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At least 361 records · Page 20

Stabilizing Graphite Anode in Electrolytes with Nanoscale Anion Networking for High-Rate Lithium Storage

Graphite is the preferred anode material in commercial lithium-ion batteries (LIBs), but its limited compatibility with various organic molecules restricts the electrolyte solvent options. The primary challenge is solvent co-intercalation with Li ions, leading to graphite layer exfoliation. As a result, electrolyte selection often relies on ethylene carbonate (EC)-based solvents. Here, in this study, we introduce electrolytes featuring a nanoscale anion network ordering that hinders the liquid-phase exfoliation of graphite. This network, formed from concentrated long-chain lithium salts, traps free dioxolane (DOL) molecules, reducing the interactions between graphite particles and solvents during Li intercalation. Our findings reveal a mechanism that stabilizes graphite in otherwise unstable solvents with concentrated salts like LiTFSI, providing key insights for improving LIB performance by addressing electrolyte limitations on graphite anodes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Single crystal purification reduces trace impurities in halide perovskite precursors, alters perovskite thin film performance, and improves phase stability

Impurities present in commercially available halide perovskite precursors are known to affect photovoltaic performance. Here, we employ bulk single crystal growth of FAPbI 3 using solvent orthogonality induced crystallization (SONIC) to remove a broad set of extrinsic impurities from commercially available halide perovskite precursors, as verified by detailed chemical analysis. Following SONIC purification, FAPbI 3 films made from PbI 2 of originally low purity (99%) and high purity (99.99%) show improved phase purity and stability under light and heat relative to films made from raw precursors or precursors purified via retrograde powder crystallization (RPC) in 2-methoxyethanol, a method commonly utilized in recent reports of the highest-efficiency perovskite solar cells. In conclusion, single-crystal purification of precursors improves film stability under operational stressors, and the large enhancements in material purity provide a cleaner slate for improved isolation of compositional and additive effects on perovskite phase stability.

14 SOLAR ENERGY↗

Natural Gas Combined Cycle Power Plants with Carbon Capture and Exhaust Gas Recycle

This is a presentation given at the 3rd International Conference on Energy and Environment. The presentation highlights analysis work conducted by NETL to assess the cost and performance for natural gas combined cycle (NGCC) power plants that incorporate solvent-based post combustion carbon dioxide (CO2) capture and exhaust gas recycle (EGR). Increasing the inlet CO2 concentration by EGR is expected to improve the efficiency of the capture system and reduce its cost, however the analysis results show that the cost improvement is minimal as is the cost of capture reduction.

Hackett, Gregory↗

An effective QWBA/UHPLC-MS/tissue punch approach: solving a pharmacokinetic issue via quantitative Met-ID

Methods to provide absolute quantitation of the administered drug and corresponding metabolites in tissue in a spatially resolved manner is a challenging but much needed necessity in pharmaceutical research. Quantitative whole-body autoradiography (QWBA) after a single-dose intravenous (3 mg/kg) and extravascular (30 mg/kg) administrations of an in vitro metabolically stable test compound (structure not reported here) indicated quick tissue distribution and excretion. Good bioavailability and short in vivo half-lives were determined formerly for the same test compound. For closing gaps in the understanding of pharmacokinetic data and in vitro results, radioactive hot spots on whole-body tissue sections had been profiled. Punches from selected tissue regions containing high radioactivity in the tissue sections previously analyzed by QWBA were extracted by a highly organic solvent and analyzed without any consecutive sample preparation step, applying ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) and off-line radioanalysis to maximize signal levels for metabolite identification and profiling. The analysis revealed that the test compound was metabolized intensively by phase I reactions in vivo and the metabolites formed were excreted in bile and in urine. The predominant metabolites showed abundant signal intensities both by MS and by radioanalysis but the MS signal intensities generally underestimated the real abundances of metabolites relative to the unchanged drug. In this work we illustrate that maximizing the sensitivity of tissue punch radioanalysis and the combination with UHPLC-MS leads to a better insight of pharmacokinetic processes by providing quantitative data with high molecular selectivity.

60 APPLIED LIFE SCIENCES↗

Development of Extraction Chromatography Resins for Metal Ion Separations in Analytical Radiochemistry

Extraction chromatography resins are widely used in pretreatment for such as the analysis of radionuclides and metal ions, as well as the quantification of isotopes. These resins have been developed for the purpose of improving selectivity, reducing the generation amount of waste liquid, and performing simpler and faster separation compared with other separation methods such as solvent extraction, ion exchange, and coprecipitation. This paper explains, in an easy-to-understand manner, this extraction chromatography, including extractants, diluents, solid supports, etc. (A.O.)

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Solvent Dynamics in Gel Polymer Electrolytes for Lithium–Sulfur Batteries

Li−sulfur (Li−S) batteries are promising as the next-generation energy storage technology but face challenges due to sluggish sulfur redox reaction (SRR) kinetics and a sulfur shuttling effect. While many studies have explored polycaprolactone (PCL)-based gel polymer electrolytes (GPEs) to address these issues, the influence of solvent properties, including dielectric constant (ϵ) and donor and acceptor numbers (DN and AN), remain unexplored despite their critical impact on performance and full-scale implementation. This study systematically compares three distinct electrolytes, dimethoxyethane (DME), dimethyl sulfoxide (DMSO), and tetraethylene glycol dimethyl ether (TEGDME)-paired with PCL, to correlate the varied solvent properties and their effects on the physical properties of the GPE, in terms of Li + transport and solvation, and polysulfide’s confinement. Among them, the DME-based GPE, with an intermediate DN, exhibited the lowest crystallinity (2.31%), highest ionic conductivity (7.49 mS/cm), and high Li + transference number (0.77). As a result, it achieved a specific capacity of 795 mAh/g sulfur and an average Coulombic efficiency of 97.5% after 120 cycles at C/5, outperforming its competitors. Operando Raman and UV−vis spectroscopy confirmed that PCL effectively confines long-chain polysulfides within its network, mitigating the shuttle effect and facilitating reversible polysulfide conversion. These findings demonstrate that GPEs with moderate DN values and balanced ϵ significantly enhance stability, extend cycle life, and improve rate performance for Li−S batteries. This work provides valuable insights into the design of advanced electrolyte systems for practical energy storage applications.

25 ENERGY STORAGE↗

Durable and Versatile Immobilized Carbonic Anhydrase on Textile Structured Packing for CO 2 Capture

High-performance carbon dioxide (CO 2 )-capture technologies with low environmental impact are necessary to combat the current climate change crisis. Durable and versatile “drop-in-ready” textile structured packings with covalently immobilized carbonic anhydrase (CA) were created as efficient, easy to handle catalysts for CO 2 absorption in benign solvents. The hydrophilic textile structure itself contributed high surface area and superior liquid transport properties to promote gas-liquid reactions that were further enhanced by the presence of CA, leading to excellent CO 2 absorption efficiencies in lab-scale tests. Mechanistic investigations revealed that CO 2 capture efficiency depended primarily on immobilized enzymes at or near the surface, whereas polymer entrapped enzymes were more protected from external stressors than those exposed at the surface, providing strategies to optimize performance and durability. Textile packing with covalently attached enzyme aggregates retained 100% of the initial 66.7% CO 2 capture efficiency over 71-day longevity testing and retained 85% of the initial capture efficiency after 1-year of ambient dry storage. Subsequent stable performance in a 500 h continuous liquid flow scrubber test emphasized the material robustness. Biocatalytic textile packings performed well with different desirable solvents and across wide CO 2 concentration ranges that are critical for CO 2 capture from coal and natural gas-fired power plants, from natural gas and biogas for fuel upgrading, and directly from air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long-term cyclability of Li 4 Ti 5 O 12 /LiMn 2 O 4 cells using carbonate-based electrolytes for behind-the-meter storage applications

Li 4 Ti 5 O 12 /LiMn 2 O 4 (LTO/LMO) chemistry was evaluated as a potential candidate for behind-the-meter storage (BTMS) applications. Its long-term cycle performance at 45 °C was tested using ethylene carbonate (EC) and propylene carbonate (PC) solvent electrolytes. Over 1000 cycles, LTO/LMO cells exhibited ~80% capacity retention and Coulombic efficiency higher than 99.96%. Electrochemical test results showed the major degradation mode of LTO/LMO cells arises from continuous electrolyte decomposition at the LTO anode and loss of Li inventory. EC and PC electrolytes created distinct surface layers, where the EC reduction products were more effective in passivating the LTO electrode surface. Dissolution and migration of Mn from the cathode was probed as Mn 2+ species distributed throughout the surface layer at the anode. By utilizing a prelithiated LTO electrode, the LTO/LMO cell performance was significantly enhanced with EC electrolyte. On the other hand, PC electrolyte resulted in accelerated electrolyte decomposition at the lithiated LTO surface due to the lack of surface passivation. Thus, mitigating parasitic reactions at the LTO electrode is the key to developing successful LTO/LMO cells.

25 ENERGY STORAGE↗

Performance and Economic Evaluation of sCO2 Bottoming Cycles for Natural Gas Combined Cycle Plants with Capture

Natural gas combined cycles (NGCCs) with carbon capture are expected to play a significant role in decarbonization of the power generation sector. NGCC plants generally use triple pressure reheat steam Rankine power cycles for the bottoming cycle. Some studies in the literature have investigated the application of recompression and cascade style supercritical CO2 (sCO2) cycles for NGCC bottoming cycle applications but these studies have focused on power plants without carbon capture. However, NGCC plants fitted with post-combustion solvent-based CO2 capture systems will require a significant amount of steam for solvent regeneration and this can have a major impact on the optimal sCO2 bottoming cycle design. This study investigates the performance and economic potential of sCO2 bottoming cycles for H-class gas turbine based NGCC plants with a post-combustion capture system. A portion of the gas turbine exhaust heat is used for generation of steam required for solvent-based capture system while the rest of the waste heat is utilized in an sCO2 bottoming cycle for power generation. Overall, the performance and LCOE of investigated sCO2 bottoming cycles is similar to that of a state-of-the-art triple pressure reheat steam Rankine cycle. As the gas turbine exhaust temperature increases (beyond 630oC), sCO2 bottoming cycles begin to show greater performance and economic benefits compared to a steam Rankine cycle.

Pidaparti, Sandeep↗

Superior performance enabled by supramolecular interactions in metal-organic cathode: the power of weak bonds

Metal–organic-based electrode materials are increasingly appealing because both metal and organic linker are capable of undergoing redox processes, thus offering a high specific capacity. High porosity which can be achieved by the rational design of these materials is generally perceived as one of the major criteria for high rate performance. However, while Li-ion transport may be possible, oftentimes the counteranions (e.g., PF 6 - ) and solvent molecules are co-inserted into the porous host lattice, potentially hindering Li-ion diffusion pathways. Here, in this study, we propose the concept of close-packed metal–organic cathode stabilized by multiple supramolecular interactions as a viable solution for exceptional electrochemical performance. This is illustrated in a modularly designed redox-active [CuL(Py) 2 ] n (LH 4 = 1,4-dicyano-2,3,5,6-tetrahydroxybenzene, Py = pyridine). The mechanistic studies and DFT calculations confirm that the supramolecular interactions between its close-packed chains are the key to the flexible host lattice which only allows desolvated Li + to intercalate, while these weak bonds also stabilize the inserted Li in the preferred hopping sites, creating optimal diffusion paths. The performance observed in this work is found to be among the best ever reported for metal–organic cathodes with a capacity as high as 255 mA h g -1 at 65 mA g -1 (0.25C) and a reversible capacity of 59 mA h g -1 at ~26 A g -1 (100C) corresponding to 81% retention after 1000 cycles. These findings reveal a potential new strategy towards metal–organic-based electrodes with high performance and enhanced cycling stability.

36 MATERIALS SCIENCE↗

ZeoNet: 3D convolutional neural networks for predicting adsorption in nanoporous zeolites

Zeolites are one of the most widely used materials in the chemical industry due to their nanometer-sized pores that can adsorb and react upon molecules selectively. With hundreds of known framework topologies and hundreds of thousands of computationally predicted structures, the ability to rapidly predict zeolite performance allows researchers to prioritize their efforts on the most promising structures for a given application. Although the accuracy of forcefield-based atomistic simulations has advanced significantly in the past two decades, these simulations can be computationally expensive, especially for long-chain, complex molecules. Here, we present ZeoNet, a representation learning framework using convolutional neural networks (ConvNets) and 3D volumetric representations for predicting adsorption in zeolites. ZeoNet was trained on the task of predicting Henry's constants for adsorption, k H , of n-octadecane in more than 330 000 known and predicted zeolite materials. Employing a 3D grid based on the distances to solvent-accessible surfaces, a volumetric representation that can be generated efficiently, the best-performing ZeoNet achieved a correlation coefficient r 2 = 0.977 and a mean-squared error MSE = 3.8 in ln k H , which corresponds to an error of 9.3 kJ mol -1 in adsorption free energy. In comparison, a model based on hand-designed geometric features has values of r 2 = 0.783 and MSE = 35.7. ZeoNet is also relatively efficient and can process ≈8 structures per second on an Nvidia RTX 2080TI GPU, orders of magnitude faster than forcefield-based simulations. A systematic analysis was conducted to investigate how the choice of ConvNet architectures, the linear dimension (L) and spatial resolution (Δd) of the distance grids, batch size, optimizer, and learning rate impact the model performance. We found that ConvNets based on the ResNet architecture offer the best tradeoff between expressiveness and efficiency. The performance for all models reaches a plateau at L = 30–45 Å and depends less sensitively on grid resolution, with a small benefit around Δd = 0.30–0.45 Å. Finally, saliency maps were visualized to identify which regions of the materials contributed the most to model predictions. It was found, interestingly, that the predictions are driven primarily by the accessible pore volume rather than the region occupied by the framework atoms.

36 MATERIALS SCIENCE↗

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile

Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbonic anhydrase textile structured packing for efficient CO 2 absorption in methyldiethanolamine solvent

Carbonic anhydrase (CA) is an attractive biodegradable catalyst for CO 2 absorption in solvent–based CO 2 capture. However, maintaining the stability of CA as a homogeneous component of the solvents is a challenge. Solvent regeneration temperature typically exceeds the enzyme thermal tolerance, which leads to CA deactivation. To reduce the need for frequent CA replenishment and to avoid inactive CA accumulation in the solvent, this work shows the benefits of an immobilization strategy where CA is fixed in a second–generation design of textile structured packing (CATSP–2) modules. The enzyme–immobilized packing showed 1.5 times better performance in CO 2 separation compared with traditional structured packing with a corresponding increased CO 2 loading in the rich solvent. The modules exhibited good CA activity retention of ~80% during the tests without any CA replenishment. As a result, applying CATSP–2 could potentially decrease the packing height and absorber column size for a lower cost per amount of CO 2 captured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications

Here, we present an update and revision to our 2010 review on the topic of proton- coupled electron transfer (PCET) reagent thermochemistry. Over the past decade, the data and thermochemical formalisms presented in that review have been of value to multiple fields. Concurrently, there have been advances in the thermochemical cycles and experimental methods used to measure these values. This Review (i) summarizes those advancements, (ii) corrects systematic errors in our prior review that shifted many of the absolute values in the tabulated data, (iii) provides updated tables of thermochemical values, and (iv) discusses new conclusions and opportunities from the assembled data and associated techniques. We advocate for updated thermochemical cycles that provide greater clarity and reduce experimental barriers to the calculation and measurement of Gibbs free energies for the conversion of X to XHn in PCET reactions. In particular, we demonstrate the utility and generality of reporting potentials of hydrogenation, E°(V vs H 2 ), in almost any solvent and how these values are connected to more widely reported bond dissociation free energies (BDFEs). The tabulated data demonstrate that E°(V vs H 2 ) and BDFEs are generally insensitive to the nature of the solvent and, in some cases, even to the phase (gas versus solution). This Review also presents introductions to several emerging fields in PCET thermochemistry to give readers windows into the diversity of research being performed. Some of the next frontiers in this rapidly growing field are coordination-induced bond weakening, PCET in novel solvent environments, and reactions at material interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the Long-term Cycle Performance of xLi 2 MnO 3 ·(1-x)LiMeO 2 /Li 4 Ti 5 O 12 Cells via Prelithiation and Electrolyte Engineering

Toward the development of high energy density and long lifetime batteries for behind-the-meter storage (BTMS) applications, Li- and Mn-rich layered oxide cathode (xLi 2 MnO 3 ·(1-x)LiMeO 2 , Me = Ni, Mn, and etc., LMR-NM) and Li 4 Ti 5 O 12 (LTO) anode system was examined. To mitigate the major degradation mechanisms at each electrode (i.e., loss of Li inventory (LLI) at the anode and transition metal dissolution and oxygen release at the cathode), two approaches were taken—prelithiating the LTO electrode and varying the electrolyte solvent compositions. The effect of prelithiation and electrolyte engineering on the long-term cycle performance of LMR-NM/LTO cells were systematically evaluated via electrochemical analyses and post-mortem characterizations. By using a prelithiated LTO anode and supplying additional Li to the system, the capacity retention of LMR-NM/LTO system was improved. The degree of enhancement was dependent on the types of electrolytes used, as their decomposition products determined the level of LLI. With increased capacity retention, however, the cathode was utilized to a greater extent, resulting in more severe loss of the cathode active material. Thus, all degradation mechanisms should be considered comprehensively when designing high performance LMR-NM/LTO cells to account for their complex interplay.

25 ENERGY STORAGE↗

Bypassing sulfides: comparing the morphology and performance of solution processed Cu(In,Ga)Se 2 films prepared via two selenide molecular precursor routes

Solution-processing of thin-film photovoltaics offers an alternative to vacuum-deposition based approaches. The amine–thiol reactive solvent system has become a focal point for the solution-processing of chalcogenide species, owing to the convenience of precursor preparation and comparatively high performance of prepared devices. Selenide species prepared via the amine–thiol route typically progress through a sulfide intermediate phase, and as such are commonly afflicted with sulfur and carbon impurities along- side the presence of a carbonaceous fine-grained layer. Here, two routes of preparing films directly to a selenide phase are examined; first by the co-dissolution of selenium in an amine–thiol solution and second via the novel use of reactive alkylammonium polyselenides. Lamella are cut from these selenide precursor films and final devices, and STEM-EDX and TEM are used to characterize film morphology and secondary phases. A champion device efficiency of 11.2% is reported for the novel polyselenide route, and clear paths of improvement are identified.

36 MATERIALS SCIENCE↗

Surface Doping Boosts Triplet Generation Yield in Perovskite-Sensitized Upconversion

Triplet–triplet annihilation-based photon upconversion (TTA-UC) can efficiently generate higher energy photons at low relative fluences. Bulk metal halide perovskites have offered promise in efficiently sensitizing molecular triplet states in the solid state, necessary for the integration of TTA-UC into device-based applications. Recent work focused on TTA-UC from a rubrene triplet annihilator sensitized by perovskite thin films has established relatively efficient charge extraction from the perovskite, forming the triplet exciton in rubrene. Yet, the specifics underpinning charge transfer at the perovskite/rubrene interface are not fully elucidated. Here, to improve device performance and study the properties governing charge transfer at the interface, various organic solvents are explored to treat the perovskite surface. Scanning tunneling microscopy and spectroscopy show a difference in the electronic band structure, where both n- and p-type terminated perovskite surfaces are observed depending on the solvent used. Supported by optical spectroscopy, the impact of the perovskite electronic structure is monitored, indicating that n-type perovskite sensitizers feature higher TTA-UC efficiencies due to favorable band bending resulting in efficient hole-mediated triplet formation. Overall, the tuning of the electronic structure of the perovskite sensitizer through solvent treatment is shown to be a key force in tuning the mechanism of efficient triplet generation.

36 MATERIALS SCIENCE↗