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At least 973 records · Page 54

Elucidating the Origins of High Capacity in Iron-Based Conversion Materials: Benefit of Complementary Advanced Characterization toward Mechanistic Understanding

Lithium-ion batteries are recognized as an important electrochemical energy storage technology due to their superior volumetric and gravimetric energy densities. Graphite is widely used as the negative electrode, and its adoption enabled much of the modern portable electronics technology landscape. However, developing markets, such as electric vehicles and grid-scale storage, have increased demands, including higher energy content and a diverse materials supply chain. Alternatives that provide the opportunity to increase capacity and address supply chain concerns are of interest. Understanding the fundamental mechanisms that govern battery function is crucial to driving further improvements in the field. Advanced characterization techniques, such as those enabled by synchrotron light sources and high-resolution electron microscopes, that can uncover these mechanisms have become a necessity for elucidating structural evolution upon electrochemical conversion at the nano- to mesoscales. Performing these experiments with relevant electrochemistry using in situ and operando experiments imparts the ability to identify critical reaction pathways and capture intermediate (dis)charge products not discernible by traditional experiments.

36 MATERIALS SCIENCE↗

Surface Passivation by Excess Sulfur for Controlled Synthesis of Large, Thin SnS Flakes

Tin sulfide (SnS) is part of the group IV chalcogenides (SnX, GeX; X: S, Se), a family of anisotropic layered materials considered for thin film photovoltaics, optoelectronics, and valleytronics, and predicted narrow bandgap multiferroic materials. Large ultrathin SnS flakes, suitable for a variety of applications, are challenging to synthesize because of the enhanced surface reactivity due to the open layer structure of SnS which gives rise to a competition between lateral and vertical growth. Here we investigate the effects of added sulfur on passivating the surface and modifying the balance between lateral expansion and thickening of SnS flakes in chemical vapor transport from a SnS precursor. In addition, we investigate the growth of SnS flakes and compare the results of synthesis from a pure SnS precursor with growth, in which a slight excess of sulfur is supplied in different ways. Our results demonstrate that small amounts of excess sulfur can profoundly affect the size and thickness distributions of SnS flakes. The largest and thinnest flakes are obtained if (i) traces of sulfur are added and (ii) the sulfur source consists either of small Sx fragments released at high temperatures from the reactor walls, or atomic S supplied by sublimation from SnS 2 . The likely mechanism for the observed growth modifications is a transient surface passivation of SnS flakes during growth, which reduces the reactivity of the top facet of the flakes, limits vertical growth, and thus gives rise to ensembles with increased lateral size and reduced thickness.

36 MATERIALS SCIENCE↗

Reducing Economy-Wide Greenhouse Gas Emissions with Electrofuels and Biofuels as the Grid Decarbonizes

Biofuels and electrofuels have the potential to complement electrification in speeding greenhouse gas emissions reductions, especially in hard-to-decarbonize sectors. Concentrated waste CO 2 streams that can be used as a feedstock for electrofuels, however, may become less available as the share of renewable electricity increases and industries undergo decarbonization. Here, we conduct an analysis with detailed treatment of biofuels and electrofuels to probe their role in decarbonizing multiple industrial sectors and transportation. We examine how the changing availability of CO 2 could affect electrofuel production and the potential role of direct air capture in stabilizing the supply of CO 2 . The results indicate that biofuels could fulfill 12% of the total final energy demand across all U.S. sectors in 2050. Using seven industrial source points of CO 2 available in 2050, 15,388 PJ of electrofuels could be produced, which amounts to 25% of the total final energy demand. This result holds even upon decarbonization that requires direct air capture to boost the CO 2 supply. Biofuels and e-fuels have the potential to reduce economy-wide GHG emissions by 7 and 21% beyond electrification alone. However, electricity consumption and land use grow markedly with decarbonization at scale.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Potential Adoption and Benefits of Co-Optimized Multimode Engines and Fuels for U.S. Light-Duty Vehicles

Exploring a diverse portfolio of technologies for decarbonization is crucial to understanding the potential impacts of different technological solutions and their associated environmental implications. Using high-octane, high-sensitivity biofuel blends in co-optimized multimode engines can increase engine efficiency and reduce vehicle emissions. Here, the multimode engine research focuses on the benefits of light-duty vehicle engines, which can operate in multiple modes depending on the vehicle's load. Low-temperature combustion can improve efficiency and reduce emissions (such as those from oxides of nitrogen and particulate matter) during low-load operation, while spark ignition performance is maintained in high-load operation. These advanced engines can be optimized to run on blends of biobased fuels. This analysis models scenarios for potential market adoption of co-optimized multimode vehicles fueled by three different bioblendstocks: ethanol, isopropanol, and isobutanol. An integrated modeling approach is used to forecast the energy and environmental impacts of the deployment of co-optimized multimode vehicles and fuels in the light-duty sector over the 2020-to-2050 time horizon. The multidisciplinary approach combines vehicle sales modeling, system dynamics modeling of the biorefining industry, and life cycle assessment to estimate the emissions and energy benefits. The models consider market forces such as consumer preferences for vehicle attributes, biofuel supply and demand dynamics subject to biorefinery capacity build-out and bioresource constraints, and forecasted changes to the U.S. bulk energy system over time. Market adoption of co-optimized vehicles is evaluated across a wide parameter space for incremental vehicle cost and engine efficiency improvement. This analysis reveals that the deployment of co-optimized multimode fuels and vehicles results in up to a 5% reduction in annual sector-wide life cycle greenhouse gas (GHG) emissions by 2050, relative to a business-as-usual scenario, but is also indicates environmental trade-offs, such as higher life cycle water-use. Emission benefits could potentially increase beyond 2050, as the new technologies penetrate the market and gain a foothold. Results also show that, under certain circumstances, vehicles with engines co-optimized for use with high-octane, high-sensitivity biofuel blends can be cost-competitive with conventional gasoline, while reducing GHG emissions. Our modeling results indicate that co-optimized multimode fuels and engines can be strategically leveraged in tandem with electrification to decarbonize the light-duty sector. Co-optimized vehicles could play a role in the early years of the time horizon, while electric vehicles (EVs) could become more competitive in the later years, highlighting the complementary benefits of these technologies for GHG reductions.

Oke, Doris↗

Effects of Climate Change on Capacity Expansion Decisions of an Electricity Generation Fleet in the Southeast U.S.

The electric power sector in the United States faces many challenges related to climate change. On the demand side, climate change could shift demand patterns due to increased air temperatures. On the supply side, climate change could lead to deratings of thermal units due to changes in air temperature, water temperature, and water availability. Past studies have typically analyzed these risks separately. Here, we developed an integrated, multimodel framework to analyze how compounding risks of climate-change impacts on demand and supply affect long-term planning decisions in the power system. In the southeast U.S., we found that compounding climate-change impacts could result in a 35% increase in installed capacity by 2050 relative to the reference case. Participation of renewables, particularly solar, in the fleet increased, driven mostly by the expected increase in summertime peak demand. Such capacity requirements would increase investment costs by approximately 31 billion (USD 2015) over the next 30 years, compared to the reference case. These changes in investment decisions align with carbon emission mitigation strategies, highlighting how adaptation and mitigation strategies can converge.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Technoeconomic and Life Cycle Analysis of Synthetic Methanol Production from Hydrogen and Industrial Byproduct CO 2

Here CO 2 capture and utilization provides an alternative pathway for low-carbon hydrocarbon production. Given the ample supply of high-purity CO 2 emitted from ethanol and ammonia plants, this study conducted technoeconomic analysis and environmental life cycle analysis of several systems: integrated methanol-ethanol coproduction, integrated methanol-ammonia coproduction, and stand-alone methanol production systems, using CO 2 feedstock from ethanol plants, ammonia plants, and general market CO 2 supply. The cradle-to-grave greenhouse gas emissions of methanol produced from the stand-alone methanol, integrated methanol-ethanol, and integrated methanol-ammonia systems are 13.6, 37.9, and 84.6 g CO 2 -equiv/MJ, respectively, compared to 91.5 g CO 2 -equiv/MJ of conventional methanol produced from natural gas. The minimum fuel selling price (MFSP) of methanol ($\$0.61-0.64$/kg) is 61-68% higher than the average market methanol price of $\$0.38$/kg, when using a Department of Energy target renewable hydrogen production price of $\$2.0$/kg. The methanol price increases to $\$1.24-1.28$/kg when the hydrogen price is $\$5.0$/kg. Without CO 2 abatement credits, the H 2 price needs to be within $\$0.77-0.95$/kg for the MFSP of methanol to equal the average methanol market price. With a CO 2 credit of $\$35$/MT according to tax credit per metric ton of CO 2 captured and used, the methanol price is reduced to $\$0.56-0.59$/kg.

54 ENVIRONMENTAL SCIENCES↗

Microbe-Encapsulated Silica Gel Biosorbents for Selective Extraction of Scandium from Coal Byproducts

Establishing an inexpensive and environmentally friendly scandium (Sc) supply is critical for the development of clean energy technologies. However, refining Sc from Sc-bearing sources using current technologies poses economic and environmental challenges due to its low concentration relative to base metals and chemically similar lanthanides. In this work, we developed a biosorption-based flow-through process for extraction of Sc from low-grade feedstocks. A novel biosorbent material was synthesized by encapsulating Arthrobacter nicotianae, a bacterium that selectively adsorbs Sc, within a porous silica matrix. Through the use of several complementary microscopy techniques, we demonstrated a highly porous biosorbent structure with a high cell-loading density and a homogenous cell distribution. Batch adsorption assays revealed selective Sc adsorption over lanthanides and common based metals, with the exception of Fe(III), as evidenced by separation factors greater than 50. The MESG particles were packed into fixed-bed columns to enable adsorption under flow-through conditions, which demonstrated effective Sc extraction at flow rates up to 0.08 cm/s and high stability for reuse; greater than 95% of the adsorption capacity was maintained after 10 consecutive adsorption/desorption cycles. When applied to a lignite coal leachate, whose Fe content was depleted through pH-mediated precipitation, the MESG particles yielded Sc breakthrough at 30 bed volumes, whereas all other metals broke through after only a few bed volumes. Following desorption, an eluate with a 124-fold increase in Sc purity was achieved relative to the lignite leachate with Sc constituting 96.4% of the total REEs. This study established a rapid, facile, and scalable cell immobilization approach that enables the use of microbial biomass for Sc recovery from low-grade sources.

Dong, Ziye↗

Climate-Induced Tradeoffs in Planning and Operating Costs of a Regional Electricity System

Electricity grid planners design the system in order to supply electricity to end users reliably and affordably. Climate change threatens both objectives through potentially compounding supply- and demand-side climate-induced impacts. Uncertainty surrounds each of these future potential impacts. Given long planning horizons, system planners must weigh investment costs against operational costs under this uncertainty. Here, we developed a comprehensive and coherent integrated modeling framework combining physically-based models with cost-minimizing optimization models in the power system. We applied this modeling framework to analyze potential tradeoffs in planning and operating costs in the power grid due to climate change in the Southeast U.S. in 2050. We find that planning decisions that do not account for climate-induced impacts would result in a substantial increase in social costs associated with loss of load. These social costs are a result of under-investment in new capacity and capacity deratings of thermal generators when we included climate change impacts in the operation stage. Finally, these results highlight the importance of including climate change effects in the planning process.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Comparative Life Cycle Evaluation of the Global Warming Potential (GWP) Impacts of Renewable Natural Gas Production Pathways

Renewable Natural Gas (RNG) sources are being considered in future energy strategy discussions as potential replacements for fossil natural gas (FNG). While today’s supply of RNG resources is insufficient to meet U.S. demands, there is significant interest in its viability to supplement and decarbonize the natural gas supply. However, the resources that compare the life cycle global warming potential (GWP) of various RNG production pathways are lacking and focus mostly on a singular pathway. This effort is an attempt to close this gap and provide a comparison between the life cycle GWP of three major RNG pathways and the FNG pathway. The three RNG pathways evaluated are Anaerobic Digestion (AD), Thermal Gasification (TG), and Power-to-Gas (P2G) using various feedstocks. The functional unit is 1MJ of compressed RNG ready for injection into the natural gas transmission network. The results show that RNG production is not always carbon neutral or negative. Depending on the pathway the GWP impact of RNG production can range from -229 to 27 g CO 2 e/MJ compressed RNG, with AD of animal manure and AD of municipal solid waste being the least and the most impactful pathways, respectively, compared to the 10.1 g CO 2 e/MJ impact for compressed FNG.

54 ENVIRONMENTAL SCIENCES↗

Microbial and Environmental Processes Shape the Link between Organic Matter Functional Traits and Composition

Dissolved organic matter (DOM) is a large and complex mixture of molecules that fuels biogeochemical reaction in virtually all ecosystems on Earth. However, the relative importance of deterministic and stochastic processes in structuring DOM composition remains poorly characterized. Here we develop a framework for partitioning molecular composition based on key molecular traits, including lability vs. recalcitrance and activity vs. inactivity. Within this framework, we examine the ecological processes governing the assembly of DOM fractions by deploying aquatic microcosms on mountainsides that span gradients of temperature and nutrient loading in subtropical and subarctic ecosystems. Across study regions, deterministic and stochastic processes primarily structure active and inactive fractions, respectively. However, recalcitrant molecules are more deterministically assembled than labile molecules in the inactive fraction. Deterministic processes leading to variable selection generally exhibit more variation across the energy supply gradient for inactive fractions, and their importance increases with energy supply for recalcitrant molecules in both active and inactive fractions. Together, our results indicate that active and inactive fractions of DOM assemblages are structured by contrasting ecological processes, and their recalcitrant components are sensitive to global change. In conclusion, our framework opens new avenues to understand the assembly and turnover of DOM in a changing world, which can be used to predict carbon cycling at local to global scales.

54 ENVIRONMENTAL SCIENCES↗

Can Common Pool Resource Theory Catalyze Stakeholder-Driven Solutions to the Freshwater Salinization Syndrome?

Freshwater salinity is rising across many regions of the United States as well as globally, a phenomenon called the freshwater salinization syndrome (FSS). The FSS mobilizes organic carbon, nutrients, heavy metals, and other contaminants sequestered in soils and freshwater sediments, alters the structures and functions of soils, streams, and riparian ecosystems, threatens drinking water supplies, and undermines progress toward many of the United Nations Sustainable Development Goals. There is an urgent need to leverage the current understanding of salinization’s causes and consequences–in partnership with engineers, social scientists, policymakers, and other stakeholders–into locally tailored approaches for balancing our nation’s salt budget. In this feature, we propose that the FSS can be understood as a common pool resource problem and explore Nobel Laureate Elinor Ostrom’s social-ecological systems framework as an approach for identifying the conditions under which local actors may work collectively to manage the FSS in the absence of top-down regulatory controls. We adopt as a case study rising sodium concentrations in the Occoquan Reservoir, a critical water supply for up to one million residents in Northern Virginia (USA), to illustrate emerging impacts, underlying causes, possible solutions, and critical research needs.

54 ENVIRONMENTAL SCIENCES↗

Unlocking Dysprosium Constraints for China’s 1.5 °C Climate Target

Some key low-carbon technologies, ranging from wind turbines to electric vehicles, are underpinned by the strong rare-earth-based permanent magnets of the Nd, Pr (Dy)–Fe–Nb type (NdFeB). These NdFeB magnets, which are sensitive to demagnetization with temperature elevation (the Curie point), require the addition of variable amounts of dysprosium (Dy), where an elevation of the Curie point is needed to meet operational conditions. Given that China is the world’s largest REE supplier with abundant REE reserves, the impact of an ambitious 1.5 °C climate target on China’s Dy supply chain has sparked widespread concern. Here, we explore future trends and innovation strategies associated with the linkage between Dy and NdFeBs under various climate scenarios in China. We find China alone is expected to exhaust the global present Dy reserve within the next 2–3 decades to facilitate the 1.5 °C climate target. By implementing global available innovation strategies, such as material substitution, reduction, and recycling, it is possible to avoid 48%–68% of China’s cumulative demand for Dy. Nevertheless, ongoing efforts in REE exploration and production are still required to meet China’s growing Dy demand, which will face competition from the United States, European Union, and other countries with ambitious climate targets. Here our analysis urges China and those nations to form wider cooperation in REE supply chains as well as in NdFeB innovation for the realization of a global climate-safe future.

54 ENVIRONMENTAL SCIENCES↗

Embracing the Intersections of Environmental Science, Engineering, and Geosciences to Solve Grand Challenges of the 21st Century

The U.S. National Academies report on Environmental Engineering for the 21st Century identified five grand challenges of sustainably supplying food, water, and energy; curbing climate change and adapting to its impacts; designing a future without pollution and waste; creating efficient, healthy, resilient cities; and fostering informed decisions and actions. (1) Addressing many of the grand challenges will require embracing the intersections of environmental science, engineering, and geosciences. These three fields are inherently interdisciplinary, and they naturally intersect with each other (Figure 1). Geosciences, or Earth sciences, study the dynamics of different spheres of Earth. One of its missions is to detect the availability of mineral, water, and fuel resources, for sustainable development, and new research opportunities were identified in “coevolution of life, environment, and climate” and “biogeochemical and water cycles in terrestrial environments and impacts of global change” by the U.S. National Research Council. (2) Environmental science and engineering focus on the spheres that intersect with human activities. Environmental science puts an emphasis on understanding the migration of naturally occurring and anthropogenic contaminants in the environment and their impact on ecosystem and human health, and environmental engineering centers on developing technologies for water supply, mineral exploration, and environmental remediation to mitigate adverse impacts.

54 ENVIRONMENTAL SCIENCES↗

Mathematical Modeling of Liquid-Phase Alkylation of Benzene with Ethylene Considering the Process Unsteadiness

Ethylbenzene is a key intermediate in the manufacture of styrene that is an important industrial monomer. Ethylbenzene is produced by benzene alkylation using either gas-phase or liquid-phase methods. The liquid-phase alkylation that uses liquid acidic catalysts needs to be improved. We develop a mathematical model for the liquid-phase benzene alkylation. The reaction scheme, designed with a due analysis of desired and side reactions, and with the analysis of the formation of deactivating agents, reflects, in particular, the influence of the concentration of heavy hydrocarbons on the catalyst activity. The account of the catalyst deactivation by heavy alkylaromatics allows predictions of the temporal changes in the outputs of the alkylation process. In particular, the decrease of the ethylbenzene concentration by 2–3 wt % and increase of the polyalkylate outlet concentration by 1.5–2 wt % are the results of the catalyst deactivation. These effects, however, can be compensated by 1.3-time increase of polyalkylate supply and by the temperature increase up to 398 K. Finally, the calculations also show that it is possible to decrease the supply of fresh catalyst from 0.498 to 0.472 t/hour without loss in the yield of ethylbenzene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Solid-State Support for Separating Astatine-211 from Bismuth

Increasing access to the short-lived α-emitting radionuclide astatine-211 ( 211 At) has the potential to advance targeted α-therapeutic treatment of disease and to solve challenges facing the medical community. For example, there are numerous technical needs associated with advancing the use of 211 At in targeted α-therapy, e.g., improving 211 At chelates, developing more effective 211 At targeting, and characterizing in vivo 211 At behavior. There is an insufficient understanding of astatine chemistry to support these efforts. The chemistry of astatine is one of the least developed of all elements on the periodic table, owing to its limited supply and short half-life. Increasing access to 211 At could help address these issues and advance understanding of 211 At chemistry in general. Here, we contribute an extraction chromatographic processing method that simplifies 211 At production in terms of purification. It utilizes the commercially available Pre-Filter resin to rapidly (<1.5 h) isolate 211 At from irradiated bismuth targets (Bi decontamination factors ≥876 000), in reasonable yield (68–55%) and in a form that is compatible for subsequent in vivo study. We are excited about the potential of this procedure to address 211 At supply and processing/purification problems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Practical Guide to Chemometric Analysis of Optical Spectroscopic Data

The methodology and mathematical treatment of several classic multivariate methods for the analysis of spectroscopic data is demonstrated in a straightforward way that can be used as a basis for teaching an undergraduate introductory course on chemometric analysis. The multivariate techniques of classical least squares (CLS), principal component regression (PCR), and partial least squares (PLS), as well as the univariate Beer’s law method have been described and compared, building students’ understanding by starting with the univariate method and progressing step by step into the multivariate methods. Equations for the production of regression vectors from training set spectral data is described and their use demonstrated for the prediction of constituent concentrations on a separate validation set of spectra. Extreme care is taken to ensure consistency in variable formatting of data matrices. This provides a key foundation to understanding how spectral data are manipulated using these different mathematical approaches for building quantitative regression models. Each method is applied to a real-world data set, and the results are discussed to show students the types of information that can be gleaned from each method. A training set comprised of 20 infrared absorbance spectra containing 3 constituents (benzene, polystyrene, and gasoline) of known composition are used to demonstrate the matrix operations for each regression method. A separate set of 12 real-world napalm samples (containing benzene, polystyrene and gasoline) are used as a validation set to demonstrate the ability to utilize the regression models on an unknown dataset. A toolbox (PNNL Chemometric Toolbox) written in MATLAB language is supplied in the Supplemental Information file and can be used as a companion for understanding the development and deployment of the chemometric algorithms described in this paper. The datasets of the infrared spectra are also supplied, allowing users to build and inspect the chemometric models on their own. Finally, the Toolbox includes scripts to assist users in loading their own datasets into MATLAB and performing CLS, PCR, and PLS on their data.

Upper-Division Undergraduate, Analytical Chemistry↗

Mass Spectrometry Adduct Calculator

We describe the Mass Spectrometry Adduct Calculator (MSAC), an automated Python tool to calculate the adduct ion masses of a parent molecule. Here, adduct refers to a version of a parent molecule [M] that is charged due to addition or loss of atoms and electrons resulting in a charged ion, e.g. [M+H] + . MSAC includes a database of 2,341 potential ions and their mass-to-charge ratios (m/z) as extracted from the NIST/EPA/NIH Mass Spectral Library (NIST17), the Global Natural Products Social Molecular Networking Public Spectral Libraries (GNPS), and MassBank of North America (MoNA). The calculator relies on user-selected subsets of the combined database to calculate expected m/z for adducts of molecules supplied as formulas This tool is intended to help researchers create identification libraries to collect evidence for the presence of molecules in mass spectrometry data. While the included adduct database focuses on adducts typically detected during liquid chromatography-mass spectrometry analyses, users may supply their own lists of adducts and charge states for calculating expected m/z. We also analyzed statistics on adducts from spectra contained in the three selected mass spectral libraries. MSAC is freely available at https://github.com/pnnl/MSAC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water and Solute Activities Regulate CO 2 Reduction in Gas-Diffusion Electrodes

Electrolysis of CO 2 at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm –2 , where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO 2 to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO 2 by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO 2 to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm –2 at the inlet had only ~0.3 A cm –2 at the outlet for a conversion in CO 2 partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗