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At least 1,315 records · Page 73

High Layer Number ( n = 1–6) 2D Ruddlesden–Popper Lead Bromide Perovskites: Nanosheets, Crystal Structure, and Optoelectronic Properties

2D Ruddlesden–Popper (RP) lead halide perovskites have highly tunable structures, compositions, and properties that enable their promising optoelectronic applications. Among various 2D halide perovskites, the materials chemistry and fundamental optoelectronic properties of high layer number (n) lead-bromide RP perovskites, where n refers to the number of inorganic octahedra layers, have been less studied. Here, we report the synthesis of thin nanosheets of (PEA) 2 Cs n–1 Pb n Br 3n+1 (n = 1–6, PEA = phenylethylammonium) perovskites and study the optical properties, assigning photoluminescence emissions of 486, 496, and 505 nm to n = 4–6 phases, respectively, and reporting the photoluminescence lifetimes. Furthermore, the crystal structure of (PEA) 2 Cs 2 Pb 3 Br 10 was determined to reveal minimal octahedral structural distortions. Ultraviolet photoelectron spectroscopy measurements reveal the positioning of the valence and conduction bands for n = 1–3 phases and confirm the type-I band alignment for the (PEA) 2 Cs n–1 Pb n Br 3n+1 series, laying the foundation for rational heterostructure device design in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Techno-economic Analysis and Life Cycle Assessment of Gluconic Acid and Xylonic Acid Production from Waste Materials

Organic acid-based bioleaching has attracted significant research interest for the recovery of rare earth elements(REEs) and other critical metals. Utilizing biologically produced leaching agents, known as biolixiviants, derived from waste materials holds great promise for enhancing the economic viability and environmental sustainability of bioleaching processes. Here this study focuses on the modeling and optimization of biolixiviant production using corn stover (CS), date palm clippings (DP), and nonrecyclable paper (NP). Techno-economic analysis revealed that gluconic acid production from NP is more cost-effective than that from CS and DP, with respective costs of $0.04/kg, $0.06−0.08/kg, and $0.06−0.09/kg of the biolixiviant, yielding gluconic acid concentrations of 135.39, 172.90, and 176.87 mM, respectively. Life cycle assessment demonstrated that biolixiviant production from NP exerts the lowest environmental impact compared with the other evaluated substrates. When applied to the bioleaching of a neodymium−iron−boron magnet swarf, the biolixiviant derived from NP exhibits the highest leaching efficiencies, confirming its cost and environmental competitiveness in comparison to CS and DP

60 APPLIED LIFE SCIENCES↗

Reactive Capture and Conversion of Carbon Dioxide to Methanol with ZnZrO 2 and Alkali-Promoted Mg 3 AlO x Mixed Oxide Catalytic Sorbents

Reactive capture and conversion (RCC) explores the use of a single-unit process to capture CO 2 and produce a product, in this case, methanol (MeOH). In this study, different configurations of a catalytic sorbent (CS) composed of ZnZrO 2 catalyst and Mg 3 AlO x sorbent with and without alkali modification are evaluated for CO 2 adsorption, steady-state catalysis with cofed CO 2 and H 2 , and transient RCC performance. A catalyst composed of a physical mixture of Mg 3 AlO x with ZnZrO 2 resulted in a slight increase in CO 2 uptake, with a low impact on the catalytic activity and RCC of the materials compared to ZnZrO 2 alone. In contrast, Na impregnation significantly increased the level of CO 2 uptake from 0.28 mmol/g (ZnZrO 2 alone) to 0.6 and 1.1 mmol/g for the CS with Na on the catalyst or Mg 3 AlO x , respectively. However, Na impregnation reduced the CO 2 conversion rate and MeOH selectivity during steady-state cofeed experiments at 300 °C and 6 bar. In contrast to steady-state catalysis conditions, RCC, which is a cyclic capture and conversion process, creates dynamic CO 2 and H 2 surface coverages, favoring CH 4 in the early stages of the conversion step and then CO and MeOH as the catalyst CO 2 coverage reduces. The highest MeOH productivity during RCC was achieved with CS that balanced the CO 2 uptake with only moderate catalyst rate reductions caused by Na addition. The optimal material, ZnZrO 2 +10%Na/Mg 3 AlO x , achieved a CO 2 uptake of 0.8 mmol/g and a MeOH productivity of 0.5 mmol/g with 100% selectivity at 260 °C and 6 bar during RCC. This marks the highest RCC MeOH productivity reported to date, although the process needs further optimization and even with optimization, may remain impractical. The results further demonstrate that optimization of catalytic sorbents under steady-state flow conditions does not easily correlate to transient capture and conversion cycles for methanol synthesis from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Similar but Different: Structural and Spectroscopic Characterization of Series of Neodymium, Europium, Americium, and Curium Coordination Complexes

Series of curium, americium, europium, and neodymium complexes with five different polyoxometalate (POM) ligands were structurally and spectroscopically characterized: Na x Cs y H z [M(XW 11 O 39 ) 2 ]· n H 2 O, where M = Nd 3+ , Eu 3+ , Am 3+ , or Cm 3+ and X = B 3+ , Ga 3+ , Si 4+ , Ge 4+ , or P 5+ . This first “serial approach” on transplutonium chemistry was allowed by minimizing the amount of f-element needed per synthesis down to ∼10 μg. This offers a unique opportunity to contrast structural and spectroscopic properties of trivalent actinide with those of lanthanide compounds under identical conditions. The results showcase that although actinide(III) and lanthanide(III) can make isostructural complexes, their solid-state coordination chemistries deviate significantly. The curium and americium compounds were found to be more uniform than their europium and neodymium counterparts, respectively. The particular symmetry of the Cm-POMs also enables the observation of rarely seen emission bands, which hints at vibronic coupling or new emissive pathways. Additionally, the Cm-POM and Eu-POM complexes were characterized via steady-state and time-resolved excitation and emission spectroscopy in solutions containing five different counterions (Li + , Na + , K + , Rb + , or Cs + ), representing 50 combinations of alkali/[M III (XW 11 ) 2 ] n − complexes. The Cm-POMs respond to the alkali counterions by improving symmetry from Li + to Cs + , while the Eu-POMs do the opposite. The luminescence lifetimes of the Cm-POMs also depart from the ideal Kimura equation. Finally, this study provides a rare, and perhaps the most comprehensive, experimental data set comparing heavy actinides and lanthanides via single crystal XRD plus, solution-state, solid-state, and time-resolved emission spectroscopy and demonstrates that lanthanides are only a coarse approximation for actinide elements.

chemical structure↗

Solvent Polarity Independent Symmetry-Breaking Charge Separation in a Slip-Stacked Covalent Terrylene Monoimide Dimer

The design of organic materials capable of efficient photoinduced charge separation in low-polarity environments is a critical challenge for advancing organic photovoltaics. Symmetry-breaking charge separation (SB-CS) offers a promising route to efficient charge separation with minimal energy loss; however, in conventional organic materials this process typically relies on polar solvents to stabilize the charge-separated state. Here, we investigate a slip-stacked terrylene monoimide dimer (TMI 2 ) engineered with intrinsic electronic asymmetry to circumvent this limitation. We demonstrate through a comprehensive suite of ultrafast spectroscopic techniques that TMI 2 undergoes remarkably efficient SB-CS regardless of solvent polarity enabled by the permanent dipole moment of TMI and the accessible intramolecular charge-transfer (ICT) character of its monomer units. Furthermore, analysis of vibronic coherences reveals that the initial state mixing is actively driven by a 193 cm –1 intermolecular mode, while the final SB-CS state is marked by a distinct vibrational fingerprint of the radical ion pair product. Our findings reveal how the intrinsic electronic asymmetry of the TMI monomers that constitute TMI 2 creates an efficient charge separation pathway that precludes the need for external stabilization from a polar solvent. Here, this work establishes a powerful molecular design principle for leveraging intrinsic monomeric asymmetry to achieve efficient charge separation in low-dielectric environments, with significant implications for the development of next-generation organic optoelectronic materials.

Aromatic compounds↗

An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries

Abstract Li metal batteries using Li metal as negative electrode and LiNi 1-x-y Mn x Co y O 2 as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluorinated to generate anion-derived LiF-rich interphases. However, their low ionic conductivities forbid fast-charging. Here, we use CsNO 3 as a dual-functional additive to form stable interphases on both electrodes. Such strategy allows the use of 1,2-dimethoxyethane as the single solvent, promising superior ion transport and fast charging. LiNi 1-x-y Mn x Co y O 2 is protected by the nitrate-derived species. On the Li metal side, large Cs + has weak interactions with the solvent, leading to presence of anions in the solvation sheath and an anion-derived interphase. The interphase is surprisingly dominated by cesium bis(fluorosulfonyl)imide, a component not reported before. Its presence suggests that Cs + is doing more than just electrostatic shielding as commonly believed. The interphase is free of LiF but still promises high performance as cells with high LiNi 0.8 Mn 0.1 Co 0.1 O 2 loading (21 mg/cm 2 ) and low N/P ratio (~2) can be cycled at 2C (~8 mA/cm 2 ) with above 80% capacity retention after 200 cycles. These results suggest the role of LiF and Cs-containing additives need to be revisited.

36 MATERIALS SCIENCE↗

Unravelling ultralow thermal conductivity in perovskite Cs2AgBiBr6: dominant wave-like phonon tunnelling and strong anharmonicity

Abstract Understanding the lattice dynamics and heat transport physics in the lead-free halide double perovskites remains an outstanding challenge due to their lattice dynamical instability and strong anharmonicity. In this work, we investigate the microscopic mechanisms of anharmonic lattice dynamics and thermal transport in lead-free halide double perovskite Cs 2 AgBiBr 6 from first principles. We combine self-consistent phonon calculations with bubble diagram correction and a unified theory of lattice thermal transport that considers both the particle-like phonon propagation and wave-like tunnelling of phonons. An ultra-low thermal conductivity at room temperature (~0.21 Wm −1 K −1 ) is predicted with weak temperature dependence( ~ T −0.34 ), in sharp contrast to the conventional ~T −1 dependence. Particularly, the vibrational properties of Cs 2 AgBiBr 6 are featured by strong anharmonicity and wave-like tunnelling of phonons. Anharmonic phonon renormalization from both the cubic and quartic anharmonicities are found essential in precisely predicting the phase transition temperature in Cs 2 AgBiBr 6 while the negative phonon energy shifts induced by cubic anharmonicity has a significant influence on particle-like phonon propagation. Further, the contribution of the wave-like tunnelling to the total thermal conductivity surpasses that of the particle-like propagation above around 310 K, indicating the breakdown of the phonon gas picture conventionally used in the Peierls-Boltzmann Transport Equation. Importantly, further including four-phonon scatterings is required in achieving the dominance of wave-like tunnelling, as compared to the dominant particle-like propagation channel when considering only three-phonon scatterings. Our work highlights the importance of lattice anharmonicity and wave-like tunnelling of phonons in the thermal transport in lead-free halide double perovskites.

Chemistry↗

Accelerating computational modeling and design of high-entropy alloys

High-entropy alloys, with N elements and compositions {$c_{ν = 1,N}$} in competing crystal structures, have large design spaces for unique chemical and mechanical properties. In this work, to enable computational design, we use a metaheuristic hybrid Cuckoo search (CS) to construct alloy configurational models on the fly that have targeted atomic site and pair probabilities on arbitrary crystal lattices, given by supercell random approximates (SCRAPs) with S sites. Our Hybrid CS permits efficient global solutions for large, discrete combinatorial optimization that scale linearly in a number of parallel processors, and linearly in sites S for SCRAPs. For example, a four-element, 128-site SCRAP is found in seconds—a more than 13,000-fold reduction over current strategies. Our method thus enables computational alloy design that is currently impractical. We qualify the models and showcase application to real alloys with targeted atomic short-range order. Being problem-agnostic, our Hybrid CS offers potential applications in diverse fields.

36 MATERIALS SCIENCE↗

Carboxylate binding prefers two cations to one

Almost all studies of specific ion binding by carboxylates (–COO - ) have considered only a single cation, but clustering of ions and ligands is a common phenomenon. We apply density functional theory to investigate how variations in the number of acetate ligands in binding to two monovalent cations affects ion binding preferences. We study a series of monovalent (Li + , Na + , K + , Cs + ) ions relevant to experimental work on many topics, including ion channels, battery storage, water purification and solar cells. We find that the preferred optimal structure has 3 acetates except for Cs + , which has 2 acetates. The optimal coordination of the cation by the carboxylate O atoms is 4 for both Na + and K + , and 3 for Li + and Cs + . There is a 4-fold coordination minimum just a few kcal mol -1 higher than the optimal 3-fold structure for Li+. For two cations, multiple minima occur in the vicinity of the lowest free energy state. Here we find that, for Li, Na and K, the preferred optimal structure with two cations is favored over a mixture of single cation complexes, providing a basis for understanding ionic cluster formation that is relevant for engineering proteins and other materials for rapid, selective ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sodium trithiocarbonate cathode for high-performance sodium–sulfur batteries

The high abundance and low cost of sodium and sulfur make room-temperature sodium-sulfur (RT Na-S) batteries an attractive technology compared to the current lithium-ion batteries for large-scale grid-storage applications. However, the commercialization of RT Na-S batteries is impeded by the slow kinetics of Na-S chemistry, severe sodium polysulfide shuttling, and uncontrollable growth of dendritic Na. Herein, sodium trithiocarbonate (Na 2 CS 3 ) is applied as a cathode material to facilitate concurrent improvement in both electrodes, leading to a high-rate performance with extended cycle life. The conductive characteristic of the carbon-sulfur resonance bond provides fast ion and electron transfer throughout the cathode, resulting in superior electrochemical reactivity. At the cathode, the presence of Na2CS3 forms an oligomer-structured layer to suppress the dissolution and shuttling of active materials. Meanwhile, when small portions of Na 2 CS 3 intermediates migrate to the anode, a stable solid electrolyte interphase (SEI) layer with uniform Na-ion flux is formed, enabling improved Na stripping and plating performance. A series of electrochemical and materials characterization, accompanied by density functional theory calculations demonstrate that Na 2 CS 3 is a promising candidate to realize high-rate performance long cycle life RT Na-S batteries.

25 ENERGY STORAGE↗

Low thermal conductivity in Bi 8 CsO 8 SeX 7 (X = Cl, Br) by combining different structural motifs

Understanding the structure–property relationships of materials in order to supress thermal conductivity is crucial for developing efficient thermoelectric generators and thermal barrier coatings. Low thermal conductivity materials can often contain a single dominant phonon scattering mechanism. Here, we highlight how combining different structural features into one material can aid in the design and identification of new materials with low thermal conductivities. We synthesise two new mixed-anion materials, Bi 8 CsO 8 SeX 7 (X = Cl and Br), with low thermal conductivities of 0.27(2) and 0.22(2) W m -1 K -1 respectively, measured along their c-axes at room temperature. The Bi 8 CsO 8 SeX 7 materials possess a combination of bond strength hierarchies, Cs + vacancies, and low frequency Cs + rattling. These different features significantly inhibit phonon transport along different crystallographic directions. Due to sharp bond strength contrast between the van der Waals gaps and [Bi 2 O 2 ] 2+ layers, the Bi 8 CsO 8 SeX 7 materials exhibit thermal conductivities <50% of the theoretical minimum when measured along the stacking direction. Conversely, the thermal conductivity associated with the ab-plane is reduced by Cs + rattling when compared to the structurally and compositionally related BiOCl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved lifetime of a high spin polarization superlattice photocathode

Negative Electron Affinity (NEA) activated surfaces are required to extract highly spin-polarized electron beams from GaAs-based photocathodes, but they suffer extreme sensitivity to poor vacuum conditions that results in rapid degradation of quantum efficiency. We report on a series of unconventional NEA activations on surfaces of bulk GaAs with Cs, Sb, and O 2 using different methods of oxygen exposure for optimizing photocathode performance. Additionally, one order of magnitude improvement in lifetime with respect to the standard Cs–O 2 activation is achieved without significant loss of electron spin polarization and quantum efficiency by codepositing Cs, Sb, and O 2 . A strained GaAs/GaAsP superlattice sample activated with the codeposition method demonstrated similar enhancement in lifetime near the photoemission threshold while maintaining 90% spin polarization.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Cesium intercalation of graphene: A 2D protective layer on alkali antimonide photocathode

Alkali antimonide photocathodes have wide applications in free-electron lasers and electron cooling. The short lifetime of alkali antimonide photocathodes necessitates frequent replacement of the photocathodes during a beam operation. Furthermore, exposure to mediocre vacuum causes loss of photocathode quantum efficiency due to the chemical reaction with residual gas molecules. Theoretical analyses have shown that covering an alkali antimonide photocathode with a monolayer graphene or hexagonal boron nitride protects it in a coarse vacuum environment due to the inhibition of chemical reactions with residual gas molecules. Alkali antimonide photocathodes require an ultra-high vacuum environment, and depositing a monolayer 2D material on it poses a serious challenge. In the present work, we have incorporated a novel method known as intercalation, in which alkali atoms pass through the defects of a graphene thin film to create a photocathode material underneath. Initially, Sb was deposited on a Si substrate, and a monolayer graphene was transferred on top of the Sb film. Heat cleaning around 550–600 °C effectively removed the Sb oxides, leaving metallic Sb underneath the graphene layer. Depositing Cs on top of a monolayer graphene enabled the intercalation process. Atomic force microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, low energy electron microscopy, and x-ray diffraction measurements were performed to evaluate photocathode formation underneath the monolayer graphene. Our analysis shows that Cs penetrated the graphene and reacted with Sb and formed Cs 3 Sb.

2D materials↗

Demonstration of thermal limit mean transverse energy from cesium antimonide photocathodes

The mean transverse energy (MTE) of electrons emitted from cathodes is a critical parameter that determines the brightness of electron beams for applications, such as x-ray free electron lasers, particle colliders, and ultrafast electron scattering experiments. Achieving a MTE close to the thermal limit is a key step toward realizing the full potential of electron sources in these applications. Cesium antimonide (Cs 3 Sb) is a technologically important material with a long history of use in photon detection and electron sources. The smallest MTE of electrons photoemitted from Cs 3 Sb has always been appreciably greater than the thermal limit and was attributed to surface non-uniformities. In this work, we present comprehensive measurements of the photoemission electron energy spectra (PEES), quantum efficiency, and MTE from Cs 3 Sb in a wide photoexcitation energy range from 1.5 to 2.3 eV. Our PEES measurements demonstrate a notably low photoemission threshold of around 1.5 eV, which is in contrast with the previously perceived threshold of 1.8–2.0 eV. Moreover, we show that the MTE at this threshold of 1.5 eV nearly converges to the thermal limit at 300 K. At 1.8 eV, the MTE measured is 40 meV, which is comparable to the previously reported value. Here, we conclude that this MTE value at 1.8 eV photon energy is not due to surface roughness effects as previously believed, but is a direct consequence of the excess energy.

43 PARTICLE ACCELERATORS↗

Growth of ultra-flat ultra-thin alkali antimonide photocathode films

Ultra-flat, ultra-thin alkali antimonide photocathodes with high crystallinity can exhibit high quantum efficiency and low mean transverse energy of outgoing electrons, which are essential requirements for a variety of applications for photocathode materials. Here, we investigate the growth of Cs 3 Sb on graphene-coated 4H–SiC (Gr/4H–SiC), 3C–SiC, and Si 3 N 4 substrates. Sb is deposited using pulsed laser deposition, while Cs is deposited thermally and simultaneously. We demonstrate, employing x-ray analysis and quantum efficiency measurements, that this growth method yields atomically smooth Cs 3 Sb photocathodes with a high quantum efficiency (>10%), even in the ultra-thin limit (<30 nm). For the Si 3 N 4 substrate, film growth is shown to be polycrystalline, while films grown on Gr/4H–SiC show a high degree of ordering with signs of epitaxy.

36 MATERIALS SCIENCE↗

Demonstration of closed shell breeding of cesium ions with an electron beam ion source

An electron beam ion source serves as a charge breeder for the Californium Rare Isotope Breeder Upgrade (CARIBU) at the Argonne Tandem Linac Accelerator System (ATLAS). The source accepts radioactive beams of 1+ or 2+ ions and raises their charge state for post-acceleration by ATLAS. The efficiency of this process impacts the length of each experiment and, hence, the type and number of experiments that can be run in each program cycle. Recent efforts to improve the charge breeding efficiency for the 80 < A < 160 species typical of CARIBU have focused on utilizing the closed shell breeding technique. Here, with this technique, the electron beam energy is manipulated to take advantage of the large gap in ionization energies at shell closures and selectively populate a single charge state. Charge breeding studies with stable cesium ions have demonstrated an absolute efficiency of 72% for Cs 27+ and a total efficiency of 93%. The Cs 27+ efficiency result represents a factor of 3 improvement over the previous best charge breeding result of 23% for Cs 27+ .

Vondrasek, R. [Argonne National Laboratory (ANL), ↗

Quantum scattering of HC 5 N and para -H 2 on a new potential energy surface

In the interstellar medium (ISM), non-local thermodynamic equilibrium situations are common due to low density, and one needs to consider the effect of molecular collisions in order to interpret the observations. Among the species detected in the ISM, cyanopolyynes, with the general molecular formula HC 2n+1 N (n = 1, 2, …), are characterized by large dipole moments and small rotational constants and constitute an indispensable class of candidates for the sensitive tracers of local density and temperature. We present a study of the collisional (de-) excitation of HC 5 N by para -H 2 (p-H 2 ) in its ground rotational state, namely HC 5 N ( j 1 ) + H 2 ( j 2 = 0) → HC 5 N (j$_1^′$) + H2 (j$_2^′$ = 0), where j 1 (or j$_1^′$) and j 2 (or j$_2^′$) denote the initial (or final) rotational quantum numbers of HC 5 N and H 2 , respectively. We performed the quantum scattering calculations at low collision energy using a new four-dimensional ab initio potential energy surface. In the regime where p-H 2 remains in its rotational ground state, converged cross sections did not require including excited rotational states of p-H 2 in the rotational basis. State-to-state cross sections were computed by means of the quantum-mechanical close-coupling (CC) method and the coupled states (CS) approximation, and rate coefficients for the first 61 levels of HC 5 N were computed for the first time up to 20 K with the CC approach and up to 50 K with the CS method. CC and CS results were found to agree well at temperatures up to 20 K. Finally, these data should allow a more accurate derivation of the HC 5 N abundance in molecular clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water content modulation enables selective ion transport in 2D MXene membranes

Separation membranes are critical for a range of processes, including but not limited to water desalination, chemical and fuel production, and recycling and recovery applications. Fundamentally, there are intrinsic trade-offs between permeability and selectivity. Local water organization and content can impact membrane structure (short- and long-range) in laminar transition metal carbide (MXene) membranes and impact selective ion permeation. Intercalation of chaotropic cesium (Cs + ) ions within the layers reduces the water content in the membrane and at the surface which cannot be found in the intercalation of other ions. Additionally, 3D imaging using focused ion beam scanning electron microscopy showed fewer defects in the Cs-MXene membrane, due to reduced local water content, leading to more efficient ion sieving. X-ray diffraction and density functional theory calculations on the nanochannel structure demonstrated that the chaotropic ion results in the smallest nanochannel size and induces a stronger resistance to water-induced nanochannel swelling. With a narrower nanochannel, the Cs-MXene membrane limits ion transport pathways, resulting in more selective transport of lithium over other metal cations, as evidenced in both experiment and molecular dynamics simulations. In conclusion, our findings highlight the potential for controlling the structural organization of 2D MXene membranes to enable on-demand transport of ions for diverse applications.

36 MATERIALS SCIENCE↗