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At least 19 records

Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form

This study demonstrates the conversion of simulated pyroprocessing salt wastes [i.e., ER(SF) and ERV2] into chemically durable iron phosphate glass waste forms through reactions with ammonium hydrogen phosphate precursors [i.e., NH4H2PO4 and (NH4)2HPO4] and added Fe2O3. The reaction of the salt simulants with the phosphate precursors resulted in dehalogenation of the salt through the production of NH4Cl and NH4I (along with water), of which the NH4Cl can be used to produce UCl3 oxidant for use in the electrorefiner during pyroprocessing. These iron phosphate glasses contain a notably higher waste loading than the baseline glass-bonded sodalite ceramic waste form, which requires about 70 vol% sodalite to accommodate Cl from the salt, because they are dehalogenated prior to vitrification. The high waste loadings coupled with higher bulk densities (~3×103 kg/m3) than glass-bonded sodalite (~2.3×103 kg/m3) mean that these glasses have a higher storage volume, i.e., the volume required to immobilize a given mass of waste. The iron phosphate glass waste forms were characterized using a variety of techniques including physical property measurements and chemical durability testing. Following initial testing, a proof-of-concept demonstration was conducted to show that the NH4Cl generated from this process could be used to produce UCl3 using depleted uranium dendrites as a feedstock.

phosphate glass, pyroprocessing, waste forms, salt↗

Expanding the Cage of 2D Bromide Perovskites by Large A-Site Cations

Two-dimensional (2D) halide perovskites have outstanding optoelectronic properties, and they feature a variety of organic cation spacers and cage A-site cations that can be incorporated into their structures. It has recently been reported that the Goldschmidt tolerance factor can be relaxed and expanded in iodide 2D perovskites. Bromide 2D perovskites, whose multilayer structures and optical properties are much less studied, provide a great platform for studying structure-property relationships for 2D perovskites with large Asite cations. Herein, we report the synthesis and structure of three new 2D bromide perovskites-(BA)(2)(MHy)(2)Pb3Br10 (BA, butylammonium; MHy, methylhydrazinium), (BA)(2)(EA)(2)Pb3Br10 (EA is ethylammonium), and (BA)(2)(DMA)Pb2Br7 (DMA is dimethylammonium). We compared them with other 2D perovskites with different A-site cations but with the same spacer and layer thickness. Single-crystal structures show that the Pb-Br bonds are elongated to accommodate the large A-site cations. Additionally, the octahedra in (BA)(2)(MHy)(2)Pb3Br10 and (BA)(2)(EA)(2)Pb3Br10 are highly distorted, and their different stacking patterns of the inner and outer layers lead to the formation of the n = 3 phases. Density functional theory calculations show that 2D perovskites with larger A-site cations (e.g., DMA, MHy, and EA) have smaller band dispersions and larger effective masses than those with Cs+ and MA. (BA)(2)(MHy)(2)Pb3Br10 also exhibits one of the largest Rashba splittings in the literature. Structures with large cage cations also exhibit high band gaps within the same n number and short photoluminescence (PL) lifetimes. Temperature- and power-dependent PL measurements reveal that the broad shoulder in the PL peak originates from the trap states.

Emission↗

Reducing Surface Recombination Velocity of Methylammonium-Free Mixed-Cation Mixed-Halide Perovskites via Surface Passivation

We control surface recombination in the mixed-cation, mixed-halide perovskite, FA0.83Cs0.17Pb(I0.85Br0.15)3, by passivating nonradiative defects with the polymerizable Lewis base (3-aminopropyl)trimethoxysilane (APTMS). We demonstrate average minority carrier lifetimes >4 µs, nearly single exponential monomolecular photoluminescence decays, and high external photoluminescence quantum efficiencies (>20%, corresponding to ~97% of the maximum theoretical quasi-Fermi-level splitting) at low excitation fluence. We confirm both the composition and valence band edge position of the FA0.83Cs0.17Pb(I0.85Br0.15)3 perovskite using multi-institutional, cross-validated, X-ray photoelectron spectroscopy and UV photoelectron spectroscopy measurements. We extend the APTMS surface passivation to higher bandgap double-cation (FA and Cs) compositions (1.7, 1.75, and 1.8 eV) as well as the widely used triple-cation (FA, MA, and Cs) composition. Finally, we demonstrate that the average surface recombination velocity decreases from ~1000 to ~10 cm/s post APTMS passivation for FA0.83Cs0.17Pb(I0.85Br0.15)3. Our results demonstrate that surface-mediated recombination is the primary nonradiative loss pathway in many methylammonium (MA)-free mixed-cation mixed-halide films with a range of different bandgaps, which is a problem observed for a wide range of perovskite active layers and reactive electrical contacts. Our study also provides insights to develop passivating molecules that help reduce surface recombination in MA-free mixed-cation mixed-halide films and indicates that surface passivation and contact engineering will enable near-theoretical device efficiencies with these materials.

14 SOLAR ENERGY↗

Cation–polymer interactions and local heterogeneity determine the relative order of alkali cation diffusion coefficients in PEGDA hydrogels

Current research efforts are focused on endowing polymer membranes with ion–ion selectivity by incorporating ion–polymer interactions into materials to bias the selective partitioning and or diffusivity of one species over another. However, little is known about the impact of such interactions on the mechanisms of ion transport. In this study, we probe the influence of cation–polymer interactions on cation, anion, and salt diffusivity in a model membrane material, poly(ethylene glycol) diacrylate (PEGDA) by modeling concentrated polyethylene oxide solutions via molecular dynamics simulations. These results are compared to published experimental data for LiCl, NaCl, and KCl diffusion in PEGDA. Experimentally, the order of salt and cation diffusion coefficients for LiCl, NaCl, and KCl deviate from the order in aqueous solutions. Here, simulations identify these deviations to arise from cation–polymer coordination in the membrane. Both the fraction of bound cations and the average binding lifetime increases with decreasing cation hydration free energy (moving down the alkali series), leading to different diffusivity trends in the membrane compared to solution. However, to recover the experimentally observed order of diffusivities cations and salt in our simulations, we needed to incorporate membrane heterogeneity explicitly via a polymer charge scaling procedure. Together, our results indicate that cation–polymer interactions, as well as spatial heterogeneity within the membrane, play a critical role in dictating the observed order of alkali cation and salt diffusion coefficients in membranes.

36 MATERIALS SCIENCE↗

Understanding the Effect of Single Atom Cationic Defect Sites in an Al 2 O 3 (012) Surface on Altering Selenate and Sulfate Adsorption: An Ab Initio Study

Adsorption is a promising under-the-sink selenate remediation technique for distributed water systems. Recently it was shown that adsorption induced water network rearrangement control adsorption energetics on the α-Al 2 O 3 (012) surface. Here, we aim to elucidate the relative importance of the water network effects and surface cation identity on controlling selenate and sulfate adsorption energy using density functional theory calculations. Density functional theory (DFT) calculations predicted the adsorption energies of selenate and sulfate on nine transition metal cations (Sc–Cu) and two alkali metal cations (Ga and In) in the α-Al 2 O 3 (012) surface under simulated acidic and neutral pH conditions. We find that the water network effects had a larger impact on the adsorption energy than the cationic identity. However, cation identity secondarily controlled adsorption. Most cations decreased the adsorption energy, weakening the overall performance, the larger Sc and In cations enabled inner-sphere adsorption in acidic conditions because they relaxed outward from the surface, providing more space for adsorption. Additionally, only Ti induced Se selectivity over S by reducing the adsorbing selenate to selenite but not reducing the sulfate. Altogether, this study indicates that tuning water network structure will likely have a larger impact than tuning cation–selenate interactions for increasing adsorbate effectiveness.

Adsorption↗

Suppressing Cation Migration in Triple-Cation Lead Halide Perovskites

Ion migration represents an intrinsic instability of metal halide perovskite solar cells. In this work, we show that triple-cation FA x MA y Cs 1–x–y PbI 3 [FA + = (NH 2 ) 2 CH + , MA + = CH 3 NH 3 + ] active layers with mixed orthorhombic, post-perovskite (δ ortho -CsPbI 3 ), and cubic perovskite (α) phases (i.e., α/δ-phase FA x MA y Cs 1–x–y PbI 3 ) exhibit improved cation stability against applied bias relative to pure α-phase perovskites (i.e., FA 0.85 Cs 0.15 PbI 3 and FA 0.76 MA 0.15 Cs 0.09 PbI 3 ). Infrared photothermal heterodyne imaging and time-of-flight secondary ion mass spectrometry are used to visualize exclusive α-phase perovskite lateral device A + cation accumulation (depletion) at perovskite negative (positive) electrode interfaces. The resulting compositional heterogeneities lead to degradation. Operational stability testing of solar cells reveals similar degradation behavior; α/δ-phase FA x MA y Cs 1–x–y PbI 3 lateral devices/solar cells, by contrast, show improved stabilities. Enhanced α/δ-FA x MA y Cs 1–x–y PbI 3 stability is rationalized by δortho-phase inclusions, acting as barriers through which A + cations do not easily migrate. This study thus provides new insights into cation migration in FA x MAyCs 1–x–y PbI 3 perovskites and suggests a materials design strategy toward suppressing cation instabilities in hybrid perovskites.

14 SOLAR ENERGY↗

Tuning the Cation–Anion Interactions by Methylation of the Pyridinium Cation: An X-ray Photoelectron Spectroscopy Study of Picolinium Ionic Liquids

Here, X-ray photoelectron spectroscopy is used to investigate the impact of methylation on the electronic environment of pyridinium cations. Because of the electron-donating effect of the methyl group, there is a significant increase in electron density on the cationic nitrogen. The shift of the N 1s binding energy is inversely proportional to the anion basicity. The methylation position on the electronic environment of the cationic nitrogen is investigated. The N 1s binding energy follows the trend: 1-octylpyridinium > 1-octyl-3-picolinium > 1-octyl-4-picolinium > 1-octyl-2-picolinium, which is in good agreement with the cation acidity. The increase in the inductive effect subsequently weakens the cation–anion interactions through charge transfer from the anion to the cation, causing a subtle change in the electronic environment of the anion. Such an effect is noticeably reflected in the Br 3d binding energy. It shows that the Br 3d 5/2 binding energy of 1-octyl-2-picolinium bromide is 0.2 eV lower than that of 1-octylpyridinium bromide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dehydration of Methyl Lactate on Alkali Cation-Exchanged Faujasite: Effects of Metal Cation Identity and Water Pressure

Turnover rates for the catalytic dehydration of methyl lactate (ML) over ion-exchanged faujasite (FAU) catalysts depend on the identity of alkali metal cations (Na + , K + , Cs + ) and local solvation effects. Analysis of rate measurements and in situ infrared spectroscopy gives evidence that the reaction involves kinetically relevant dissociation of adsorbed methyl lactate upon alkali metal cations. This process involves concerted methyl transfer to the surface and dissociation of the alkali metal from the framework, which occurs at cationic active sites that remain predominantly unoccupied under relevant conditions (0.5–10 kPa ML, 0.5–15 kPa H 2 O, 563–583 K). Despite the mechanistic similarities, apparent activation enthalpies (ΔH app ‡ ) decrease linearly (47 kJ mol –1 from Na + to Cs + ) with ionization energy and cationic radius, and apparent activation entropies (ΔS app ‡ ) decrease 74 J mol –1 K –1 . These trends reflect electrostatic interactions that stabilize the cations to the anionic sites on the zeolite: stronger association between these charges leads to increasingly endothermic processes to displace the alkali metal to form a cationic methoxy and an intrapore metal lactate intermediate. Water physisorption measurements suggest alkali metal ions bind superstoichiometric quantities of water within FAU pores, and in situ infrared spectra suggest the concerted adsorption of ML requires reorganization of this water. Consequently, these processes introduce entropic gains that partially offset entropy losses associated with ML adsorption. Hence, turnover rates differ only by a factor of 2 among Na-, K-, and Cs-FAU at 573 K (ΔΔG app ‡ = 5 kJ mol –1 ). These findings demonstrate the interplay of alkali metal ions with zeolite active sites and intrapore water clusters for ML dehydration, indicating that these interactions can be leveraged to deliver optimal performance under different reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cation–Ligand Interactions Dictate Salt Partitioning and Diffusivity in Ligand-Functionalized Polymer Membranes

Membranes are an attractive alternative to current thermal separations due to their scalability and energy efficiency in desalinating water. Unfortunately, many of the conventional membrane materials available today are unable to differentiate between ionic solutes, especially alkali cations, compromising their use in ion–ion separations. Inspired by the ion-specific interactions exhibited by biological ion channels, recent research efforts have focused on synthesizing and characterizing new polymeric materials that incorporate ligands into polymer networks to bias solubility and/or diffusivity of one cationic species over another. Despite these efforts, little is known about the influence of incorporating ligands into polymer membranes on solubility and diffusivity of the complexing species. In this study, we first build a qualitative model of salt partitioning, diffusivity, and permeability in generic cation-complexing ligand-functionalized polymer membranes. Next, to validate our model and hypotheses, we perform atomistic molecular dynamics simulations of a 12-crown-4-functionalized membrane in the presence of alkali halide salts at low concentration. Generally, cation complexation enhances cation solubility but decreases diffusivity. Interestingly, the reduction in diffusivity is predicted to be larger than the enhancement in solubility for materials which operate by the mechanisms proposed in our physical picture, ultimately resulting in a reduction in the permeability of the selectively complexing ion.

36 MATERIALS SCIENCE↗

Role of Cations in the Cation-Driven Assembly Process and their Effect on the Charge Storage Properties of Bilayered Vanadium Oxide and Reduced Graphene Oxide Heterostructures in Alkali Ion Systems

Exfoliated δ-Li x V 2 O 5 ·nH 2 O (ex-LVO) and reduced graphene oxide (rGO) heterostructures were constructed using different assembling cations (i.e., Li⁺, Na⁺, and K⁺ ions). The ex-LVO and rGO nanoflakes were stacked together using a concentrated chloride solution of each assembling cation and vacuum annealed at 200 °C to form three distinct two-dimensional (2D) layered architectures. X-ray diffraction and thermogravimetric analysis confirmed that the assembling ions can control the interlayer spacing of the bilayered vanadium oxide (BVO) phase as well as impact the crystallographic water content, which in turn affects the electrochemical performance. Scanning electron microscopy, scanning transmission electron microscopy (STEM), electron energy-loss spectroscopy (EELS), and X-ray photoelectron spectroscopy confirmed that a 2D heterointerface formed between LVO and rGO and that the cations used to assemble the heterostructure are trapped in the interlayer BVO region. High-resolution STEM imaging also showed the rGO dispersion throughout the LVO layers. Moreover, STEM-EELS identified a V 2 O 3 phase that forms along the rGO interface and can stabilize the materials during cycling. A charge storage mechanism analysis, combined with the galvanostatic intermittent titration technique, found that increased interlayer spacings of the BVO phase and using the assembling cations to define intercalation sites for identical charge-carrying ions lead to improved ion diffusion and increased capacities during cycling. Therefore, the Li⁺ and Na⁺ ion assembled heterostructures showed improved charge-carrying ion diffusion and charge storage capacities in each of their respective charge storage systems (i.e., Li-ion and Na-ion half-cells). In total, the cation used for heterostructure assembly can modify the final material structure and tailor the ion diffusion and charge storage capacity to tune its properties for the desired electrochemical system using a variety of 2D materials.

25 ENERGY STORAGE↗

Thermodynamic consequences of Tyr to Trp mutations in the cation–π-mediated binding of trimethyllysine by the HP1 chromodomain

Evolution has converged on cation–p interactions for recognition of quaternary alkyl ammonium groups such as trimethyllysine (Kme3). While computational modelling indicates that Trp provides the strongest cation–p interaction of the native aromatic amino acids, there is limited corroborative data from measurements within proteins. Herein we investigate a Tyr to Trp mutation in the binding pocket of the HP1 chromodomain, a reader protein that recognizes Kme3. Binding studies demonstrate that the Trpmediated cation–p interaction is about -5 kcal mol -1 stronger, and the Y24W crystal structure shows that the mutation is not perturbing. Quantum mechanical calculations indicate that greater enthalpic binding is predominantly due to increased cation–π interactions. NMR studies indicate that differences in the unbound state of the Y24W mutation lead to enthalpy–entropy compensation. These results provide direct experimental quantification of Trp versus Tyr in a cation–π interaction and afford insight into the conservation of aromatic cage residues in Kme3 reader domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

IPL-Annealed Mixed-Cation Perovskites with Robust Coating Window toward Scalable Manufacturing of Commercial Perovskite Solar Cells

Perovskite solar cells (PSCs) are a promising alternative solar technology, but the technical challenges of (1) stability/durability, (2) efficiency at scale, and (3) manufacturability must be overcome to achieve widespread PSC commercialization. The challenge of balancing solution ink formulation and scalable manufacturing is often overlooked in the literature, where focus is on adopting inks from processes that will not scale. In this study, we apply a classical roll-to-roll manufacturing perspective, utilizing both compositional engineering and intense pulsed light (IPL) annealing, to develop a mixed-cation perovskite ink with a robust coating window that simultaneously solve issues of stability and manufacturability for PSCs. Our method resulted in blade-coated, flexible, mixed-cation PSCs on ITO-PET substrates with a champion power conversion efficiency (PCE) efficiency of 16.7% using IPL annealing of the absorber layer and, to our knowledge, is one of the fastest processing methods for the perovskite layer. This overall reduction in processing time with a stable ink represents an advance toward the scaled production of perovskite solar cells on flexible substrates.

flexible perovskite solar cells↗

Fluorination effect for stabilizing cationic and anionic redox activities in cation-disordered cathode materials

We see that cation-disordered Li-excess cathodes with oxygen redox reactions are promising candidates for high-energy-density Li ion batteries. Nevertheless, the oxygen redox process that is required for the high capacity often comes with the oxygen loss, which leads to severe capacity degradation and voltage decay. In this work, we have successfully synthesized a series of Li-excess cation-disordered cathodes (Li 1.2 Mn 0.4+x Ti 0.4-x O 2-x Fx) (0 ≤ x ≤ 0.2) with different fluorine (F) contents. The electrochemical performance results show that the Li 1.2 Mn 0.55 Ti 0.25 O 1.85 F 0.15 (LMTOF0.15) exhibits the highest reversible capacity (275 mAh g -1 , under 30 mA g -1 ), cyclability, and voltage retentions. The mapping of resonant inelastic X-ray scattering (mRIXS) and differential electrochemical mass spectroscopy (DEMS) results reveal that the fluorination enhances the reversible lattice oxygen redox reaction while suppressing irreversible gas release and surface reactions. The X-ray Absorption Spectroscopy (XAS) during the initial two cycles shows that F-substitution alleviates the reduction of the Mn valence state during the whole (dis)charge processes in the bulk and at the surface of the material, results in higher average discharge voltage. In addition, the introduction of F improves the structural stability and suppresses local lattice distortion of the material. Therefore, LMTOF 0.15 is able to cycle with smaller polarization, less interfacial side reaction and Mn dissolution, and therefore results in enhanced cyclability. This work provides a comprehensive understanding of the fluorination effect on the cationic and anionic redox activities in cation-disordered Li-excess cathodes.

25 ENERGY STORAGE↗

Comparative Study of Neutral and Cationic Sn 2 H 2 : Toward Laboratory Detection of the Cation

Group 14 M 2 H 2 isomers (M = Si, Ge, Sn, and Pb) have attracted interest due to their radically differing electronic structures from acetylene. To better understand the Sn–H interactions of the neutral and cationic Sn 2 H 2 structures, we present the most rigorous study of these systems to date. CCSD(T)/cc-pwCVTZ harmonic frequencies are presented as the first predictions for the neutral and cationic species to date. CCSDT(Q)/CBS relative energies are reported using the focal point approach, confirming the butterfly isomer as the global minimum on the potential energy surface for both the neutral and cationic species. In all, there exist 7 minima and 15 transition states. NBO analysis is also performed to elucidate the changes in bond order going from neutral to cation across all isomers of Sn 2 H 2 . Our results provide insights into the important Sn–H interaction and provide guidance for future work that may detect Sn 2 H$^{+}_{2}$ in the laboratory for the first time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation

Here, we provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high-accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring-opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered. These findings are discussed in light of the early predictions by Longuet-Higgins alongside Woodward and Hoffman; we also propose a simple phase space explanation for the appearance of the cyclopropyl photoionization spectrum. The results of this work allow the refinement of the cyclopropane C–H bond dissociation energy, in addition to the cyclopropyl radical and cation cyclization energies, via the Active Thermochemical Tables approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Guidelines for Making, Interpreting, and Quantifying Activity Measurements of Molten Salts Containing Mixed Cations and Anions Using Cation-Based Electrodes by Electromotive Force

Measurements of thermochemical properties in molten salt electrolytes with mixtures of cations and anions are difficult to interpret. Electromotive force measurements of salts containing common anions were driven by the least stable anion compound (e.g., LiCl in LiCl-KCl), while measurements in common cation salts were driven by the most noble anion half-cell reaction (e.g., F − /F 2 in LiCl-LiF). Measurements in mixed cation and anion salts were driven by the least stable anion compound for the most noble anion half-cell reaction (e.g., KF in KCl-LiF). These guidelines enable quantification of the activity of electroactive species in salts containing multiple cations or anions.

Lichtenstein, Timothy [Argonne National Laboratory↗

Controlling Cation-Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

The chemistry of linear uranyl(V/VI) dioxo cations, [O yl –U–O yl ] +/2+ , is dominated by coordination of uranium in the equatorial plane. Effects of this constraint were evaluated by experiment and theory for gas-phase mixed-valence U V/VI coordination dimers in which uranyl moieties are linked by alkyl dicarboxylates, [(UO 2 + )(UO 2 2+ )(OOC-(CH 2 ) n-2 -COO 2– ) 2 ] – (n = 3–12). Faster O 2 -addition to dimers with short linkers n = 3 and 4, vs. n ≥ 5, suggests a structural difference. Computed structures with the shortest linkers have bridging dicarboxylates and nearly parallel, non-interacting uranyls. Longer linkers, n = 5–7, accommodate uranyl orientations with distinct U V –U VI end-on cation-cation interactions (CCIs), whereby Lewis base O yl from U V coordinates to the acid U VI , denoted as U V O yl ···U VI . The dimer structure for n = 8 has a U V –U VI side-on diamond-shape CCI, with U V O yl ···U VI and U VI O yl ···U V interactions. Addition of O 2 to the n = 4 and 5 dimers yields [(UO22+)2(OOC-(CH2)n-2-COO2–)2(O2–)]–, with U V oxidized to U VI and O 2 reduced to O 2 – . Whereas O 2 can associate to and oxidize the exposed U V center for dimers with n = 3 and 4, the more crowded U V site in the CCI structures inhibits O 2 addition. Finally, the results demonstrate rational structural control of uranyl-uranyl bonding and reactivity in small coordination complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗