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An Artificial Protective Coating toward Dendrite-Free Lithium-Metal Anodes for Lithium–Sulfur Batteries
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Mesoporous Organosilica Nanoparticles with Internal Metal–Chelating Groups: Transition Metal Uptake and Gd 3+ Relaxivity
We prepared novel mesoporous organosilica nanoparticles with internal metal-chelating diethylenetriametetraacetic acid groups (DTTA-MSNPs) by co-condensation and decorated them with fluorescent moieties. Here, we studied the binding of transition metal ions such as copper(II), cobalt (II) and gadolinium (III) by DTTA-MSNPs, and found high uptake of these metals. In particular, DTTA-MSNPs uptake ~1.1×10 5 Gd 3+ per particle and possess a high r 1 relaxivity of 15.27 mM –1 s –1 . Thus, DTTA-MSNPs may find applications in metal sequestration and in MR imaging and neutron capture therapy.
Efficient electrochemical CO[subscript 2] reduction to CO by metal and nitrogen co-doped carbon cata
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Metal-Centered Photoredox Catalysis using d 6 Transition Metal-based Chromophores
Controlling excited-state reactivity in transition metal chromophores is central to light-driven chemistry, with applications spanning from solar energy conversion to photoredox catalysis. Ru(II) and Ir(III) chromophores currently dominate applications within this field due to their long-lived charge-transfer (CT) excited states, which support bimolecular electron transfer chemistry. However, their elemental scarcity and relative lack of selectivity for differentiating oxidative versus reductive pathways has in part motivated the exploration of alternative platforms that could, in principle, offer distinct mechanistic opportunities. Earth-abundant, valence-isoelectronic 3d 6 complexes of Fe(II) and Co(III) have attracted significant attention due to their electronic similarity to Ru(II) and Ir(III), suggesting the potential for complementary photophysical behavior. In contrast to their heavier congeners, however, the weaker ligand fields of first-row transition metals promote rapid relaxation from initially populated CT states to low-lying metal-centered (MC) excited states, typically of 5 T 2 or 3 T 1 character. Because these MC states involve redistribution of electron density within MC d-orbitals rather than charge separation between metal and ligand orbitals, they were historically considered poor candidates for use in photochemical transformations.
Predicting a Key Catalyst-Performance Descriptor for Supported Metal Nanoparticles: Metal Chemical Potential
The chemical potential of metal atoms in supported nanoparticles provides a convenient descriptor of their performance as heterogeneous catalysts that captures the effects of particle size, support and alloying. Based on microcalorimetric measurements, the chemical potential is shown in this work to be predictable as a function of monometallic particle diameter and the adhesion energy of the particle to the support, and, for oxide supports, this adhesion energy correlates predictably with metal oxophilicity. These correlations provide predictions of metal chemical potential that can enable catalyst design. They also suggest an improvement in the Gibbs-Thomson relation for free-standing nanoparticles, whether metals or molecular solids.
Enhanced Activity in Layered Metal-Oxide-Based Oxygen Evolution Catalysts by Layer-by-Layer Modulation of Metal-Ion Identity
Few-layered potassium nickel and cobalt oxides show drastic differences in catalytic activity based on metal ion preorganization. Uniform compositions [(CoO 2 /K) 6 or (NiO 2 /K) 6 ] show limited activity, while homogeneously mixed-metal cobalt/nickel oxides [(Co n Ni (1–n) O 2 /K) 6 ] display moderate improvement. However, a layer-by-layer arrangement of alternating cobalt and nickel oxide sheets [e.g., (CoO 2 /K/NiO 2 /K)] provides superior catalytic performance, reducing the oxygen evolution overpotential by ∼200–400 mV. Density functional theory simulations provide an illustration of the electronic properties (density of states and localization of orbitals) that promote catalysis in the layer-segregated materials over those of homogeneous composition. This study reveals that atomic preorganization of metal ions within layered catalysts plays a more crucial role than the overall metal composition in enhancing catalytic efficiency for oxygen evolution.
Crystallographic Mapping and Tuning of Water Adsorption in Metal–Organic Frameworks Featuring Distinct Open Metal Sites
Crucial steps toward designing water sorption materials and fine-tuning their properties for specific applications include precise identification of adsorption sites and establishment of rigorous molecular-level insight into the water adsorption process. We report stepwise crystallographic mapping and DFT computations of adsorbed water molecules in ALP-MOF-1, a metal-organic framework decorated with distinct open metal sites and carbonyl functional groups that serve as water anchoring sites for seeding the nucleation of a complex water network. Identification of an unusual water adsorption step in ALP-MOF-1 motivated the tuning of metal ion composition to carefully adjust water uptake. These studies provide direct evidence that the identity of the open metal sites in MOFs can dramatically affect water adsorption behavior between 0 and ~20% RH and that multiple proximal water anchoring sites along the MOF skeleton facilitate water uptake steps which could be potentially useful for applications requiring rapid and energetically facile water sorption.
Evolution and interplay of lithium metal interphase components revealed by experimental and theoretical studies
ABSTRACT: Lithium metal batteries (LMB) have high energy densities and are crucial for clean energy solutions. The characterization of lithium metal interphase is fundamentally and practically important but technically challenging. Taking advantage of synchrotron x-ray which has the unique capability of analyzing crystalline/amorphous phases quantitative-ly with statistical significance, we study the composition and dynamics of LMB interphase for a newly developed im-portant LMB electrolyte that is based on fluorinated ether. Pair distribution function analysis revealed the sequential role of anion and solvent in interphase formation during cycling. The relative ratio between Li2O and LiF first increases and then decreases during cycling, suggesting suppressed Li2O formation in both initial and long extended cycles. Theoretical studies revealed that in initial cycles, this is due to the energy barrier in many-electron transfer. In long extended cycles, the anion decomposition product Li2O encourages solvent decomposition by facilitating solvent adsorption on Li2O which is followed by concurrent depletion of both. This work highlights the important role of Li2O in transitioning from anion-derived interphase to a solvent-derived one.
Preparation of Nonprecious Metal Electrocatalysts for the Reduction of Oxygen Using a Low-Temperature Sacrificial Metal
Non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) are generally composed of iron, nitrogen, and carbon synthesized through high-temperature pyrolysis. Among the various types of precursors, metal-organic frameworks (MOFs), zeolitic imidazolate framework (ZIF)-8 in particular, have often been used in the synthesis. The pyrolysis of ZIF-8 precursor relies on the use of Zn as a sacrificial metal (SM), and the optimal processing temperatures often exceed 1000 degrees C to generate active non-PGM catalysts. The high pyrolysis temperature tends to result in heterogeneous active moieties ranging from Fe single atoms to nanoparticles. In this study, we present the synthesis of non-PGM catalysts using Cd as the sacrificial metal instead of Zn. By using Cd, we were able to generate active non-PGM electrocatalysts from the MOF precursors at a low pyrolysis temperature of 750 degrees C, which helps preserve the single atomic iron active sites.
Benchmarking nitrous oxide adsorption and activation in metal–organic frameworks bearing coordinatively unsaturated metal centers
Anthropogenic emissions of N 2 O, the third most abundant greenhouse gas after CO 2 and CH 4 , are contributing to global climate change. Although metal–organic frameworks (MOFs) have been widely studied as adsorbents for CO 2 and CH 4 , less effort has focused on the use of MOFs to remove N 2 O from emission streams or from air. Further, N 2 O activation would enable its use as an inexpensive oxidant for fine chemical synthesis. Here, in this paper, we identify features that contribute to strong binding and high uptake of N 2 O at coordinatively unsaturated metal sites in the M 2 Cl 2 (btdd) (M = Mn, Co, Ni, Cu; btdd 2– = bis(1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) and M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn; dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate) series of MOFs. Combined experimental and computational studies suggest that N 2 O adsorption at open-metal-sites is primarily based on electrostatic interactions, rather than π-backbonding, causing MOFs with more Lewis acidic metal centers to be superior N 2 O adsorbents. As a result, Mg 2 (dobdc) demonstrates strong binding and record-setting N 2 O uptake (8.75 mmol g –1 at 1 bar and 298 K). Using density functional theory (DFT) to characterize reactive intermediates and transition states, we demonstrate that N 2 O activation to form a M(IV)–oxo species and N 2 is thermodynamically favorable in Mn 2 (dobdc) and Fe 2 (dobdc) but appears to be kinetically limited in Mn 2 (dobdc). Our work lays a foundation for understanding N 2 O adsorption and activation in MOFs, paving the way for the design of promising next-generation materials for N 2 O capture and utilization.
Metallicity beats sSFR: the connection between superluminous supernova host galaxy environments and the importance of metallicity for their production
ABSTRACT We analyse 33 Type I superluminous supernovae (SLSNe) taken from Zwicky Transient Facility (ZTF)’s Bright Transient Survey to investigate the local environments of their host galaxies. We use a spectroscopic sample of galaxies from the Sloan Digital Sky Survey (SDSS) to determine the large-scale environmental density of the host galaxy. Noting that SLSNe are generally found in galaxies with low stellar masses, high star formation rates (SFRs), and low metallicities, we find that SLSN hosts are also rarely found within high-density environments. Only $3\substack{+9 \\ -1}$ per cent of SLSN hosts were found in regions with two or more bright galaxies within 2 Mpc. For comparison, we generate a sample of 662 SDSS galaxies matched to the photometric properties of the SLSN hosts. This sample is also rarely found within high-density environments, suggesting that galaxies with properties required for SLSN production favour more isolated environments. Furthermore, we select galaxies within the IllustrisTNG simulation to match SLSN host galaxy properties in colour and stellar mass. We find that the fraction of simulated galaxies in high-density environments quantitatively match the observed SLSN hosts only if we restrict to simulated galaxies with metallicity 12 + log (O/H) ≤ 8.12. In contrast, limiting to only the highest specific star formation rate (sSFR) galaxies in the sample leads to an overabundance of SLSN hosts in high-density environments. Thus, our measurement of the environmental density of SLSN host galaxies appears to break the degeneracy between low metallicity and high sSFR as the driver for SLSN hosts and provides evidence that the most constraining factor on SLSN production is low metallicity.
Spatiotemporal characterization of the field-induced insulator-to-metal transition
Watching a metal filament grow Resistive switching is a process in which the electrical resistance of a sample changes abruptly in response to a voltage pulse, often by orders of magnitude. This process is at the heart of many neuromorphic computing approaches but visualizing it in both space and time is tricky. del Valle et al . monitored the resistive switching in three different vanadium oxide compounds by measuring time- and space-resolved optical reflectivity (see the Perspective by Hilgenkamp and Gao). A characteristic conducting filament was quickly nucleated on the inhomogeneities in the sample and then propagated due to Joule heating. —JS
Recent Progress in Cathode Materials for Sodium-Metal Halide Batteries
Transitioning from fossil-fuels to renewable energy sources is a critical goal of greenhouse gas re-duction and climate control. Major improvements have made wind and solar power increasingly cost-competitive with fossil fuels. However, the inherent intermittency of renewable power sources such motivates pairing these resources with energy storage. Electrochemical energy storage in batteries is widely used in many fields and increasingly for grid-level storage, but current battery technologies still fall short of performance, safety, and cost. This review focuses on sodium metal halide (Na-MH) batteries, such as well-known Na-NiCl2 batteries, as a promising solution to safe and economical grid-level energy storage. Important features of conventional Na-MH batteries are discussed, and recent literature on the development of intermediate temperature, low-cost cathodes for Na-MH batteries is highlighted. By employing lower cost metal halides (e.g. FeCl2, ZnCl2, and CuCl2, etc.) in the cathode and operating at lower temperatures (e.g. 190 °C vs. 280 °C), new Na-MH batteries have the potential to offer comparable performance at much lower overall costs, providing an exciting alternative technology to enable widespread adoption of renewables plus storage for the grid.
Methods of sheet metal production and sheet metal products produced thereby
Processes for producing sheet metal products by machining a solid metal body with a cutting tool in a single step to continuously produce a continuous bulk form from material obtained from the solid metal body, and without performing a hot rolling operation thereon, cold rolling the continuous bulk form to produce a sheet metal product. The machining step is a large-strain machining process capable of being directly performed on an as-cast ingot or other solid body to produce a continuous intermediate product that can be directly cold rolled without any intervening hot rolling operation, and optionally without homogenization or annealing.
Solvothermal synthesis and solid-state characterization of metal-metal bonded tetracarboxylatoditechnetium(II,III) polymers
Investigations of solvothermal reactions with pertechnetate, [TcO 4 ] - , have produced four new low-valent Tc extended metal atom chain (EMAC) complexes with multiple metal-metal bonds. The thermal reaction of potassium pertechnetate with glacial acetic acid, under in-situ hydrogen production from the decomposition of sodium borohydride, yields purple elongated crystals determined to be tetraacetato ditechnetium (II,III) acetate (1), [Tc 2 (O 2 CCH 3 ) 4 (μ-O 2 CCH 3 ] n . Compound 1 was characterized by single crystal X-ray diffraction and its magnetic properties recorded between 10 and 300 K. Single crystal X-ray diffraction analysis of 1 indicates the Tc 2 +5 tetraacetato unit is linked by the carboxylate oxygens of the bridging acetate, similar to known chloride and bromide linkage polymers of composition [Tc 2 (μ-O 2 CCH 3 ) 4 Cl] n , and [Tc 2 (μ-O 2 CCH 3 ) 4 Br] n . Here, using the same synthetic method three similar compounds have been synthesized from propionic, benzoic and pivalic acid.