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At least 1,189 records · Page 66

A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes

Abstract Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H 2 and CO 2 .

Desnoyer, Addison N.↗

A Dicopper Platform that Stabilizes the Formation of Pentanuclear Coinage Metal Hydride Complexes

Abstract Reduction of a dicopper(II) bis(hydroxide) complex with silanes in the presence of external copper or silver cations results in the formation of multinuclear hydride clusters, which were characterized by a variety of NMR spectroscopic experiments and X‐ray crystallography. In particular, the pentanuclear complexes adopt an unusual planar “bow tie” configuration. The copper hydride complexes are efficient catalysts for the dehydrogenation of formic acid to H 2 and CO 2 .

Desnoyer, Addison N.↗

Modeling Planar Electrodes and Zero–Gap Membrane Electrode Assemblies for CO 2 Electrolysis

Multiphysics modeling enables probing of conditions inside a CO 2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one-dimensional model for a zero-gap membrane electrode assembly (MEA) CO 2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO 3 concentration.

30 DIRECT ENERGY CONVERSION↗

Chemical and mechanical interfacial degradation in bifacial glass/glass and glass/transparent backsheet photovoltaic modules

Abstract Glass/glass (G/G) photovoltaic modules are quickly rising in popularity, but the durability of modern G/G packaging has not yet been established. In this work, we examine the interfacial degradation modes in G/G and glass/transparent backsheet modules under damp heat (DH) with and without system bias voltage, comparing emerging polyolefin elastomer (POE) and industry‐standard poly(ethylene‐co‐vinyl acetate) (EVA) encapsulants. We investigate the transport of ionic species at cell/encapsulant interfaces, demonstrating that POE limits both sodium and silver ion migration compared with EVA. Changes to the chemical structures of the encapsulants at the cell/encapsulant interfaces demonstrate that both POE and EVA are more susceptible to degradation in modules with a transparent backsheet than in the G/G configuration. Adhesion testing reveals that POE and EVA have comparable critical debond energies after the DH exposures regardless of system bias polarity. The results of this study indicate that the interfacial degradation mechanisms of G/G appear to be similar to those of conventional glass/backsheet modules. For emerging materials, our results demonstrate that POE offers advantages over EVA but that transparent backsheets may accelerate encapsulant degradation due to increased moisture ingress when compared with the G/G structure.

14 SOLAR ENERGY↗

Does plasma jet sintering follow an Arrhenius-type expression?

Atmospheric pressure, ambient temperature plasma jets have become a promising candidate for material processing in parallel with developments in additive manufacturing. Recent work has shown that plasma jets can be used to sinter printed nanoparticles at temperatures much lower than typically required for conventional thermal sintering. In this report we conduct a mechanistic study on plasma jet sintering that correlates specific energy input with the electrical conductivity of printed silver films after sintering. Increasing the specific energy input accelerated the sintering process following an Arrhenius-like exponential trend across a large range of conditions, including both helium and argon plasma jets. Although an exponential relationship is also found with the plasma heated substrate temperature, independent studies indicate that heating is not the primary mechanism. These results suggest there is a general behavior that couples the plasma jet with the surface.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Installation protocol for charge transfer dissociation mass spectrometry on ion trapping mass spectrometers

Abstract Rationale Charge transfer dissociation (CTD) is a novel fragmentation technique that demonstrates enhanced structural characterization for a wide variety of molecules compared to standard fragmentation techniques like collision‐induced dissociation (CID). Alternative fragmentation techniques, such as electron transfer dissociation, electron capture dissociation, and ultraviolet photodissociation, also overcome many of the shortfalls of CID, but none of them are a silver bullet that can adequately characterize a wide variety of structures and charge states of target compounds. Given the diversity of structural classes and their occasional obstinance towards certain activation techniques, alternative fragmentation techniques are required that rely on novel or alternative modes of activation. Methods Herein, we present a step‐by‐step protocol for the installation of CTD on a quadrupole ion trap mass spectrometer and best practices for optimizing the signal‐to‐noise ratio and acquisition times for CTD mass spectra. Results In addition to two CTD installations in the Jackson laboratory, CTD has also been installed, and is currently in operation, on two 3D ion trap mass spectrometers in France: one in the laboratory of Dr. David Ropartz and Dr. Hélène Rogneaux at INRAE in Nantes, and the other in the laboratory of Dr. Jean‐Yves Salpin at Université d'Évry Val‐d'Essonne, part of the Paris‐Saclay University system. Conclusions Here, we provide a visual protocol to help others accomplish the instrument modification.

47 OTHER INSTRUMENTATION↗

Understanding Superatomic Ag Nanohydrides

Abstract Bulk Ag hydrides are extremely challenging to make even at very high pressures, but they may become stable as the particle size shrinks to the nanometer regime. Here, the formation and electronic structure of Ag nanohydrides are investigated from a superatomic perspective by density functional theory. It is found that as the coverage increases, adsorption energy of hydrogen atoms on Ag 38 cluster to form Ag 38 H 2 n nanohydride ( n is from 1 to 15) can be energetically favorable with respect to bare Ag 38 and H 2 . Furthermore, the adsorbed hydrogen atoms contribute their 1s electrons to the superatom electron count and behave as a metal instead of a ligand. The electronic structure of the silver nanohydrides follows the superatomic complex model, leading to magic or relatively more stable compositions such as Ag 38 H 2 , Ag 38 H 20 , and Ag 38 H 30 , which correspond to 40‐electron, 58‐electron, and 68‐electron shell closings, respectively. Angular momentum analyses of the superatomic orbitals suggest a convoluted interaction of geometry, symmetry, and orbital splitting.

He, Xiang↗

Ionic‐Liquid Free and Flexible Transistors Made of 2D Material Inks

The development of thin-film transistors (TFTs) using 2D materials is crucial for enabling scalable, low-cost, and flexible electronics. Currently, 2D TFTs with the highest performance have been achieved by using ionic-liquid gating (ILG), a technique suited for proof-of-concept studies. However, ILG suffers from slow switching speeds, temperature sensitivity, poor long-term stability, and integration challenges, making it unsuitable for practical use. Moreover, typical fabrication methods for 2D TFTs involve harsh conditions such as strong acids or high temperatures (>300 °C), limiting integration with flexible substrates. This work provides the first demonstration of an ILG-free, all-2D-material TFT fabricated onto a flexible substrate. Water-based graphene and hexagonal boron nitride (h-BN) inks are printed to deposit the electrodes and dielectric layers, respectively. The MoS 2 channel is produced via supramolecular interfacial self-assembly, yielding uniform, monolayer-rich films transferable to rigid and flexible substrates. The resulting TFTs operate below 3 V, exhibit negligible leakage current, and achieve field-effect mobilities up to 0.46 cm 2 V −1 s −1 (rising to 2.47 cm 2 V −1 s −1 with silver electrodes) measured under ambient conditions, while maintaining excellent mechanical flexibility. This work establishes a low-cost and scalable solution-processable platform for flexible electronics based on 2D materials that match requirements for practical applications.

2D materials↗

Engineering Supramolecular Hybrid Architectures with Directional Organofluorine Bonds

Understanding how chemical modifications alter the atomic‐scale organization of materials is of fundamental importance in materials engineering and the target of considerable efforts in computational prediction. Incorporating covalent and noncovalent interactions in designing crystals while “piggybacking” on the driving force of molecular self‐assembly has augmented efforts to understand the emergence of complex structures using directed synthesis. In this work, microcrystalline powders of the silver 2‐, 3‐, and 4‐fluorobenzenethiolates are prepared and their structures are resolved by small‐molecule serial femtosecond X‐ray crystallography. These three compounds enable the emergence and role of supramolecular synthons in the crystal structures of 3D metal‐organic chalcogenolates to be examined. The unique divergence in their optoelectronic, morphological, and structural behaviors is assessed. The extent of CHF interactions and their influence on the structure and the observed trends in the thermal stability of the crystals are quantified through theoretical calculations and thermogravimetric analysis.

Kotei, Patience A.↗

Nanocomposite Materials for Radionuclide Sequestration from Groundwater Environments

The half-lives of radionuclides range from fractions of a second to billions of years. Since no practical method of altering radioactive decay exists, and since exposure to either the energy emitted from radioactive decay or chemical properties of radionuclides poses dire health risks, radioactive materials must be segregated and controlled. The capture, treatment, and disposition of radioactive materials remain an extraordinary challenge. In here, we focus our attention on the synthesis and characterization of a unique class of nanocomposite materials that have potential for removal of radionuclide contamination. Specifically, we report a simple approach to decorate the surface of iron-based (Fe/FexOy) material with various nano-catalysts. Specifically, copper (Cu), tin (Sn), and silver (Ag) nanoparticles were prepared through two different reduction approaches, namely, citrate and cetyltrimethylammonium bromide (CTAB) methods, on the iron-based material surface. All samples were characterized by a variety of analytical tools, which included scanning electron microscopy (SEM), electron-dispersive X-ray microanalysis (EDS), and EDS mapping to elucidate materials’ morphology as well as nano-catalysts’ loading and location on the iron-based structures.

Hunyadi Murph, Simona E.↗

The effects of electrically exploding gold bridgewires into inert and explosive powder beds

Abstract The particle velocity created in beds of both low-density inert sugar and explosive PETN as a function of distance from an exploding bridgewire was measured using optical velocimetry and a silvered PMMA window. As expected, more violent bridge-bursts (from a greater-stored-energy capacitive discharge unit) resulted in greater particle velocities and a better supported compaction wave in sugar. In all cases, ramp waves, not shocks, were observed in the inert sugar. Large window velocities were observed for very powerful bursts (up to 270 m/s), but bursts required for stochastic detonator operation conditions resulted in sugar/PMMA window velocities of only 8–10 m/s 0.85 mm from the bridge location. In contrast, after a distance of only 0.65 mm, a building shock wave was observed in PETN under both threshold and reliable firing conditions. Subsequently a hot-spot-driven shock-to-detonation (SDT) process was observed prior to full detonation. The measured buildup process accounts for $$\approx $$ ≈ 66% of the so-called excess transit time (ETT) between the observed and theoretical total function time for the particular exploding-bridge-wire (EBW) detonator studied. The remainder must occur in the powerful output pellet region. In contrast to a common understanding, the ETT is found to be a weak function of the discharge energy. Thus, the operation of the detonator after a bridge-burst energy-to-powder reaction transition process is found to be hot-spot-driven SDT in both the low- and high-density pellets.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Extrapolating Contaminant Effects from Individuals to Populations: A Case Study on Nanoparticle Toxicity to Daphnia Fed Environmentally Relevant Food Levels

Ecological risk assessment (ERA) is charged with assessing the likelihood a chemical will have adverse environmental or ecological effects. When assessing the risk of a potential contaminant to biological organisms, ecologists are most concerned with the sustainability of populations of organisms, rather than protecting every individual. However, ERA most commonly relies on data on the effect of a potential contaminant on individuals because these experiments are more feasible than costly population-level exposures. In this work, we address the challenge of extrapolating these individual-level results to predict population-level effects. Previous per-capita population growth rate estimates calculated from individual-level exposures of Daphnia pulicaria to silver nanoparticles (AgNPs) at different food rations predict a critical daily food requirement for daphnid populations exposed to 200 μg/L AgNPs to avoid extinction. To test this, we exposed daphnid populations to the same AgNP concentration at three different food inputs, with the lowest ration close to the extinction threshold predicted from data on individuals. The two populations with the higher food inputs persisted, and the population with the lowest food input went extinct after 50 days but did persist through two generations. Further, we demonstrate that we can extrapolate between these levels of biological organization by parameterizing an individual-level biomass model with data on individuals’ response to AgNPs and using these parameters to predict the outcome for control and AgNP-exposed populations. Key to successful extrapolation is careful modeling of temporal changes in resource density, driven by both the experimental protocols and feedback from the consumer. The implication for ecotoxicology is that estimates of extinction thresholds based on studies of individuals may be reliable predictors of population outcomes, but only with careful treatment of resource dynamics.

54 ENVIRONMENTAL SCIENCES↗

All-aerosol-jet-printed highly sensitive and selective polyaniline-based ammonia sensors: a route toward low-cost, low-power gas detection

In this work, we report the design and scalable fabrication of a low-cost and low-power polyaniline-based (PANI) ammonia (NH3) gas sensor on polyimide (PI) substrates using additive manufacturing techniques. The silver interdigitated electrode (IDE) arrays and conducting polymer films are printed onto PI using a direct-write technology of aerosol-jet printing. Morphological characteristics are examined by scanning electron microscopy and energy-dispersive X-ray analysis which reveal homogeneously printed PANI film on the IDE platform. The gas sensing performance is evaluated in the analytical early leak detection range of 5–1000 ppm NH3 in air as a function of both thermal (23 °C, 50 °C, 80 °C) and relative humidity (RH = 0%, 30%, 50%) exposures. The sensor exhibits sensitivity down to 5 ppm NH3 with a sub-ppm detection limit and good repeatability. We observe rapid NH3 detection at 0% RH with very extended times for equilibration and recovery. However, at both 30 and 50% RH, the room temperature response and recovery times are reduced to only about 1 min and 5 min, respectively. Experiments also reveal good sensitivity toward the analyte even at higher operating temperatures. Present results merit the practical application of aerosol-jet-printed, low-power sensors for industrial applications where low-level hazardous gas detection is essential.

36 MATERIALS SCIENCE↗