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An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri: An In-Situ Neutron Diffraction and DFT Study of Hydrogen Adsorption in a Sodalite-Type Metal-Organic Framework, Cu-BTTri
Herein we present a detailed study of the hydrogen adsorption properties of Cu-BTTri, a robust crystalline metal-organic framework containing open metal-coordination sites. Diffraction techniques, carried out on the activated framework, reveal a structure that is different from what was previously reported. Further, combining standard hydrogen adsorption measurements with in-situ neutron diffraction techniques provides molecular level insight into the hydrogen adsorption process. The diffraction experiments unveil the location of four D2 adsorption sites in Cu-BTTri and shed light on the structural features that promote hydrogen adsorption in this material. Density functional theory (DFT), used to predict the location and strength of binding sites, corroborate the experimental findings. By decomposing binding energies in different sites in various energetic contributions, we show that van der Waals interactions play a crucial role, suggesting a possible route to enhancing the binding energy around open metal coordination sites.
Fast Diagnosis of Failure Mechanisms and Lifetime Prediction of Li Metal Batteries
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Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions
A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2 :1 guaiacol, weight hourly space velocity 5 h $-$1 ). Ligand-capped Ni, Pt, Rh, Ni 2 P, and Rh 2 P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2 prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2 , NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.
Dephosphorization Kinetics between Bloated Metal Droplets and Slag Containing FeO: The Influence of CO Bubbles on the Mass Transfer of Phosphorus in the Metal
Dephosphorization kinetics of bloated metal droplets was investigated in the temperature range from 1813 K to 1913 K (1540 °C to 1640 °C). The experimental results showed that the overall mass transfer coefficient, k{sub o}, decreased with increasing temperature because of decreasing phosphorus partition ratio, L P . It was also found that the mass transfer coefficient for phosphorus in the metal, k m , had the highest value at the lowest temperature [i.e., 1813 K (1540 °C)] because the formation of smaller CO bubbles increased the rate of surface renewal, leading to faster mass transport. Meanwhile, metal droplets without carbon were also employed to study the effect of decarburization on dephosphorization. The results show that although decarburization lowers the driving force significantly, k{sub m} (6.2 × 10 -2 cm/s) for a carbon containing droplet is two orders of magnitude higher than that for carbon free droplets (5.3 × 10 -4 cm/s) because of the stirring effect provided by CO bubbles. This stirring offers a faster surface renewal rate, which surpasses the loss of driving force and then leads to a faster dephosphorization rate.
Substantial tensile ductility in sputtered Zr-Ni-Al nano-sized metallic glass
Abstract not provided
PowderJet: Spherical metal powder production via multi-orifice droplet-on-demand metal jetting
Leading metal additive manufacturing techniques, such as laser powder bed fusion and directed energy deposition, rely on high-quality spherical metal powders. However, traditional powder production methods like gas atomization face limitations, including low in-spec yield, asphericity, and internal porosity. We introduce PowderJet, a powder production platform that uses electromagnetic pulses to eject liquid metal droplets from a multi-orifice nozzle. Unlike stochastic methods, PowderJet tightly controls powder size, distribution, and purity through a droplet-on-demand approach. We detail the system’s design, operation, and performance using a combined experimental and computational fluid dynamics (CFD) framework. Initial results with Al4008 and Cu110 alloys demonstrate successful production, yielding unsieved aluminum powder batches with a mean diameter of 200 µm and a narrow size distribution (15 µm standard deviation). The produced powders are highly spherical, achieving a roundness > 0.95. PowderJet operates with a small melt volume (3 mL) and supports continuous refilling, enabling production rates between 30 and 140 cm³/hr depending on jetting frequency, number of orifices and particle size. CFD simulations show that future systems could achieve rates exceeding 1000 cm³/hr for particle sizes as small as 40 µm. PowderJet’s high yield of in-spec powder makes it ideal for producing precious or hazardous materials that are inefficient to manufacture using conventional methods. This platform offers a scalable, precise, and efficient solution for producing high-quality powders tailored for advanced manufacturing applications.
Variation in metal tolerance associated with population exposure history in Southern toads (Anaxyrus terrestris)
Not provided.
Localized High-Concentration Sulfone Electrolytes for High-Efficiency Lithium-Metal Batteries
To enable next-generation high-energy-density lithium (Li) metal batteries (LMBs), an electrolyte that has simultaneous high Li metal Coulombic efficiency (CE) and high anodic stability on cathodes is of significant importance. Sulfones are known for their high dielectric constants, low flammability and in particular strong resistance against oxidation, but their application in LMBs is restricted due to their poor compatibility with Li metal anode. Uncontrolled Li plating in sulfones results in poor Li CE and induces catastrophic battery failure, and their high viscosity and poor wettability towards electrodes and separators introduce serious issues for the practical applications. Here, we demonstrate that stable Li plating/stripping cycles can be achieved in concentrated sulfone-based electrolytes at a high CE over 98%, where nodule instead of dendritic Li deposition occurs. Furthermore, the viscosity and wettability issues of sulfones could be resolved by the addition of a fluorinated ether, which is a poor solvating agent for ionic species but well miscible with sulfones at microscopic scale. This localized high-concentration electrolyte (LHCE) not only provides further improvement in Li CE (to 98.8%), but also remains anodically stable with high voltage cathode and enables LMBs to operate in a wide temperature range. As a result, significantly improved cycling performance of LMBs using sulfone-based LHCE has been realized.
Leaching Model of Radionuclides in Metal-Organic Framework Particles
Metal-organic frameworks (MOFs) have been used to sequester radionuclides and seal them inside of porous scaffolds using postsynthetic modification procedures. Experiments show that certain Zr-MOF with different capping linkers significantly affects the radionuclide release kinetics. In this work, we developed a leaching model of radionuclides in Zr-MOF particles. The model assumes that uranyl species occupy two energetically favored sites: the metal node and the MOF pores. For a given overall concentration of uranyl species, the partitions of uranyl species at the metal nodes and within the pores are determined by their chemical potentials. The model also considers the effect of particle surface and concentration on chemical potentials and diffusivity. The effects of spatial and structural dependent chemical potentials and diffusivity as well as particle sizes on leaching kinetics are investigated with the model. Predicted and measured uranyl leaching kinetics in Zr-MOF particles under batch experiments are compared. The results demonstrate the model’s capability for exploring the mechanisms of leaching and provide guidance for material design.
Metallic nanocatalysts for electrochemical CO2 reduction in aqueous solutions
Not provided.
N and p-type properties in organo-metal halide perovskites studied by Seebeck effects
Not Available
Ambient and High Pressure CuNiSb 2 : Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides
The mineral Zlatogorite, CuNiSb 2 , was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb 2 -AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb 2 -AP crystallizes in the NiAs-derived structure ( P 3 m 1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb 6 and CuSb 6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure ( P 6 3 / mm c, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb 2 -AP. The magnetic measurement indicates that CuNiSb 2 -AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb 2 -AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb 2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb 2 -8 GPa) was prepared by pressing CuNiSb 2 -AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb 2 -8 GPa are best fit with a disordered metal structure in the P 3 m 1 space group, corroborated by transmission electron microscopy.
Breaking Simple Scaling Relations through Metal–Oxide Interactions: Understanding Room-Temperature Activation of Methane on M/CeO 2 (M = Pt, Ni, or Co) Interfaces
The clean activation of methane at low temperatures remains an eminent challenge and a field of competitive research. In particular, on late transition metal surfaces such as Pt(111) or Ni(111), higher temperatures are necessary to activate the hydrocarbon molecule, but a massive deposition of carbon makes the metal surface useless for catalytic activity. However, on very low-loaded M/CeO 2 (M = Pt, Ni, or Co) surfaces, the dissociation of methane occurs at room temperature, which is unexpected considering simple linear scaling relationships. This intriguing phenomenon has been studied using a combination of experimental techniques (ambient-pressure X-ray photoelectron spectroscopy, time-resolved X-ray diffraction, and X-ray absorption spectroscopy) and density functional theory-based calculations. The experimental and theoretical studies show that the size and morphology of the supported nanoparticles together with strong metal–support interactions are behind the deviations from the scaling relations. These findings point toward a possible strategy for circumventing scaling relations, producing active and stable catalysts that can be employed for methane activation and conversion.
Direct Identification of Mixed-Metal Centers in Metal–Organic Frameworks: Cu 3 (BTC) 2 Transmetalated with Rh 2+ Ions
Raman spectroscopy was used to establish direct evidence of heterometallic metal centers in a metal–organic framework (MOF). The Cu 3 (BTC) 2 MOF HKUST-1 (BTC 3– = benzenetricarboxylate) was transmetalated by heating it in a solution of RhCl 3 to substitute Rh 2+ ions for Cu 2+ ions in the dinuclear paddlewheel nodes of the framework. In addition to the Cu–Cu and Rh–Rh stretching modes, Raman spectra of (Cu x Rh 1– x ) 3 (BTC) 2 show the Cu–Rh stretching mode, indicating that mixed-metal Cu–Rh nodes are formed after transmetalation. Density functional theory studies confirmed the assignment of a Raman peak at 285 cm –1 to the Cu–Rh stretching vibration. Electron paramagnetic resonance spectroscopy experiments further supported the conclusion that Rh 2+ ions are substituted into the paddlewheel nodes of Cu 3 (BTC) 2 to form an isostructural heterometallic MOF, and electron microscopy studies showed that Rh and Cu are homogeneously distributed in (Cu x Rh 1– x ) 3 (BTC) 2 on the nanoscale.
Plating Precious Metals on Nonprecious Metal Nanoparticles for Sustainable Electrocatalysts
Precious metals have broad applications in modern industry and renewable energy technologies. The high cost and limited availability of these materials, however, have caused a grand challenge for sustainability. In this work, we report on the plating of a precious metal on nonprecious metal nanoparticles for the development of sustainable electrocatalysts. Cobalt/platinum core/shell (denoted as Co@Pt) nanoparticles were synthesized via seed-mediated growth. The Co seeds were first synthesized by thermal decomposition of cobalt carbonyl, and the Pt shell was overgrown in situ by adding platinum acetylacetonate (Pt(acac) 2 ). The galvanic replacement reaction between Co and the Pt precursor was successfully suppressed by taking advantage of CO (generated from the decomposition of cobalt carbonyl) as the stabilizing ligand and/or reducing agent. Moreover, the obtained Co@Pt nanoparticles were found to exhibit enhanced catalytic activity for the oxygen reduction reaction (ORR).
The Bonding Nature and Adhesion of Polyacrylic Acid Coating on Li-Metal for Li Dendrite Prevention
The success of polyacrylic acid (PAA) to suppress Li dendrite growth suggests that the mechanical properties of polymer-based coatings, including the modulus, toughness, and interfacial adhesion are important design criteria. However, the measurement of the adhesion of thin PAA, as well as other polymer coatings to the reactive Li-metal anode surface is limited experimentally and challenging computationally. In this paper, a strategy was proposed to estimate the adhesion and delamination of the PAA(polymer)/Li interface, based on the bonding nature at the simpler PAA (oligomer)/Li interfaces using density functional theory calculations. It has been shown that the carboxylic acid groups in PAA reacted strongly with metallic Li, which significantly enhances the interfacial adhesion through the Li–O bonds formation, Li ionization and its incorporation into PAA, and –H or –OH termination of Li after decomposition of the COOH functional group. During delamination, it was found that the most likely PAA delamination route involved breaking partial Li–O bonds and lifting some ionized Li atoms from the Li-metal, especially for the Li atoms that showed a charge closer to +1 or are bonded with two O atoms from PAA. Based on the average bonding energies from PAA(oligomer)/Li interface delamination calculations, the work of separation, W sep , of the PAA(polymer)/Li interface was estimated to be ~1.0 (J/m 2 ). The high W sep of PAA (polymer)/Li was comparable with the Li 2 O/Li interface and higher than Li 2 CO 3 /Li and LiF/Li interfaces. This order correlated well with the areal density of Li–O bonds, which can serve as a descriptor for the interfacial adhesion. Furthermore, this computational approach can be applied to other interfaces with polymer-based coatings.
Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal–Organic Frameworks
Photoredox catalytic activation of organic molecules via single-electron transfer processes has proven to be a mild and efficient synthetic methodology. However, the heavy reliance on expensive ruthenium and iridium complexes limits their applications for scale-up synthesis. To this end, photoactive metal–organic frameworks (MOFs) exhibit unique advantages as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations has been limited. Here we describe the preparation and synthetic applications of four isostructural porphyrinic MOFs, namely, UNLPF-10a, -10b, -11, and -12, which are composed of free base, In III -, Sn IV Cl 2 -, and Sn IV -porphyrin building blocks, respectively. We demonstrate that the metalation with high valent metal cations (In III and Sn IV ) significantly modifies the electronic structure of porphyrin macrocycle and provides a highly oxidative photoexcited state that can undergo efficient reductive quenching processes to facilitate organic reactions. In particular, UNLPF-12 exhibits both outstanding photostability and efficient photocatalytic activities toward a range of important organic transformations including aerobic hydroxylation of arylboronic acids, amine coupling, and the Mannich reaction.