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At least 91 records · Page 5

Small Reservoirs Offer a New Perspective on Flood Reduction in Large Basins

The flood reduction potential of individual reservoirs within a large river network continuum remains poorly understood due to the complex interplay between reservoir characteristics and network properties. Here we investigate whether a collection of relatively small reservoirs can play a significant role in mediating downstream floods and assess how that role may be influenced by reservoir network properties compared to traditionally known reservoir characteristics. Our unique contribution was the simulation of downstream flood inundation maps alongside peak flows for each of the 81 major reservoirs (6 × 104 to 8 × 109 m3) across 15,000 river reach segments, integrated into a process-based hydrologic model covering a 415,000 km2 region in the Texas Gulf Coast, United States. The three key takeaways from our study are as follows. (a) Smaller reservoirs can substantially reduce downstream flooding, suggesting that inclusion of large reservoirs—the traditional approach in flood risk management studies—may present only a partial picture. (b) Flood reduction by smaller reservoirs is more effective upstream, although this phenomenon may be linked with aridity and overall water availability. (c) While reservoir size matters, it is not the primary factor determining its downstream flood reduction potential; the influence of network properties, such as catchment area, the count of upstream reservoirs, the cumulative maximum storage capacity of upstream reservoirs, and Stream Order (i.e., location), is equally and often more important. The broader impact of our findings goes beyond just floods, providing foundational insights for addressing emerging challenges such as aging dams and river connectivity.

Patel, Krutikkumar [University of Texas at Arlingt↗

Mitigating life cycle GHG emissions of roads to be built through 2030: Case study of a Chinese province

We report the expansion of road networks in emerging economies such as China causes significant greenhouse gas (GHG) emissions. This development is conflicting with China's commitment to achieve carbon neutrality. Thus, there is a need to better understand life cycle emissions of road infrastructure and opportunities to mitigate these emissions. Existing impact studies of roads in developing countries do not address recycled materials, improved pavement maintenance, or pavement-vehicle interaction and electric vehicle (EV) adoption. Combining firsthand information from Chinese road construction engineers with publicly available data, this paper estimates a comprehensive account of GHG emissions of the road pavement network to be constructed in the next ten years in the Shandong province in Northern China. Further, we estimate the potential of GHG emission reductions achievable under three scenario sets: maintenance optimization, alternative pavement material replacement, and EV adoption. Results show that the life cycle GHG emissions of highways and Class 1–4 roads to be constructed in the next 10 years amount to 147 Mt CO2-eq. Considering the use phase in our model reveals that it is the dominant stage in terms of emissions, largely due to pavement-vehicle interaction. Vehicle electrification can only moderately mitigate these emissions. Other stages, such as materials production and road maintenance and rehabilitation, contribute substantially to GHG emissions as well, highlighting the importance of optimizing the management of these stages. Surprisingly, longer, not shorter maintenance intervals, yield significant emission reductions. Another counter-intuitive finding is that thicker and more material-intensive pavement surfaces cause lower emissions overall. Taken together, optimal maintenance and rehabilitation schedules, alternative material use, and vehicle electrification provide GHG reduction potentials of 11%, 4%–16% and 2%–6%, respectively.

54 ENVIRONMENTAL SCIENCES↗

Multi-Electron Transfer at H-Terminated p-Si Electrolyte Interfaces: Large Photovoltages under Inversion Conditions

Here, photovoltages for hydrogen terminated p-Si(111) in an acetonitrile electrolyte were quantified with methyl viologen [1,1'-(CH 3 ) 2 -4,4'-bipyridinium](PF 6 ) 2 , abbreviated MV 2+ , and [Ru(bpy) 3 ](PF 6 ) 2 , where bpy is 2,2'-bipyridine, that respectively undergo two and three one-electron transfer reductions. The reduction potentials, E°, of the two MV 2+ reductions occurred at energies within the forbidden bandgap, while the three [Ru(bpy) 3 ] 2+ reductions occurred within the continuum of conduction band states. Bandgap illumination resulted in reduction that were more positive than that measured with a degenerately doped n + -Si demonstrative of a photovoltage, Vph, that increased in the order: MV 2+/+ (260 mV) < MV +/0 (400 mV) < Ru 2+/+ (530 mV) ~ Ru +/0 (540 mV) ~ Ru 0/– (550 mV). Pulsed 532 nm excitation generated electron-hole pairs whose dynamics were nearly constant under depletion conditions and increased markedly as the potential was raised or lowered. A long wavelength absorption feature assigned to conduction band electrons provided additional evidence for the presence of an inversion layer. Collectively, the data reveal that the most optimal photovoltage, as well at the longest electron-hole pair lifetime and the highest surface electron concentration, occur when E° lies energetically within the unfilled conduction band states where an inversion layer is present. The bell-shaped dependence for electron-hole pair recombination with the surface potential was predicted by the time-honored SRH model providing a clear indication that this interface provides access to all four bias conditions, i.e., accumulation, flat band, depletion, and inversion. The implications of these findings for photocatalysis applications and solar energy conversion are discussed.

14 SOLAR ENERGY↗

Mechanistic Insights into Co and Fe Quaterpyridine-Based CO 2 Reduction Catalysts: Metal–Ligand Orbital Interaction as the Key Driving Force for Distinct Pathways

Both [Co II (qpy)(H 2 O) 2 ] 2+ and [Fe II (qpy)(H 2 O) 2 ] 2+ (with qpy = 2,2':6',2'':6'',2'''-quaterpyridine) are efficient homogeneous electrocatalysts and photoelectrocatalysts for the reduction of CO 2 to CO. The Co catalyst is more efficient in the electrochemical reduction, while the Fe catalyst is an excellent photoelectrocatalyst. This work uses density functional theory to shed light on the contrasting catalytic pathways. While both catalysts experience primarily ligand-based reductions, the second reduction in the Co catalyst is delocalized onto the metal via a metal-ligand bonding interaction, causing a spin transition and a distorted ligand framework. This orbital interaction explains the experimentally observed mild reduction potential and slow kinetics of the second reduction. The decreased hardness and doubly occupied d z 2 -orbital facilitate a σ-bond with the CO 2 -π* in an η 1 - κC binding mode. CO 2 binding is only possible after two reductions resulting in an EEC mechanism (E = electron transfer, C = chemical reaction), and the second protonation is rate-limiting. In contrast, the Fe catalyst maintains a Lewis acidic metal center throughout the reduction process because the metal orbitals do not strongly mix with the qpy-π* orbitals. Further, this allows binding of the activated CO 2 in an η 2 -binding mode. This interaction stabilizes the activated CO 2 via a π-type interaction of a Fe-t 2g orbital and the CO 2 -π* and a dative bond of the oxygen lone pair. This facilitates CO 2 binding to a singly reduced catalyst resulting in an ECE mechanism. The barrier for CO 2 addition and the second protonation are higher than those for the Co catalyst and rate-limiting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

U.S. Industrial and Commercial Motor System Market Assessment Report. Volume 3: Energy Saving Opportunity

This report seeks to inform the potential for motor systems to support decarbonization by estimating their potential energy, electricity cost, and CO 2 emissions reduction potential from adoption of proven energy efficiency actions and advanced technologies. This is the third and final report in a series of reports disseminating the findings of the U.S. Department of Energy’s (DOE’s) Motor System Market Assessment (MSMA). The MSMA and this report focus on polyphase motor systems greater than or equal to 1 horsepower (hp) in the industrial and commercial sectors. In the U.S. Industrial and Commercial Motor System Market Assessment Report Volume 1: Characteristics of the Installed Base (Volume 1 report), it was determined that these motor systems consume more than 1,000 terawatt-hours (TWh) annually. This equates to 29% of the U.S. electric grid load and results in 765 million metric tons (MMT) of CO 2 emissions and $166 billion in electricity costs. This report finds that substantial reductions to these energy, cost, and emissions impacts are possible, with three areas of significant opportunity being (1) improved load matching, (2) replacing older inefficient motors with more efficient motors, and (3) improving the condition of fluid (e.g., air, water, compressed air) distribution systems. A summary of the savings potential from these three opportunities placed within the context of the overall consumption for motor systems is illustrated in Figure ES 1 (industrial) and Figure ES 2 (commercial).

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Time-series dissolved oxygen, other bigeochemically-relevant analytes, and pressure gradients associated with the manuscript “Dissolved oxygen sensor in an automated hyporheic sampling system reveals biogeochemical dynamics”

This dataset contains time-series data from a vertical profile within the bed and banks of the Columbia river near Richland, WA. Water was sampled through 3 small tubes embedded in the sediment at 50,100, and 200 cm below the sediment-water interface. The goal of this study was to observe the correlations between hydraulic drivers and biogeochemical responses. The results of this study are published in the manuscript “Dissolved oxygen sensor in an automated hyporheic sampling system reveals biogeochemical dynamics”. The file types included in the data package are all time-series spreadsheet data, including hydraulic head gradients, physical parameters (temperature, pressure, SpC (specific conductivity)), and biogeochemical parameters (dissolved oxygen, pH, NO3 (nitrate) and ORP (oxidation-reduction potential)).

54 ENVIRONMENTAL SCIENCES↗

Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion

Reduction of nitrite anions (NO 2 - ) to nitric oxide (NO), nitrous oxide (N 2 O) and ultimately dinitrogen (N 2 ) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. In this report we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO 2 2- ), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N 2 O) and nitrite (NO 2 - ). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO 2 - to NO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A series of four-coordinate heteroleptic copper(I) complexes with diimine and β-diketiminate ligands

In this paper, a series of heteroleptic bis-chelate copper(I) complexes of the general formula Cu(N^N)(NacNac R ), where N^N is the diimine ligand and NacNac R is the β-diketiminate ligand are introduced. The complexes are easily prepared by reacting NacNac ligands with CuO t Bu in the presence of diimine ligands. The molecular structures of all complexes are characterized by NMR spectroscopy and X-ray crystallography. The studies of cyclic voltammetry and UV–vis absorption spectra show that the HOMO and the LUMO energy level can be tailored by changing the substitution pattern of each ligand. The oxidation potential is dependent on the NacNac ligand, and the reduction potential shows the dependence on the diimine ligand. In conclusion, tunable redox potentials and a wide range of visible absorption can make these copper(I) complexes promising candidates for applications in solar light harvesting.

14 SOLAR ENERGY↗

A perspective on the redox properties of tetrapyrrole macrocycles

Tetrapyrrole macrocycles serve a multitude of roles in biological systems, including oxygen transport by heme and light harvesting and charge separation by chlorophylls and bacteriochlorophylls. Synthetic tetrapyrroles are utilized in diverse applications ranging from solar-energy conversion to photomedicine. Nevertheless, students beginning tetrapyrrole research, as well as established practitioners, are often puzzled when comparing properties of related tetrapyrroles. Questions arise as to why optical spectra of two tetrapyrroles often shift in wavelength/energy in a direction opposite to that predicted by common chemical intuition based on the size of a π-electron system. Gouterman's four-orbital model provides a framework for understanding these optical properties. Similarly, it can be puzzling as to why the oxidation potentials differ significantly when comparing two related tetrapyrroles, yet the reduction potentials change very little or shift in the opposite direction. In order to understand these redox properties, it must be recognized that structural/electronic alterations affect the four frontier molecular orbitals (HOMO, LUMO, HOMO-1 and LUMO+1) unequally and in many cases the LUMO+1, and not the LUMO, may track the HOMO in energy. This perspective presents a fundamental framework concerning tetrapyrrole electronic properties that should provide a foundation for rational molecular design in tetrapyrrole science.

chlorophyll↗

Technology Case Study: Techno-Economic and Life Cycle Analysis for Microalgae Conversion Pathways to Fuels and Products

This technology case study report details the cost and sustainability prospects for an emerging feedstock - microalgae - converted to fuels and products via a fractionation and upgrading approach termed combined algae processing (CAP). Detailed techno-economic analysis (TEA) and life cycle analysis (LCA) are conducted for the conversion of farmed algae biomass, with two primary scenarios considering the conversion of either high-compositional-quality biomass enriched in lipids (high-lipid [HL]) or lower-quality biomass enriched in protein (high-protein [HP]). Each scenario employs a different biorefinery configuration tailored towards extracting the maximum value from the given biomass composition. The HL scenario produces fuels and non-isocyanate polyurethane (NIPU) as the primary products, while the HP scenario products fuels and a residual solid coproduct which can be used as a co-feed for producing thermoplastics. The results for the HL scenario were particularly promising, with a minimum fuel selling price (MFSP) of $\$$3.68 per gasoline gallon equivalent (GGE) and fuel GHG emissions translating to 54%-76% reduction compared to petroleum fuels depending on the coproduct handling method used. In contrast, the HP scenario faced more challenges in producing biofuels economically, projecting an MFSP of $\$$7.92/GGE despite significant revenues from the residual algae solids. LCA results for the HP case reflected a 24% reduction potential in biorefinery-level GHG emissions. However, these GHG reductions were primarily associated with the thermoplastic coproduct, which accounted for 93% of all biorefinery outputs by mass. Using a process-level allocation method, carbon intensity results were less promising, indicating a net increase in fuel GHG emissions versus petroleum fuels and highlighting the reliance of this scenario on the thermoplastic coproduct.

09 BIOMASS FUELS↗

Catalytic Bias in Enzymatic Metal Cofactor-Based Oxidation-Reduction Catalysis

Catalytic bias refers to the relative rate preference of a catalyst for either the forward or reverse direction. In enzymatic metal cofactor-based oxidation-reduction catalysis, the tuning of catalytic bias plays an underlying role in controlling rates of reactivity. For this, enzymes have evolved complex active sites that can exist in multiple oxidation states with differing reduction potentials in order to achieve challenging multi-step, oxidation-reduction reactions. Conceivably, the relative stability of the intermediates that contribute to determining the rate-limiting step of the catalytic cycle could impose catalytic bias, although mechanisms for this concept are just beginning to be realized. As one example, recent work on Clostridium pasteurianum [FeFe]-hydrogenases which catalyze reversible hydrogen oxidation have shown that the differential stabilization/destabilization of active site oxidation states through either static or dynamic protein interactions can preferentially promote either the hydrogen oxidation or proton reduction direction of the reaction. This revealed how an enzymatic cofactor can impose bias in oxidation-reduction catalysis through various tuning mechanisms by protein scaffold interactions. The hypothesis based on achieving catalytic bias through the modulation of cofactor oxidation states critical for the reaction cycle can be extended more generally to other cofactor-based oxidation-reductions catalysts. The current understanding of catalytic bias has significant implications for the design of synthetic catalysts used in industrial settings, as well as providing a greater fundamental understanding of the factors that control metabolic processes in all life.

catalysis↗

200-DV-1 Laboratory Treatability Study: Proof-of-Principle Results

This document presents the Phase 1 technical approach and results of laboratory-scale treatability testing of nine in situ remedial technologies for their consideration in a future Feasibility Study (FS) for the 200-DV-1 OU. The primary objective of this initial assessment was a proof-of-principle testing evaluation primarily via batch experiments to determine the potential reduction and sequestration of primary contaminants of interest with and without potential co-contaminants of interest. An effectiveness rate of 35% transformation to immobile or nontoxic end products, along with other experimental indicators, was used by the project team to determine the technologies that advanced to Phase 2 for further evaluations. For most technologies, the performance was evaluated based on a series of sequential extractions designed to evaluate the mobility of contaminants before and after treatment, with each subsequent extraction representing a relative decrease in mobility. The results of this study will be used to inform testing for Phase 2 of the treatability study for further evaluation of selected technologies. The final results from the treatability study, following the completion of remaining experimental phases, will be used to determine whether the technologies tested can be appropriately evaluated in a FS to expand on the limited number of viable DVZ remediation technologies. After completion of the laboratory treatability study and the 200-DV-1 OU Remedial Investigation (RI) and Resource Conservation and Recovery Act Facility Investigation (RFI) of the waste sites, results will be evaluated to determine whether field studies are needed to provide additional information on effectiveness, implementability, or costs for evaluating these technologies in the FS for their site-specific application.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Constructing synthetic organosulfur additive for high voltage lithium-ion batteries

Despite its high anodic stability, common organosulfur solvents such as ethyl methyl sulfone and sulfolane typically exhibit poor solid-electrolyte interphase (SEI) formation capability. Here, to address this, the fluorinated organic sulfate 4-(trifluoromethyl)-1,3,2-dioxathiolane 2,2-dioxide (TFDTD) was developed as an effective additive for tailoring organosulfur-based electrolytes in lithium-ion batteries. This development was guided by the functionality selection principle and careful evaluation of feasibility in organic synthesis. TFDTD can be readily synthesized through the reaction between trifluoropropylene glycol and sulfuryl chloride. The ring structure of the organic sulfate enables the formation of a stable SEI on the anode, while the fluorination of the sulfate not only enhances its chemical stability and oxidation potential, but also its effectiveness to protect the anode by increasing its reduction potential, rendering it preferentially reduced on the anode surface before the decomposition of other electrolyte components. Introducing TFDTD facilitates the generation of a robust solidelectrolyte interphase on the graphite anode, significantly enhancing cell performance. Moreover, coupling the use of TFDTD with vinylene carbonate provides further protection on the cathode surface, enabling exceptionally stable, high-voltage, long-term cycling of Gr||NMC full cells.

Functionality selection principle↗

Optimal Power Sharing Speed Compensation in On-road Wireless EV Charging Systems

Dynamic wireless charging of electric vehicles (EV) is an emerging technology with the potential to address range anxiety and reduce the size of batteries or provide charge-sustaining operation. Charging demand for dynamic wireless charging systems (DWCS) varies greatly in response to location-specific traffic behaviors including the number and speed of vehicles. This paper highlights the potential reduction of load variation with speed compensation and simulates opportunities to maximize the number of cars charged concurrently through “power sharing” or altering power output to slower cars while maintaining a maximum delivered energy. An improved sub-minute model for synthetic traffic is proposed to effectively model DWCS load on high speed roadways and a power electronics model is created based on an existing prototype developed by ORNL to investigate the potential for power sharing. Reductions in the average speed of traffic can greatly increase instantaneous DWCS load by as much as 26%, complicating capacity sizing. Parametric studies with a LCC-S power electronics model shows feasible power reduction of more than 20%, while maintaining a maximum achievable efficiency greater than 90%. Speed compensation on a roadway with large speed variation can reduce average power expected by 21% and increase the maximum number of cars charged simultaneously by 30%. The application of power sharing may significantly reduce load variability due to speed, allow for increased car hosting capability, and guarantee a maximum energy delivered.

Lewis, Donovin D.↗

CO 2 Activation with Manganese Tricarbonyl Complexes through an H–Atom Responsive Benzimidazole Ligand

Herein, we report the synthesis and characterization of two manganese tricarbonyl complexes, Mn I (HL)(CO) 3 Br (1 a-Br) and Mn I (MeL)(CO) 3 Br (1 b-Br) (where HL=2-(2’-pyridyl)benzimidazole; MeL=1-methyl-2-(2’-pyridy)benzimidazole) and assayed their electrocatalytic properties for CO 2 reduction. A redox-active pyridine benzimidazole ancillary ligand in complex 1 a-Br displayed unique hydrogen atom transfer ability to facilitate electrocatalytic CO 2 conversion at a markedly lower reduction potential than that observed for 1 b-Br. Notably, a one-electron reduction of 1 a-Br yields a structurally characterized H-bonded binuclear Mn(I) adduct (2 a’) rather than the typically observed Mn(0)-Mn(0) dimer, suggesting a novel method for CO 2 activation. Furthermore, combining advanced electrochemical, spectroscopic, and single crystal X-ray diffraction techniques, we demonstrate the use of an H-atom responsive ligand may reveal an alternative, low-energy pathway for CO 2 activation by an earth-abundant metal complex catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal Identity and Coordination Environment Modulate Single-Atom Catalyst Stability During Electrocatalysis

A major hurdle to the implementation of single-atom catalysts (SACs) in real-world systems is a poor understanding of their stability under operating conditions, which is particularly relevant due to the high surface free energy of SACs. Here, we evaluated the aggregation behavior of a suite of SACs varied by metal identity (Fe, Co, Ni, and Cu) during electrocatalytic nitrate reduction using in situ X-ray absorption spectroscopy. The metal center had significant influence on reconstruction, where under identical applied reductive potentials, SACs underwent varying levels of reconstruction, ranging from no discernible change to complete reduction into metallic nanoparticles. Such in situ experiments revealed Cu SACs to be the most susceptible to aggregation, prompting a deeper investigation into how coordination environment (O-, B-, and N-graphene) affected Cu SAC aggregation. We further conducted density functional theory calculations to elucidate the relationship between Cu SAC structure and stability. This work deconvolutes the relationship between SAC architecture and stability, which is essential to evaluate and explain for the realization of SACs for electrocatalysis.

36 MATERIALS SCIENCE↗

Au x Pd (300‐ x ) Alloy Nanoparticles for the Oxygen Reduction Reaction in Alkaline Media

Abstract Au x Pd (300‐ x ) nanoalloys were prepared using a dendrimer‐templating method and their electrocatalytic efficiencies towards the oxygen reduction reaction (ORR) were analyzed in alkaline media. The composition‐dependent PdO x reduction potentials of the Au x Pd (300‐ x ) nanoalloys were correlated to the oxygen‐binding (O‐binding) energy of the catalysts. Multiple PdO x reduction peaks were present for the Au 150 Pd 150 and Au 50 Pd 250 catalysts. These peaks were assigned to the alloyed and bulk‐like Pd active sites on the alloyed surface. The results described here are significant because modulation of the O‐binding energies improved the ORR activity on the nanoalloys. Specifically, a linear trend in O‐binding energies of Au x Pd (300‐ x ) dendrimers (DENs) as a function of Pd composition resulted in a volcano‐shaped trend in ORR activity. The optimal O‐binding energy of Au 50 Pd 250 resulted in an approximate 89 mV shift in PdO x reduction relative to Pd 300 and a shift of approximately 76 mV in ORR peak potential.

Trindell, Jamie A.↗

Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode

High electrochemical reversibility is required for the application of high-energy-density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability-induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm -2 . This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries.

25 ENERGY STORAGE↗