 times scale-up) will need to be realized. To achieve the stretch goal of 35 billion gallons of SAF per year by 2050, volumetric production must increase by a factor of 12 from the 3-billion-gal/year 2030 target of SAF Grand Challenge. The comparatively longer runway for 2050 combined with significant production volume growth suggests a more inclusive "all-hands-on-deck"-style approach will likely play a role. A key component in success lies in the coordinated research, development, demonstration, and deployment efforts by multiple federal agencies and industry partnerships.

09 BIOMASS FUELS↗