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At least 127 records · Page 7

Protection against Chemical Warfare Agents and Biological Threats Using Metal–Organic Frameworks as Active Layers

The SARS-CoV-2 pandemic outbreak and the unfortunate misuse of toxic chemical warfare agents (CWAs) highlight the importance of developing functional materials to protect against these chemical and pathogen threats. Metal–organic frameworks (MOFs), which comprise a tunable class of crystalline porous materials built from inorganic nodes and organic linkers, have emerged as a class of heterogeneous catalysts capable of rapid detoxification of multiple classes of these harmful chemical or biological hazards. In particular, zirconium-based MOFs (Zr-MOFs) feature Lewis acidic nodes that serve as active sites for a wide range of catalytic reactions, including the hydrolysis of organophosphorus nerve agents within seconds in basic aqueous solutions. In addition, postsynthetic modification of Zr-MOFs enables the release of active species capable of reacting with and deactivating harmful pathogens. Despite this impressive performance, utilizing Zr- MOFs in powder form is not practical for application in masks or protective uniforms. To address this challenge, our team sought to develop MOF/fiber composite systems that could be adapted for use under realistic operating conditions to protect civilians, military personnel, and first responders from harmful pathogens and chemical warfare agents. Over the last several years, our group has designed and fabricated reactive and biocidal MOF/fiber composites that effectively capture and deactivate these toxic species. In this Account, we describe the evolution of these porous and reactive MOF/fiber composites and focus on key design challenges and considerations. First, we devised a scalable method for the integration of Zr-MOFs onto textile substrates using aqueous precursor solutions and without using pretreated textiles, highlighting the potential scalability of this method. Moving beyond standard textiles, we also developed a microbial synthesis strategy to prepare hierarchically porous MOF/bacterial cellulose nanofiber composite sponges that can both capture and detoxify nerve agents when exposed to contaminated gas flows. The mass loading of the MOF in the nanofibrous composite sponge is up to 90%, affording higher work capacities compared to those of textile-fiber-based composites with relatively lower MOF loadings. Next, we demonstrated that heterogeneous polymeric bases are suitable replacements for volatile liquid bases typically used in solution-phase reactions, and we showed that these composite systems are capable of effectively hydrolyzing nerve agents in the solid state by using only water that is present as humidity. Moreover, incorporating a reactive dye precursor into the composite affords a dual function sensing and detoxifying material that changes color from white to orange upon reaction with the byproduct following nerve agent hydrolysis, demonstrating the versatility of this platform for use in decontamination applications. We then created chlorine-loaded MOF/fiber composites that act as biocidal and reactive textiles that are capable of not only detoxifying sulfur-mustard-based chemical warfare agents and simulants but also deactivating both bacteria and the SARS-CoV-2 virus within minutes of exposure. Lastly, we synthesized a mixed-metal Ti/Zr-MOF coating on cotton fibers to afford a photoactive biocidal cloth that shows fast and broad-spectrum biocidal performance against viruses and Gram-positive and Gram-negative bacteria under visible light irradiation. Given the tunable, multifunctional nature of these MOF/fiber composites, we believe that this Account will offer new insights for the rational design and preparation of functional MOF/fiber composites and pave the way toward the development of next-generation reactive and protective textiles.

36 MATERIALS SCIENCE↗

Pulsed-Neutron Experiments at the Inherently Safe Subcritical Assembly

The pulsed neutron technique is a powerful, dynamic method to assay the reactivity of a multiplying system. This work presents the novel application of the pulsed neutron technique to the Inherently Safe Subcritical Assembly, an experimental configuration accepted by the International Criticality Safety Benchmark Evaluation Project Handbook. The experiments were replicated with COG11.3, a continuous-energy Monte Carlo code. The pulsed neutron data were analyzed using the Sjöstrand and Gozani area-ratio methods and by extracting the prompt neutron decay constant. Subsequent static k-eigenvalue and 𝛼-eigenvalue simulations were also performed for the same configurations. Neutron detector dead-time effects from the experiments were corrected using the Backwards Extrapolation Method and shown to have a negligible impact on the estimated reactivities. The results highlight that capturing time-dependent effects like delayed neutron precursor buildup are essential to accurately reproduce experimental results. They also highlight the importance of shielding the detectors from generator source neutrons in deeply subcritical configurations.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Computational Investigation of a CO 2 Conversion Strategy via Diels–Alder Reaction in a Carbon Capture Solvent

Molecular-level insights into reactive separations are crucial for the design of new conversion pathways of carbon dioxide (CO 2 ). This work explores a postulated pathway that directs CO 2 to undergo inverse-electron-demand Diels–Alder reactions to produce heterocycles using the CO 2 chemically fixed on water-lean solvent molecules. Density functional theory calculations are applied to evaluate the lowest unoccupied molecular orbital (LUMO) energies of three types of reactants (1,3-butadiene, 1,3-cyclohexadiene, and 1,2,4,5-tetrazine) with various functional substituents. These calculations also provide a data set (5.8k data) for developing a machine learning model to efficiently predict LUMO energies. A computational screening of LUMO energies for an additional 47k diene and tetrazine candidates is performed, and a list of candidates with lowered LUMO energies by electron-withdrawing substituents is provided. These candidates are further examined by their reaction energy barriers computed from the interatomic potential or density functional theory. Two major energy barriers are identified, one for the proton transfer within the water-lean solvent and the other for the CO 2 transfer from the solvent molecule to the reactant candidate (diene or tetrazine). The functional substituents have a more significant impact on the second barrier but a very slight one on the first barrier. This exploratory work demonstrates a new possibility for guiding experimental efforts toward the chemical conversion of fixated CO 2 to value-added compounds.

Chemical reactions↗

Integrated Technology for Cost-Effective CO2 Capture and Formic Acid Production: Modeling, Optimization, and Economic Analysis

A novel reactive technology is being investigated that electrochemically converts CO2 into valuable chemicals, particularly formic acid. This work focuses on identifying the optimal design and operation of an integrated membrane-based CO2 capture unit with the electrochemical conversion process. In this setup, the CO2 in the flue gas permeates through a CO2-selective membrane and enters an electrolyzer to produce formic acid, creating an integrated reaction module. To refine the chemical product, gas products from the electrolyzer are directed to a pressure swing adsorption unit, while the liquid product undergoes refinement to achieve commercial-grade formic acid using reactive distillation. A membrane CO2 capture model and an electrochemical conversion model have been developed using the IDAES Integrated Platform (Institute for the Design of Advanced Energy System), facilitating rigorous flowsheet modeling and process design and optimization.

Wang, Maojian↗

Distributed Mafic Rock Resources for Carbon Mineralization in Arizona

Ex-situ carbon mineralization is a process by which CO2 is reacted with alkaline silicate minerals and rocks to produce stable carbonate materials, which can be used for other industrial processes. Arizona, U.S.A., hosts abundant surficial mafic rocks in three young volcanic fields, Geronimo-San Bernardino, San Francisco, and Springerville, and other distributed locations throughout the state. We created a Mafic Rock Resource Inventory (MRRI) that categorizes geochemical, physical, and textural characteristics of a diverse suite of surficial mafic rock samples and provide a benchmark reaction dataset parameterizing the temperature, pressure, and pH conditions best suited ex-situ mineralization in different rock types. MRRI data is publicly available online via a map-viewer. We establish two reaction condition sets, varied in temperature, pressure, and pH, where crystal-rich and glassy rocks reach maximum reaction extent and different carbonate phases are formed. Systematic ex-situ mineralization experiments on 21 diverse rock types show trends in geochemical, mineralogical, and reactivity behavior and establish maximum effective capture capacity. From this, scoria cones in three Arizona volcanic fields have a ~62 Gt effective CO₂ storage capacity with one of the fields having a ~42 Gt storage capacity in lava flows. Reactivity results have applications to alkaline mafic rock resources exposed globally, including producing additional effective storage capacity estimates and scaled commercialization of mafic rock ex-situ mineralization, should reaction extents be improved through advances in mineralization techniques. MRRI data were used to create a Direct Air Capture to Mineralization (DACM) systems model, technoeconomic analysis, and life-cycle assessment. These documents are presented as three appendices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Modeling of fluid injection-induced fault reactivation using coupled fluid flow and mechanical interface model

The present study is aimed at developing a numerical model to reproduce coupled hydro-mechanical processes associated with fault reactivation by fluid injection in low permeability rock, as part of the DECOVALEX-2019 project Task B. We proposed a modeling approach for simulating the processes using the TOUGH-FLAC simulator, and modeled a fault reactivation experiment conducted at Mont Terri Rock Laboratory in Switzerland. The first step of the study involved benchmark calculations considering a simplified fault plane and geometry. Fluid flow along a fault was modeled using elements of aperture-sized thickness on the basis of Darcy's law and the cubic law in TOUGH2, whereas the mechanical behavior of a single fault was represented by zero-thickness interface elements in FLAC3D upon which a slip and/or separation is allowed. A methodology to connect a TOUGH2 volume element to a FLAC3D interface element was developed for handling the hydro-mechanical interactions on the fault during fluid injection. Two different fault models for describing the evolutions of hydraulic aperture by elastic fracture opening and failure-induced aperture increase were considered in the benchmark calculations. In the coupling process, the changes in geometrical features and hydrological properties induced by mechanical deformation were continuously updated. The transient responses of the fault and host rock to stepwise pressurization were examined during the simulation. The hydro-mechanical behavior, including the injection flow rate, pressure distribution around the borehole, stress conditions, and displacements in normal and shear directions were monitored in the surrounding rock and along the fault. The results of benchmark calculations suggest that the developed model reasonably represents the hydro-mechanical behavior of a fault and the surrounding rock. This modeling approach was applied to the fault reactivation experiment of the Mont Terri Rock Laboratory. In this interpretive modeling, a parametric study was conducted to examine the effects of input parameters regarding in situ stress and fault properties on the hydro-mechanical responses of the fault to water injection. Then, an optimal parameter set to reproduce the field experiment results was chosen by trial-and-error. The injection flow rate and pressure response during fault reactivation closely matched those obtained at the site, which indicates the capability of the model to appropriately capture the progressive pathway evolution during fault reactivation tests at the site. Finally, the anchor displacements were overestimated by the model, but a fair agreement was obtained in terms of the order of magnitude and the variation tendency.

58 GEOSCIENCES↗

First-Principles study of interface capture of Ni during high-temperature oxidation of NiCr alloys

The formation of precipitated phases of less reactive metals within an oxide scale during alloy oxidation can disrupt its structural integrity, significantly compromising the protective function of the oxide. To better understand this phenomenon, it is crucial to investigate the atomic-level diffusion mechanisms that drive precipitate formation. In this study, we employ first-principles calculations to examine the diffusion and aggregation of Ni atoms across the NiCr/Cr 2 O 3 interface during the high-temperature oxidation of NiCr alloys. Our results reveal that, in the absence of Cr vacancies, Ni atoms predominantly remain within the NiCr substrate, with minimal migration toward the Cr 2 O 3 layer. However, when Cr vacancies are present at both the NiCr/Cr 2 O 3 interface and within the Cr 2 O 3 bulk, Ni atoms exhibit a strong propensity to migrate from the NiCr substrate into the Cr 2 O 3 bulk, where they aggregate into Ni-rich regions with a corundum structure. This study provides valuable atomic-level insights into the diffusion and aggregation of less-reactive metals at the alloy/oxide interface, enhancing our understanding of solute capture and its contribution to the degradation of oxidation resistance in alloys.

Chen, Jianmin [Xiangtan University (China)] (ORCID↗

An Eulerian multimaterial framework for simulating high-explosive aquarium tests

Aquarium tests of cylindrical high-explosive charges provide optical data of the detonation front velocity and shape, propagation of the shock wave in the surrounding water, and expansion rates of the detonation products behind the front. Data from aquarium experiments is often used for calibration of reactive burn models based on phenomenological equations of state (EOS) and reaction rate laws. This paper presents a multimaterial numerical modeling framework to solve the 2D axisymmetric reactive Euler equations for high-explosive aquarium tests, in particular for ammonium nitrate - fuel oil (ANFO) explosives. An extension of the Ghost Fluid Method (GFM) is used to handle the dynamic material interfaces for the ANFO explosion products, the charge-confining material (polymethyl methacrylate PMMA), and the surrounding water. This study analyzes the sensitivity of calculations (both computational efficiency and numerical accuracy) to different algorithms for the material interface models including the original GFM versus Riemann solver-based strategies. A novel method for defining the left and right states in the interfacial Riemann problem eliminates the need for sorting or nodal interpolation during the projection along the material interface. Numerical tests indicate that populating the interface node values using the Riemann solution mitigate the overheating error observed in steady-state calculations. Solution convergence and computational efficiency are explored as a function of the spatial and temporal order of the schemes. Results from the computational model with analytical equations of state and fitted reaction rate parameters show very good quantitative agreement with experimentally observed detonation front velocity, reaction products expansion, and shock wave propagation in the surrounding water for a cylindrical ANFO charge encased in PMMA. Finally, the proposed modeling framework, in conjunction with experimental tests, provides a reliable tool to assess equations of state and reaction rate expressions for reactive burn models of confined high explosives.

42 ENGINEERING↗

PFLOTRAN-SIP: A PFLOTRAN Module for Simulating Spectral-Induced Polarization of Electrical Impedance Data

Spectral induced polarization (SIP) is a non-intrusive geophysical method that collects chargeability information (the ability of a material to retain charge) in the time domain or its phase shift in the frequency domain. Although SIP is a temporal method, it cannot measure the dynamics of flow and solute/species transport in the subsurface over long times (i.e., 10–100 s of years). Data collected with the SIP technique need to be coupled with fluid flow and reactive-transport models in order to capture long-term dynamics. To address this challenge, PFLOTRAN-SIP was built to couple SIP data to fluid flow and solute transport processes. Specifically, this framework couples the subsurface flow and transport simulator PFLOTRAN and geoelectrical simulator E4D without sacrificing computational performance. PFLOTRAN solves the coupled flow and solute-transport process models in order to estimate solute concentrations, which were used in Archie’s model to compute bulk electrical conductivities at near-zero frequency. These bulk electrical conductivities were modified while using the Cole–Cole model to account for frequency dependence. Using the estimated frequency-dependent bulk conductivities, E4D simulated the real and complex electrical potential signals for selected frequencies for SIP. These frequency-dependent bulk conductivities contain information that is relevant to geochemical changes in the system. This study demonstrated that the PFLOTRAN-SIP framework is able to detect the presence of a tracer in the subsurface. SIP offers a significant benefit over ERT in the form of greater information content. It provided multiple datasets at different frequencies that better constrained the tracer distribution in the subsurface. Consequently, this framework allows for practitioners of environmental hydrogeophysics and biogeophysics to monitor the subsurface with improved resolution.

54 ENVIRONMENTAL SCIENCES↗

Full‐dimensional coupled‐channel statistical approach to atom‐triatom systems and applications to H/D + O 3 reaction

Abstract The statistical quantum model (SQM), which assumes that the reactivity is controlled by entrance/exit channel quantum capture probabilities, is well suited for chemical reactions with a long‐lived intermediate complex. In this work, a time‐independent coupled‐channel implementation of the SQM approach is developed for atom‐triatom systems in full dimensionality. As SQM treats the capture dynamics quantum mechanically, it is capable of handling quantum effects such as tunneling. A detailed study of the H/D + O 3 capture dynamics was performed by applying the newly developed SQM method on an accurate global potential energy surface. Agreement with previous ring polymer molecular dynamics (RPMD) results on the same potential energy surface is excellent except for very low temperatures. The SQM results are also in reasonably good agreement with available experimental rate coefficients. The strong H/D kinetic isotope effect underscores the dominant role of quantum tunneling under an entrance channel barrier at low temperatures.

Yang, Dongzheng↗

Visualizing Millisecond Atomic Dynamics of Nanocrystals in Liquid

Atomic structures of nanomaterials are inherently dynamic and continuously reshaped through interactions with chemical species and external stimuli. Such dynamics are further amplified as the size and dimensionality of nanomaterials decrease. Despite advances in analytical methods, it remains challenging to capture the structural dynamics of nanomaterials in reactive environments with both atomic spatial resolution and commensurate temporal resolution. Here, in this study, we directly visualize atomic-scale dynamics of gold (Au) nanocrystals in reactive liquid environments with millisecond-speed liquid-cell electron microscopy (EM) and deep-learning denoising. We uncover reversible fluctuations in the local crystallinity of Au nanocrystals dependent on the surrounding chemical environment. These transient fluctuations, driven by interactions at nanocrystal–liquid interfaces, critically influence the dissolution kinetics and grain boundary relaxation. By overcoming the spatiotemporal limitations in conventional liquid-cell EM, our findings provide insights into how transient nanoscale structures dictate the stability and reactivity of nanomaterials.

Kang, Sungsu [University of Chicago, IL (United St↗

Atomic dynamics of gas-dependent oxide reducibility

Understanding oxide reduction is critical for advancing metal production, catalysis and energy technologies. Although carbon monoxide (CO) and hydrogen (H 2 ) are widely used reductants, the mechanisms by which they work are often presumed to be similar, both involving lattice oxygen removal. However, because of growing interest in replacing CO with H 2 to lower CO 2 emissions, distinguishing gas-specific reduction pathways is critical. Yet, capturing these atomic-scale processes under reactive gas and high-temperature conditions remains challenging. Here we use environmental transmission electron microscopy, which is capable of real-time, atomic-resolution imaging of gas–solid redox reactions to directly visualize the gas-dependent oxide reduction dynamics in NiO. We show that CO drives surface nucleation and the growth of metallic Ni islands, leading to self-limiting surface metallization. Conversely, H 2 activates a coupled surface-to-bulk transformation, where protons from dissociated H 2 infiltrate the oxide lattice to promote the inward migration of surface-generated oxygen vacancies and enabling bulk metallization. By contrast, oxygen vacancies formed by CO remain confined near the surface, where they rapidly form a metallic Ni layer that inhibits further reduction. Furthermore, these results reveal distinct atomistic pathways for CO and H 2 and provide insights that may guide metallurgical processes and catalyst design.

36 MATERIALS SCIENCE↗

Alkali-induced catalytic tuning at metal and metal oxide interfaces

Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.

03 NATURAL GAS↗

Improving the Performance of Integrated Power-Hardware-in-the-Loop and Quasi-Static Time-Series Simulations

This paper introduces a novel multirate cosimulation architecture that overcomes previous challenges integrating faster real-time, microseconds-scale, power-hardware-in-the-loop (PHIL) with larger scale but slower, real-time, seconds-scale, quasi-static time-series (QSTS) simulation. Specifically, an intermediate reduced-equivalent electromagnetic transient (EMT) model duplicates the key power system topology to capture high-speed dynamics and converge hardware-power system interactions between QSTS updates. Exchanging multidimensional parameter vectors (loads, control status, etc.) between the QSTS and EMT models enables capturing the interactions of the rich, high-node-count (thousands of electrical nodes) QSTS model with the hardware. This architecture offers full spatial resolution from QSTS, including individual load dynamics, actual distribution management system controls, and nodal voltages. Simultaneously, the intermediate EMT model provides more detailed high-speed transients of key distributed energy resource hardware interactions. In addition, we use careful PHIL interface design and the exchange of complex power data, rather than current, to further improve performance. This cosimulation architecture is demonstrated by testing a simulated distribution system with an interconnected 500-kVA advanced photovoltaic (PV) inverter in PHIL. In conclusion, the architecture successfully captured PV local volt-volt ampere reactive (volt-VAR) control interactions with the larger network under time-varying electrical and weather conditions.

42 ENGINEERING↗

dynamics of organic-mineral interactions at the metal oxide-solution interface as studied via binding energetics (Final report)

This project focused on addressing longstanding fundamental and experimental uncertainties on how dissolved organic substances (DOS) interact with metal oxide surface under environmentally relevant conditions. By leveraging a custom-built real-time, in-tandem flow adsorption microcalorimetry-UV-Vis/fluorescence spectroscopy platform, we characterized the binding energetics, kinetics and mechanistic pathways driving DOS-metal oxide interactions at temporal resolution on the order of 1-5 seconds. We studied a diverse suite of model organic compounds/substances – including monocarboxylates (e.g. acetate and benzoate), di-carboxylates (oxalate and succinate), amino acids, amino-based nanparticles and natural organic matter – interacting at the mineral-water interface of structurally- and/or chemically distinct metal oxides (including SiO2, boehmite, ferrihydrite, and γ-Al2O3). Our results indicated that DOS-metal oxide interactions are governed by multi-step reaction pathways, often switching between distinct, resolvable enthalpy- and entropy-driven non-electrostatic or electrostatic configurations. To quantify these interactions, we developed and implemented an analytical workflow that integrates peak deconvolution and Monte-Carlo based error propagation to determine site-specific thermodynamic and kinetic parameters for individual binding/debinding events. In addition to resolving apparent first-order rate constants of each event, we were able to quantify associated apparent equilibrium constants as well as free energy, enthalpy and entropy contribution to the activation and subsequent progression of the binding/debinding process across compounds, compound class and metal oxide surfaces. The kinetic-thermodynamic data produced in this study captured how the interplay between oxide surface reactivity and DOS molecular structure jointly drives binding-debinding dynamics. Notably, that at pH below PZC of the oxide surface, neutral species were heavily involved in monocarboxylate binding, while anionic species drove dicarboxylate binding. Also, that among amino acids 1) positional isomers show distinctive binding characteristics to each other while enantiomers show no significant differences in binding characteristics, 2) molecules that bind via outer-sphere complexation show a larger entropic shift between binding and debinding with no impact on oxide surface while 3) inner-sphere interactions increased anion exchange capacity of the oxide surface. The new insights and data from this work has great potential for improving predictive modeling of carbon dynamics and specifically organic-mineral interactions in environmental and industrial systems.

54 ENVIRONMENTAL SCIENCES↗

Solid State Solar Thermochemical Fuel (SoFuel) for Long Duration Storage

Efficient thermal storage systems, when coupled with renewable energy, enable the decarbonization of numerous industrial processes requiring high temperature steam or air, and provide a path for seasonal building heating, especially for colder climates. Existing thermal storage systems face a significant challenge due to losses inherent to all high temperature systems. A viable route to long-term storage is to use thermochemical reactions to convert concentrated solar energy to a fuel that is shelf-stable and can be stored at room temperature, thus eliminating losses associated with high temperature storage. The Solid-State Solar Thermochemical Fuel (SoFuel) technology developed by Michigan State University, Oregon State University, and Mississippi State University provides reactors and processes with minimal sensible heat losses and allows storing solar energy as a solid-state fuel at room temperature for long duration. The production of SoFuel occurs within a cylindrical cavity reduction chemical reactor that captures concentrated solar radiation from a solar field. Reactive magnesium manganese oxide (Mg-Mn-O) resides within the cylindrical cavity chemical reactor and undergoes thermal reduction as the temperature exceeds 1350°C. The thermally reduced Mg-Mn-O pellets (the SoFuel) are cooled down through a recuperative process and stored within a bin until used. The SoFuel can directly supply up to 1100°C heat to an adjacent power plant for electricity generation or industrial heating. Oxidation of SoFuel pellets occurs in a counter flow reactor and supplies heat to the user for electricity generation or industrial processing, after which the fuel is returned to the concentrating solar field where it is regenerated for re-use. Both reactors can be controlled well using a variety of strategies. With the low cost of the material, its cyclability, and the possibility of using the pelletized with on-sun reactors, or with electricity that would be curtailed, this project offers a viable option of medium- and long-term thermal energy storage.

14 SOLAR ENERGY↗