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At least 757 records · Page 42

Demand-side solutions in the US building sector could achieve deep emissions reductions and avoid over $100 billion in power sector costs

Buildings are energy-intensive and a primary source of US end-use sector carbon emissions. Although building emissions today are 25% below their 2005 peak, far deeper reductions are needed to reach the US 2050 net-zero emissions goal. However, plausible decarbonization pathways that consider both buildings and their interactions with the power grid remain poorly understood. Here, we couple detailed modeling of building energy use and the grid to quantify building decarbonization potential and associated grid impacts. We find up to a 91% reduction in building CO 2 emissions from 2005 levels by 2050 using a portfolio of building efficiency, demand flexibility, and electrification measures alongside rapid grid decarbonization. Building efficiency and flexibility could generate up to $107 billion in annual power system cost savings by 2050, offsetting over a third of the incremental cost of full grid decarbonization. Our results underscore multiple benefits of demand-side solutions for deep decarbonization of US buildings.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Data-driven evaluation of HVAC operation and savings in commercial buildings

Commercial buildings consumed 36% of electricity, or 1.35 trillion kWh, in the United States in 2017, and almost 30% of this energy was wasted. Much of this loss can be attributed to inefficient heating ventilation and air con­ditioning (HVAC) systems. By improving the operational conditions of HVAC, significant savings can be achieved. However, most buildings and building equipment do not use costly sub-meters to monitor and address performance issues, and on-site auditing can be expensive and insufficient. Alternatively in this study, we propose a data-driven method to identify savings opportunities using only whole building meter data and without setting foot in the building. For this purpose, we introduced two algorithms that virtually quantify the value of a thermostat setpoint setback and HVAC rescheduling. Additionally, we developed novel methods for detecting occupancy patterns and quantifying the baseload of the HVAC operation. Using a clustering algorithm, we identified those buildings for which HVAC savings was significant and further categorized the buildings based on their potential for savings. A population study of over 432 commercial buildings demonstrated a median percentage energy savings of 1.6% from a baseload reduction and 2.1% from HVAC rescheduling. Additionally, results indicate that retail buildings have the highest potential for savings among the building types studied.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2

Abstract Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water‐gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine‐learning interatomic potentials (MLIPs) integrated with an active‐learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high‐resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.

Lee, Yonghyuk [Chemistry and Biochemistry Universi↗

Catalytic reduction of carbon dioxide to methanol over defect-laden hexagonal boron nitride: insights into reaction mechanisms

Abstract We present a density functional theory-based mechanistic understanding of CO 2 hydrogenation to value-added products on a nitrogen-vacancy (V N ) defect in hexagonal boron nitride ( dh -BN). Activation occurs through back-donation to the π * orbitals of CO 2 from the frontier orbitals (defect state) of the h- BN sheet that are localized near a nitrogen-vacancy. Subsequent hydrogenation to methanol (CH 3 OH) and formic acid (HCOOH) proceed through vacancy-facilitated co-adsorption of hydrogen and CO 2 . More importantly, our reaction pathway analyses complimented by microkinetic modeling indicate that dh -BN is potentially a low-temperature, selective catalyst for CO 2 reduction to methanol. Our findings are in agreement with experiments conducted in a mechanical reactor that show high selectivity towards methanol formation for CO 2 hydrogenation on defect induced h- BN.

Jiang, Tao (ORCID:0000000304197288)↗

Assessing the Returns to Land and Greenhouse Gas Savings from Producing Energy Crops on Conservation Reserve Program Land

Using land already enrolled in the Conservation Reserve Program (CRP) in the eastern region of the U.S. for producing energy crops for bioenergy while reducing land rental payments offers the potential for lowering the program costs, increasing returns to CRP landowners, and displacing greenhouse gas (GHG) emissions from fossil fuels. We develop an integrated modeling approach to analyze the combination of biomass prices and CRP land rental payment reductions that can incentivize energy crop production on CRP land and its potential to increase soil carbon stocks and displace fossil fuel emissions. Here, we find that conversion of 3.4 million ha in the CRP can be economically viable at a minimum biomass price of 75 Mg –1 with full CRP land rental payment or at 100 Mg –1 with 75% of this land rental payment; this conversion can result in savings of 0.52 and 1.25 billion Mg CO 2 -eq in life-cycle emissions through the displacement of energy-equivalent fossil fuels and coal-based electricity, respectively, and an additional 0.11 billion Mg CO 2 -eq soil carbon sequestration relative to the status quo, with CRP left unharvested over the 2016–2030 period. The soil carbon debt due to the transition from unharvested CRP land to energy crops is short-lived and more than offset by the reduction in fossil fuel emissions. The net discounted benefits from producing energy crops on CRP land through a reduced need for government payments to maintain existing enrollment, higher returns to CRP landowners, and the value of the reduction in GHG emissions could be as high as 16–30 billion by using them for cellulosic biofuels to displace gasoline and 35–68 billion by displacing coal-based electricity over the 2016–2030 period if biomass prices are 75–125 Mg –1 and land rental payments are reduced by 25%.

54 ENVIRONMENTAL SCIENCES↗

Investigating Abiotic and Biotic Mechanisms of Pyrite Reduction

Pyrite (FeS 2 ) has a very low solubility and therefore has historically been considered a sink for iron (Fe) and sulfur (S) and unavailable to biology in the absence of oxygen and oxidative weathering. Anaerobic methanogens were recently shown to reduce FeS 2 and assimilate Fe and S reduction products to meet nutrient demands. However, the mechanism of FeS 2 mineral reduction and the forms of Fe and S assimilated by methanogens remained unclear. Thermodynamic calculations described herein indicate that H 2 at aqueous concentrations as low as 10 –10 M favors the reduction of FeS 2 , with sulfide (HS – ) and pyrrhotite (Fe 1–x S) as products; abiotic laboratory experiments confirmed the reduction of FeS 2 with dissolved H 2 concentrations greater than 1.98 × 10 –4 M H 2 . Growth studies of Methanosarcina barkeri provided with FeS 2 as the sole source of Fe and S resulted in H 2 production but at concentrations too low to drive abiotic FeS 2 reduction, based on abiotic laboratory experimental data. A strain of M. barkeri with deletions in all [NiFe]-hydrogenases maintained the ability to reduce FeS 2 during growth, providing further evidence that extracellular electron transport (EET) to FeS 2 does not involve H 2 or [NiFe]-hydrogenases. Physical contact between cells and FeS 2 was required for mineral reduction but was not required to obtain Fe and S from dissolution products. The addition of a synthetic electron shuttle, anthraquinone-2,6-disulfonate, allowed for biological reduction of FeS 2 when physical contact between cells and FeS 2 was prohibited, indicating that exogenous electron shuttles can mediate FeS 2 reduction. Here, transcriptomics experiments revealed upregulation of several cytoplasmic oxidoreductases during growth of M. barkeri on FeS 2 , which may indicate involvement in provisioning low potential electrons for EET to FeS 2 . Collectively, the data presented herein indicate that reduction of insoluble FeS 2 by M. barkeri occurred via electron transfer from the cell surface to the mineral surface resulting in the generation of soluble HS – and mineral-associated Fe 1–x S. Solubilized Fe(II), but not HS – , from mineral-associated Fe 1–x S reacts with aqueous HS – yielding aqueous iron sulfur clusters (FeS aq ) that likely serve as the Fe and S source for methanogen growth and activity. FeS aq nucleation and subsequent precipitation on the surface of cells may result in accelerated EET to FeS 2 , resulting in positive feedback between cell activity and FeS 2 reduction.

59 BASIC BIOLOGICAL SCIENCES↗

Machine‐Learning‐Driven Exploration of Surface Reconstructions of Reduced Rutile TiO 2

Titanium dioxide (TiO 2 ) is widely used as a catalyst support due to its stability, tunable electronic properties, and surface oxygen vacancies, which are crucial for catalytic processes such as the reverse water-gas shift (RWGS) reaction. Reduced TiO 2 surfaces undergo complex surface reconstructions that endow unique properties but are computationally challenging to describe. In this study, we utilize machine-learning interatomic potentials (MLIPs) integrated with an active-learning workflow to efficiently explore reduced rutile TiO 2 surfaces. This approach enabled the prediction of a phase diagram as a function of oxygen chemical potential, revealing a variety of reconstructed phases, including a previously unreported subsurface shear plane structure. We further investigate the electronic properties of these surfaces and validate our results by comparing experimental and theoretical high-resolution transmission electron microscopy (HRTEM). Our findings provide new insights into how extreme surface reductions influence the structural and electronic properties of TiO 2 , with potential implications for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the influence of interfacial solvation on electrochemical CO 2 reduction using plasmon‐enhanced vibrational sum frequency generation spectroscopy

Although interfacial solvation plays an important role in determining carbon dioxide reduction (CO 2 R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO 2 R remains limited. This article summarizes the development and recent applications of plasmon-enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO 2 R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation-mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO 2 R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In planta production of the nylon precursor beta-ketoadipate

Beta-ketoadipate (βKA) is an intermediate of the βKA pathway involved in the degradation of aromatic compounds in several bacteria and fungi. Beta-ketoadipate also represents a promising chemical for the manufacturing of performance-advantaged nylons. We established a strategy for the in planta synthesis of βKA via manipulation of the shikimate pathway and the expression of bacterial enzymes from the βKA pathway. Using Nicotiana benthamiana as a transient expression system, we demonstrated the efficient conversion of protocatechuate (PCA) to βKA when plastid-targeted bacterial-derived PCA 3,4-dioxygenase (PcaHG) and 3-carboxy-cis,cis-muconate cycloisomerase (PcaB) were co-expressed with 3-deoxy-D-arabinoheptulosonate 7-phosphate synthase (AroG) and 3-dehydroshikimate dehydratase (QsuB). This metabolic pathway was reconstituted in Arabidopsis by introducing a construct (pAtβKA) with stacked pcaG, pcaH, and pcaB genes into a PCA-overproducing genetic background that expresses AroG and QsuB (referred as QsuB-2). The resulting QsuB-2 x pAtβKA stable lines displayed βKA titers as high as 0.25 % on a dry weight basis in stems, along with a drastic reduction in lignin content and improvement of biomass saccharification efficiency compared to wild-type controls, and without any significant reduction in biomass yields. Using biomass sorghum as a potential crop for large-scale βKA production, techno-economic analysis indicated that βKA accumulated at titers of 0.25 % and 4 % on a dry weight basis could be competitively priced in the range of $2.04-34.49/kg and $0.47-2.12/kg, respectively, depending on the selling price of the residual biomass recovered after βKA extraction. This study lays the foundation for a more environmentally-friendly synthesis of βKA using plants as production hosts.

Kazaz, Sami↗

Composite biopolymer electrolytes for high-performance reversible zinc-air batteries

Zinc-air batteries (ZABs) are regarded as one of the most promising candidates for next-generation energy storage systems due to their inherent safety, high energy density, and low cost. In this study, we optimized the composition of gel polymer electrolytes (GPEs), which play a crucial role in enhancing ZAB reversibility due to their water retention capabilities. The GPEs are synthesized using a combination of polyacrylic acid (PAA), polyacrylamide (PAM), and biopolymer kappa-carrageenan (KC), with and without additional additives. Among these, the composite GPE containing KC, PAA, and PAM demonstrated superior ionic conductivity (6.68 mS/cm at 30 °C) and enhanced water retention compared to the PAA–PAM-based GPE. Furthermore, this composite electrolyte operates within a wider electrochemical window of −1.0 V–2.2 V. A bifunctional catalyst, nickel–iron layered double hydroxide (NiFe-LDH), is electrochemically synthesized on a modified activated carbon cloth (CC). The catalyst loading is optimized based on oxygen evolution reaction (OER) performance, showing an overpotential of 555 mV. The oxygen reduction reaction (ORR) occurred at a half-wave potential of 0.620 V, which is lower than that of Pt/C (0.852 V), indicating better catalytic activity. The KC based cell exhibit better cycling stability than PAA–PAM-based GPE. The electrochemical performance of ZAB cells is evaluated under various atmospheres: ambient air and humid conditions and temperatures. Notably, in a humid environment, the cells achieved extended cycling stability, operating for over 500 h—significantly longer than under open-air conditions. Overall, this study highlights the importance of tailored GPE design and efficient bifunctional catalysts to enhance the performance and longevity of zinc-air batteries for long-duration energy storage applications.

Catalyst↗

Electrochemical Evolution of Fuel Cell Platinum Nanocatalysts on Carbon Nanotubes at the Atomic Scale

The evolution of Pt nanoparticles supported on carbon nanotubes is analyzed before and after electrochemical potential cycling, using identical location aberration-corrected transmission electron microscopy, for applications in proton exchange membrane fuel cells. The work is focused on the half-cell accelerated stress test protocol of potential cycles ranging between 1.0 and 1.5 V RHE to represent the start-up/shutdown settings of a fuel cell vehicle. The research work reveals that particle migration and coalescence are key mechanisms for a reduction in the Pt nanoparticle surface area at the early stages of potential cycling. Further, the mechanism for particle movement and coalescence is attributed to carbon corrosion, catalyzed either by Pt or by bulk corrosion of the carbon nanotubes. Carbon corrosion results in the appearance of carbon vacancies at the carbon nanotube/Pt nanoparticle interface during cycling, as well as the formation of edge and surface defects. During cycling, the concentration of the dissoluble Pt increases. As soon as a significant amount is reached, subnanometer/atomic clusters emerge on the carbon nanotube support, which can move and coalesce, or redeposit on the surface of larger particles through Ostwald ripening.

25 ENERGY STORAGE↗

Impact of Interposer Microstructure on Ionic Transport in Liquid-Phase Bicarbonate Electrolysis

The electrochemical reduction of CO 2 (CO 2 RR) is a potentially scalable approach for converting captured carbon dioxide into value-added products. Conventional gas-phase electrolysis systems can suffer from carbonate crossover, which limits the efficiency of the system. Liquid-phase (bi)carbonate electrolysis using bipolar membrane electrode assemblies (BPMMEA) has emerged as a promising alternative. The interposer layer, a porous mass-transport material between the BPM and the catalyst, is an essential component of the MEA, as it allows evolved CO 2 to reach the catalyst surface for reaction. In the absence of this layer, evolved CO 2 generated by the pH swing process at the BPM can be converted back into (bi)carbonate (CO 2 recapture) due to the high bulk pH. Thus, clear design guidelines are needed to maximize CO 2 conversion, minimize CO 2 recapture in the catholyte, and improve energy efficiency. Here, the transport properties of the interposer are systematically characterized by X-ray tomography and symmetric-cell impedance spectroscopy to quantify porosity, tortuosity, and the resulting MacMullin number. We then examine the correlation between these material properties and the electrolyzer performance. We focus on characterizing two commercial porous membrane filters, mixed cellulose ester (MCE) and poly(ether sulfone) (PES).

CO2 electrolysis↗

Recent Increasing Trend in October–November Caribbean Tropical Cyclone Activity

October–November Caribbean tropical cyclone (TC) activity has significant impacts for both the Caribbean islands and Central America (e.g., Hurricanes Eta and Iota in 2020). October–November Caribbean TCs can also track northward and make continental United States landfall, resulting in substantial damage and fatalities (e.g., Hurricane Michael in 2018 and Delta and Zeta in 2020). We find significant increasing trends in October–November Caribbean hurricanes, rapidly intensifying hurricanes (winds increasing by ≥15 m s −1 within 24 hr), and landfalling hurricanes during the global satellite era (1979–present). Since 1979, we also observe significant warming trends in the western Atlantic Warm Pool and anomalous relative cooling in the eastern Pacific during October–November. These trends yield a more conducive dynamic and thermodynamic environment for Caribbean TCs, including reductions in Caribbean vertical wind shear, increases in Caribbean potential intensity, and a more TC-conducive African easterly jet.

Klotzbach, P. J. [Colorado State Univ., Fort Colli↗

Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO 2 2+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides ( 238 U, 237 Np, 242 Pu and 243 Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tuning microwave losses in superconducting resonators

Abstract The performance of superconducting resonators, particularly cavities for particle accelerators and micro cavities and thin film resonators for quantum computations and photon detectors, has been improved substantially by recent material treatments and technological advances. As a result, the niobium cavities have reached the quality factors Q ∼ 10 11 at 1–2 GHz and 1.5 K and the breakdown radio-frequency (rf) fields H close to the dc superheating field of the Meissner state. These advances raise the questions of whether the state-of-the-art cavities are close to the fundamental limits, what these limits actually are, and to what extent the Q and H limits can be pushed by the materials nano structuring and impurity management. These issues are also relevant for many applications using high-Q thin film resonators, including single-photon detectors and quantum circuits. This topical review outlines basic physical mechanisms of the rf nonlinear surface impedance controlled by quasiparticles, dielectric losses and trapped vortices, as well as the dynamic field limit of the Meissner state. Sections cover methods of engineering an optimum quasiparticle density of states and superfluid density to reduce rf losses and kinetic inductance by pairbreaking mechanisms related to magnetic impurities, rf currents, and proximity-coupled metallic layers at the surface. A section focuses on mechanisms of residual surface resistance, which dominates rf losses at ultra low temperatures. Microwave losses of trapped vortices and their reduction by optimizing the concentration of impurities and pinning potential are also discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Downwind control of oceanic air by land: the land wake and its sensitivity to CO 2

Oceans are well-known to be directly altered by global climate forcings such as greenhouse gas changes, but how oceans are indirectly influenced by land and its response to such forcings remains less explored. Here, we assess the present-day and projected future state of a little-explored feature of the climate system—a 'land wake' in relative humidity downwind of the east coast of North America, consisting of low-humidity continental air extending roughly 1000 km over the Atlantic ocean. The wake exists throughout the year, but is supported by high continental temperatures in summer and low continental moisture in winter. The wake is well represented in an ensemble of global climate models (GCMs), qualitatively matching reanalysis data. Under increasing atmospheric CO 2 , the land wake intensifies in GCM simulations through two pathways: the radiative effects of CO 2 on surface temperatures, and the biogeochemical effect of CO 2 on terrestrial vegetation. Vegetation responses to increased CO 2 alter the summer wake from Florida to Newfoundland, and both the radiative and biogeochemical effects of CO 2 drive reductions in coastal cloud cover. These changes illustrate the potential of rapidly changing terrestrial climate to influence coastal regions and the ocean environment downwind of continents through both light conditions and the energy balance of the surface ocean.

54 ENVIRONMENTAL SCIENCES↗

Chemical control of the Rashba spin splitting size of α-GeTe(111) surface states by adjusting the potential at the topmost atomic layer

As control of the Rashba spin splitting size is highly desirable for spintronic devices, intensive studies have been performed to vary the splitting size by, for example, applying an electric field or designing novel heterostructures. However, direct observation of Rashba spin splitting size change via spectroscopic measurements has not been done so far. Here, we report results of angle-resolved photoemission studies on ferroelectric α-GeTe(111). We observe that the Rashba splitting size of α-GeTe(111) surface states is reduced upon dosing with potassium (K) which has a very low electron affinity. Based on density functional theory calculations, we find that the electric potential energy at the topmost atomic layer and the surface potential energy barrier is reduced upon K dosing. Furthermore, this change in the surface potential induces both delocalization of the surface states and reduction of the splitting size. We expect to increase the splitting size by dosing other elements or molecules with high electron affinity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cell wall ester modifications and volatile emission signatures of plant response to abiotic stress

Abstract Growth suppression and defence signalling are simultaneous strategies that plants invoke to respond to abiotic stress. Here, we show that the drought stress response of poplar trees ( Populus trichocarpa ) is initiated by a suppression in cell wall derived methanol (MeOH) emissions and activation of acetic acid (AA) fermentation defences. Temperature sensitive emissions dominated by MeOH (AA/MeOH <30%) were observed from physiologically active leaves, branches, detached stems, leaf cell wall isolations and whole ecosystems. In contrast, drought treatment resulted in a suppression of MeOH emissions and strong enhancement in AA emissions together with volatiles acetaldehyde, ethanol, and acetone. These drought‐induced changes coincided with a reduction in stomatal conductance, photosynthesis, transpiration, and leaf water potential. The strong enhancement in AA/MeOH emission ratios during drought (400%–3500%) was associated with an increase in acetate content of whole leaf cell walls, which became significantly 13 C 2 ‐labelled following the delivery of 13 C 2 ‐acetate via the transpiration stream. The results are consistent with both enzymatic and nonenzymatic MeOH and AA production at high temperature in hydrated tissues associated with accelerated primary cell wall growth processes, which are downregulated during drought. While the metabolic source(s) require further investigation, the observations are consistent with drought‐induced activation of aerobic fermentation driving high rates of foliar AA emissions and enhancements in leaf cell wall O ‐acetylation. We suggest that atmospheric AA/MeOH emission ratios could be useful as a highly sensitive signal in studies investigating environmental and biological factors influencing growth‐defence trade‐offs in plants and ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗