Multiple Electron Research Articles

Dramatic Influence of Temperature on Charging

Charging of cables outside of a spacecraft has been cited as the cause of multiple spacecraft anomalies based upon correlations with peaks in the energetic electron environment and because the electron flux exposure of external cables is much higher than internal cables. However, external cables are subject to much wider temperature changes than hardware located inside a thermally regulated spacecraft. Temperature affects bulk resistivity and radiation-induced conductivity, but temperature is often ignored in charging analyses and tests. In this paper, temperature effects are combined with a diurnal temperature variation and an external electron environment to simulate the charging of an external coax. The simulation shows that the coax dielectrics behave as perfect insulators during the cold portion of the 24 h cycle, but the accumulated charge leaks out during the hot portion of the cycle. There is no memory or hysteresis of charge density from one day to the next. This behavior is compared to the behavior of materials inside the spacecraft, where low flux and stable temperatures lead to charging time constants ranging from weeks to months that produce a slow, stair-step increase of trapped charge in response to multiple electron storms. These variations in charging response explain why some anomalies correlate best with peak 24 h average flux, whereas others correlate well with 14- or 21-day averaged flux. Analyses and tests used to qualify designs or investigate anomalies must account for the dramatic effects that temperature variation can have on the charging of insulators and isolated conductors.

Overexpression of RuBisCO form I and II genes in Rhodopseudomonas palustris TIE-1 augments polyhydroxyalkanoate production heterotrophically and autotrophically.

With the rising demand for sustainable renewable resources, microorganisms capable of producing bioproducts such as bioplastics are attractive. While many bioproduction systems are well-studied in model organisms, investigating non-model organisms is essential to expand the field and utilize metabolically versatile strains. This investigation centers on Rhodopseudomonas palustris TIE-1, a purple non-sulfur bacterium capable of producing bioplastics. To increase bioplastic production, genes encoding the putative regulatory protein PhaR and the depolymerase PhaZ of the polyhydroxyalkanoate (PHA) biosynthesis pathway were deleted. Genes associated with pathways that might compete with PHA production, specifically those linked to glycogen production and nitrogen fixation, were deleted. Additionally, RuBisCO form I and II genes were integrated into TIE-1's genome by a phage integration system, developed in this study. Our results show that deletion of phaR increases PHA production when TIE-1 is grown photoheterotrophically with butyrate and ammonium chloride (NH4Cl). Mutants unable to produce glycogen or fix nitrogen show increased PHA production under photoautotrophic growth with hydrogen and NH4Cl. The most significant increase in PHA production was observed when RuBisCO form I and form I & II genes were overexpressed, five times under photoheterotrophy with butyrate, two times with hydrogen and NH4Cl, and two times under photoelectrotrophic growth with N2 . In summary, inserting copies of RuBisCO genes into the TIE-1 genome is a more effective strategy than deleting competing pathways to increase PHA production in TIE-1. The successful use of the phage integration system opens numerous opportunities for synthetic biology in TIE-1.IMPORTANCEOur planet has been burdened by pollution resulting from the extensive use of petroleum-derived plastics for the last few decades. Since the discovery of biodegradable plastic alternatives, concerted efforts have been made to enhance their bioproduction. The versatile microorganism Rhodopseudomonas palustris TIE-1 (TIE-1) stands out as a promising candidate for bioplastic synthesis, owing to its ability to use multiple electron sources, fix the greenhouse gas CO2, and use light as an energy source. Two categories of strains were meticulously designed from the TIE-1 wild-type to augment the production of polyhydroxyalkanoate (PHA), one such bioplastic produced. The first group includes mutants carrying a deletion of the phaR or phaZ genes in the PHA pathway, and those lacking potential competitive carbon and energy sinks to the PHA pathway (namely, glycogen biosynthesis and nitrogen fixation). The second group comprises TIE-1 strains that overexpress RuBisCO form I or form I & II genes inserted via a phage integration system. By studying numerous metabolic mutants and overexpression strains, we conclude that genetic modifications in the environmental microbe TIE-1 can improve PHA production. When combined with other approaches (such as reactor design, use of microbial consortia, and different feedstocks), genetic and metabolic manipulations of purple nonsulfur bacteria like TIE-1 are essential for replacing petroleum-derived plastics with biodegradable plastics like PHA.

Mitigating Side Reactions in Electrocatalytic Ammonia Synthesis by Nitrate Reduction

Electrocatalytic nitrate reduction holds significant promise for generating green ammonia and mitigating pollution, reducing energy input, and exhibiting zero-carbon emissions. However, the intricate multiple electron and proton transfer processes complicate the pathways from nitrate to ammonia, hindering the development of electrocatalysts with high activity and selectivity for practical use. The primary side reactions, such as the conversion of nitrate to gaseous nitrogen species and the hydrogen reduction reaction, limit the Faradaic efficiency of nitrate-to-ammonia conversion. In this work, we have developed a controllable methodology for preparing highly active Cu-based nanocatalysts. These nanocatalysts exhibit remarkable activity and selectivity in the electrochemical nitrate reduction reaction within a flow-cell device, with a high ammonia yield and high Faradaic efficiency.

A Metal–Sulfur–Carbon Catalyst Mimicking the Two‐Component Architecture of Nitrogenase

The production of ammonia (NH3) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N2. We draw inspiration from this structural enzymology, and design a two‐component metal–sulfur–carbon (M–S–C) catalyst composed of sulfur‐doped carbon‐supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO3–) to NH3. The catalyst demonstrates a remarkable NH3 yield rate of ~37 mg L–1 h–1 and a Faradaic efficiency of ~97% for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP‐surface nearby. This study proves a better understanding of how M–S–Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism‐based catalyst design.

A Metal-Sulfur-Carbon Catalyst Mimicking the Two-Component Architecture of Nitrogenase.

The production of ammonia (NH3) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N2. We draw inspiration from this structural enzymology, and design a two-component metal-sulfur-carbon (M-S-C) catalyst composed of sulfur-doped carbon-supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO3 -) to NH3. The catalyst demonstrates a remarkable NH3 yield rate of ~37 mg L-1 h-1 and a Faradaic efficiency of ~97 % for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP-surface nearby. Such process results in a more energetically accessible pathway for NO3 - reduction on Ru NPs co-existing with SAs. This study proves a better understanding of how M-S-Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism-based catalyst design.

Regulating the Oxygen Vacancy on Bi2MoO6/Co3O4 Core‐Shell Nanocage Enables Highly Selective CO2 Photoreduction to CH4

AbstractPhotocatalytic CO2 reduction reaction (CO2RR) into high‐value‐added fuels has received significant attention, yet multiple electron and proton processes involved in CO2RR result in low selectivity. Herein, a strategy involving oxygen vacancies (Ovs)‐enriched Bi2MoO6 coated on ZIF‐67‐derived Co3O4 to construct well‐defined core‐shell nanocage is developed, which drives effective CO2 photoconversion to CH4 with nearly 100% selectivity and high apparent quantum efficiency of 2.5% at 420 nm in pure water under simulated irradiation. Theoretical calculations and experiments exhibit that the potential difference stemming from the built‐in electric field provides guarantee for CO2 reduction occurring on Bi2MoO6 and H2O oxidation set in Co3O4. Numerous exposed Bi2MoO6 with Ovs formed in Bi─O bond by ethylene glycol mediated approach promotes the CO2 adsorption and charge separation efficiency, which can optimize the reaction kinetics and thermodynamics, facilitating the hydrogenation of key intermediate *CO to generate CH4. This work provides a new strategy for controlled oxygen vacancy generation on photocatalysts to achieve high‐performance CO2 methanation.

Constructing Multi-Electron Reactions by Doping Mn2+ to Increase Capacity and Stability in K3.2V2.8Mn0.2(PO4)4/C of Phosphate Cathodes for Potassium-Ion Batteries.

Vanadium-based phosphate cathode materials (e.g., K3V2(PO4)3) have attracted widespread concentration in cathode materials in potassium-ion batteries owing to their stable structure but suffer from low capacity and poor conductivity. In this work, an element doping strategy is applied to promote its electrochemical performance so that K3.2V2.8Mn0.2(PO4)4/C is prepared via a simple sol-gel method. The heterovalent Mn2+ is introduced to stimulated multiple electron reactions to improve conductivity and capacity, as well as interlayer spacing. Galvanostatic intermittent titration technique (GITT) and in situ X-ray diffraction results further confirm that Mn-doping in the original electrode can obtain superior electrode process kinetics and structural stability. The prepared K3.2V2.8Mn0.2(PO4)4/C exhibits a high-capacity retention of 80.8% after 1500 cycles at 2 C and an impressive rate capability, with discharge capacities of 87.6 at 0.2 C and 45.4mA h g-1 at 5 C, which is superior to the majority of reported vanadium-based phosphate cathode materials. When coupled K3.2V2.8Mn0.2(PO4)4/C cathode with commercial porous carbon (PC) anode as the full cell, a prominent energy density of 175Wh kg-1 is achieved based on the total active mass. Overall, this study provides an effective strategy for meliorating the cycling stability and capacity of the polyanion cathodes for KIB.

Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction.

The electrocatalytic oxygen evolution reaction (OER) supplies the protons and electrons needed to transform renewable electricity into chemicals and fuels. However, the OER is kinetically sluggish; it operates at significant rates only when the applied potential far exceeds the reversible voltage. The origin of this overpotential is hidden in a complex mechanism involving multiple electron transfers and chemical bond making/breaking steps. Our desire to improve catalytic performance has then made mechanistic studies of the OER an area of major scientific inquiry, though the complexity of the reaction has made understanding difficult. While historically, mechanistic studies have relied solely on experiment and phenomenological models, over the past twenty years ab initio simulation has been playing an increasingly important role in developing our understanding of the electrocatalytic OER and its reaction mechanisms. In this Review we cover advances in our mechanistic understanding of the OER, organized by increasing complexity in the way through which the OER is modeled. We begin with phenomenological models built using experimental data before reviewing early efforts to incorporate ab initio methods into mechanistic studies. We go on to cover how the assumptions in these early ab initio simulations─no electric field, electrolyte, or explicit kinetics─have been relaxed. Through comparison with experimental literature, we explore the veracity of these different assumptions. We summarize by discussing the most critical open challenges in developing models to understand the mechanisms of the OER.

Brain endothelial cell activation and dysfunction associate with and contribute to the development of enlarged perivascular spaces and cerebral small vessel disease.

Multiple injurious stimuli to the brain's endothelium results in brain endothelial cell activation and dysfunction (BECact/dys) with upregulation of inflammatory signaling cascades and a decrease in bioavailable nitric oxide respectively. These injurious stimuli initiate a brain injury and a response to injury wound healing genetically programed cascade of events, which result in cellular remodeling of the neurovascular unit and blood-brain barrier with increased inflammation and permeability. These remodeling changes also include the perivascular spaces that become dilated to form enlarged perivascular spaces (EPVS) that may be identified noninvasively by magnetic resonance imaging. These EPVS are associated with and considered to be a biomarker for cerebral small vessel disease (SVD) and a dysfunctional glymphatic system with impaired removal of neurotoxic waste, which ultimately results in neurodegeneration with impaired cognition and dementia. The penultimate section discusses the understudied role of venous cerebral circulation in relation to EPVS, SVD, and the vascular contribution to cognitive impairment (VCID). The focus of this review will be primarily on BECact/dys that associates with and contributes to the development of EPVS, SVD, and impaired glymphatic system efflux. Importantly, BECact/dys may be a key piece of the puzzle to unlock this complicated story of EPVS and SVD. Multiple transmission electron micrographs and illustrations will be utilized to depict anatomical ultrastructure and allow for the discussion of multiple functional molecular cascades.

Synthesis and characterization of a series of CpW(CO)2PR3H, [CpW(CO)2PR3]−, [CpW(CO)2PR3(CH3CN)]+, and [CpW(CO)2PR3]2 complexes

A series of tungsten cyclopentadienyl carbonyl complexes were prepared and characterized to quantify their thermochemical properties and explore their reactivity. The PR3 ligand was systematically varied across a series of CpW(CO)2PR3H metal hydride complexes, where PR3 = P(OEt)3, P(Bu)3, and P(Cy)3. These complexes are known to undergo multiple proton, electron, and proton-coupled electron transfer reactions to access a variety of species including [CpW(CO)2PR3]−, [CpW(CO)2PR3(CH3CN)]+, and [CpW(CO)2PR3]2. Cyclic voltammograms of the CpW(CO)2PR3H+/0 and [CpW(CO)2PR3]0/− couples are chemically irreversible, indicating chemical reactivity upon oxidation; the anodic peak potential shifts to lower potentials as the donating ability of phosphine is increased, agreeing with previous literature on similar complexes. Additionally, voltammograms of [CpW(CO)2P(Cy)3]− become chemically reversible at scan rates above 500 mV/s, indicating that the dimerization of the [CpW(CO)2PR3] product, formed by the oxidation of [CpW(CO)2PR3]−, is slower with the sterically bulky phosphine P(Cy)3, and at high scan rates the species can be reduced before dimerization occurs. Further, as the donating ability of the phosphine increases, the pKa of the CpW(CO)2PR3H complexes increases. This work shows how ligand sterics and electronics can tune the thermochemical properties that underpin proton, electron, and proton-coupled electron transfer reactivity of these complexes.

Synergistic structure engineering and electrochemical activation modulating vanadium oxide cathode toward superior zinc-ion storage

Aqueous zinc-ion batteries (ZIBs) have emerged as competitive systems for grid-scale energy storage due to their high safety and low cost. However, the lack of suitable high-performance cathode composites limits the practical progress of ZIBs. Herein, a novel cathode material, ammonium cation-inserted and oxygen vacancy co-modulated VO2 (named NVE), was firstly synthesized through the ethylene glycol (EG) sacrificial solvent-assisted structure transformation with the ammonium vanadate (named NV) as the precursor. The sacrificial solvent promotes the structural transformation of ammonium vanadate to NH4+-intercalated vanadium oxide and enhances the number of oxygen vacancies in the resulting material. Moreover, the electrochemical activation process was performed for in-situ construction of NH4+-inserted hydrated vanadium oxide (V2O5·nH2O) material. The electrochemical activation process with high anodic voltage enables multiple electron reactions, increasing the utilization of vanadium elements and achieving high capacity. Additionally, the formed hydrogen bonds between the V-O host and inserted NH4+ ions can enhance the structural integrity, while the oxygen vacancies decrease the interaction between the V-O host and inserted Zn2+ ions to boost ion diffusion. Consequently, the resulting activated cathode demonstrates higher capacity (441 mAh/g at 0.1 A/g), superior cycling durability (85.6 % retention over 4000 cycles), and exceptional rate capability (205 mAh/g at 20 A/g). Besides, the fabricated devices based on the activated NVE cathode show decent capacity and excellent flexible stability. Furthermore, the reversible electrochemical Zn2+ storage mechanism upon battery cycling was evaluated by several kinetic measurements and in/ex-situ characterizations. This work provides novel perspectives for the fabrication of advanced cathode materials for superior aqueous ZIBs.

Superior nitrate and chromium reduction synergistically driven by multiple electron donors: Performance and the related biochemical mechanism

Nitrate and Cr(VI) are the typical and prevalent co-contaminants in the groundwater, how to synchronously and effectively diminish them has received growing attention. The most problem that currently limits the nitrate and Cr(VI) reduction technology for groundwater remediation is with emphasis on exploring the optimal electron donors. This study investigated the feasibility of utilizing the synergistical effect of inorganic electron donors (pyrite, sulfur) and inherently limited organics to promote synchronous nitrate and Cr(VI) removal, which meets the requirement of naturally low-carbon and eco-friendly technologies. The NO3−-N and Cr(VI) removal efficiencies in the pyrite and sulfur involved mixotrophic biofilter (PS–BF: approximately 90.8 ± 0.6% and 99.1 ± 2.1%) were substantially higher than that in a volcanic rock supported biofilter (V–BF: about 49.6% ± 2.8% and 50.0% ± 9.3%), which was consistent with the spatial variations of their concentrations. Abiotic and biotic batch tests directly confirmed the decisive role of pyrite and sulfur for NO3−-N and Cr(VI) removal via chemical and microbial pathways. A server decline in sulfate production correlated with decreasing COD consumption revealed that there was sulfur disproportionation induced by limited organics. Metagenomic analysis suggested that chemoautotrophic microbes like Sulfuritalea and Thiobacillus were key players responsible for sulfur oxidation, nitrate and Cr(VI) reduction. The metabolic pathway analysis suggested that genes encoding functional enzymes related to complete denitrification, S oxidation, and dissimilatory sulfate reduction were upregulated, however, genes encoding Cr(VI) reduction enzymes (e.g. chrA, chrR, nemA, and azoR) were downregulated in PS-BF, which further explained the synergistical effect of multiple electron donors. These findings provide insights into their potential cooperative interaction of multiple electron donors on greatly promoting nitrate and Cr(VI) removal and have implications for the remediation technology of nitrate and Cr(VI) co-contaminated groundwater.

Design of Linear-Polymer-Coated Graphene Nanosheets with π-Conjugated Structure and Multi-Active-Center for Long-Lifespan and High-Rate Li-Storage Performance.

Organic material holds immense potential for Li-ion batteries (LIBs) due to their eco-friendly nature, high structural designability, abundant sources, and high theoretical capacity. However, the limited redox-active sites, low electronic conductivity, sluggish ionic diffusion, and high solubility hinder their practical application. Here, we reported the use of a linear polymer called poly(naphthalenetetracarboxylic dianhydride-pyrene-4,5,9,10-tetraone)-coated graphene nanosheets (NPT/rGO) as a cathode material for LIBs. The NPT polymer has a rotation angle of approximately 63° between each plane, which helps in exposing the active sites and preventing structural pulverization during cycling. The highly conjugated skeleton of the polymer, along with graphene, forms a synergistic effect through a π-π interaction. This combination enhances the conductivity and restricts solubility. Additionally, the linear structure of NPT and the two-dimensional rGO substrates work together to enhance charge transfer and ion diffusion rates, resulting in faster reaction kinetics. Consequently, NPT/rGO exhibits excellent electrochemical performance in terms of high capacity, superior cyclic stability, and good rate capability for LIBs. Moreover, through the combination of experimental investigations and theoretical simulations, a multiple electron reaction mechanism, an efficient Li-ion storage behavior, and a reversible dynamic evolution have been revealed. This study introduces a rational molecular design approach to enhance the electrochemical performance of polyimide derivatives, thereby contributing to the advancement of cutting-edge organic electrode materials for LIBs.

Bridging Nickel-MOF and Copper Single Atoms/Clusters with H-Substituted Graphdiyne for the Tandem Catalysis of Nitrate to Ammonia.

Interfacial engineering of synergistic catalysts is one of the keys to achieving multiple proton-coupled electron transfer processes in nitrate-to-ammonia conversion. Herein, by joining ultrathin nickel-based metal-organic framework (denoted Ni-MOF) nanosheets with few-layered hydrogen-substituted graphdiyne-supported copper single atoms and clusters (denoted HsGDY@Cu), a tandem catalyst of Ni-MOFs@HsGDY@Cu with dual-active interfaces was developed for the concerted catalysis of nitrate-to-ammonia. In such a system, the sandwiched HsGDY layer could serve as a bridge to connect the coordinated unsaturated Ni2+ sites with Cu single atoms/clusters in a limited range of 0 to 3.6 nm. From Ni2+ to Cu, via the hydrogen spillover process, the hydrogen radicals (H⋅) generated at the unsaturated Ni2+ sites could migrate across HsGDY to the Cu sites to participate in the transformation of *HNO3 to NH3. From Cu to Ni2+, bypassing the higher reaction energy for *HNO3 formation on the Ni2+ sites, the NO2 - detached from the Cu sites could diffuse onto the unsaturated Ni2+ sites to form NH3 as well. The combined results make this hybrid a tandem catalyst with dual active sites for the catalysis of nitrate-to-ammonia conversion with improved Faradaic efficiency at lower overpotentials.

Manipulating interface-induced multi-channel charge transfers toward highly hierarchical synchronous g-C3N4/STO@Pt modulation for boosting artificial photosynthesis

For the transformation of energy conversion and photocatalytic decomposition, photocatalyst-based artificial photosynthesis for solar-to green fuels and environmental treatment has aroused great attention. Herein, a novel ternary heterojunction based on constructing an interaction between 2D-graphitic carbon nitride (CN), 3D-strontium titanate (STO) and Pt nanoparticles (NPs) (2D/3D CN/STO@Pt) is designed for the first time to greatly promote photocatalytic water cracking hydrogen (H2) evolution in an alkalescent environment, such as triethanolamine (TEO) as well as integrating with Rhodamin B (RhB) decomposition. Under optimized conditions, the H2 productivity over 3D/2D CN/STO@Pt-3 heterostructures (10,005 μmol h−1 g−1) with an apparent quantum yield of H2 production approaching 47.5% is found to be ∼29.7, 8.5, 1.1, and 1.5-fold as much as that in the CN, CN/STO, CN/STO@Pt-1, and CN/STO@Pt-5 heterojunctions, respectively. An up to 2.5-fold enhancement in the photocatalytic RhB decomposition rate, obtaining 90% within 60 min under visible-light-driven is observed for 3D/2D CN/STO@Pt-3 heterostructures, surpassing that of other samples. The CN/STO@Pt-3 sample shows the highest degradation rate of 3.5 min−1, which is 1.8, 2.8, 4.27 and 4.9 -time higher than that of the CN/STO@Pt-1, CN/STO@Pt-5, CN, and STO samples, respectively. The improved photocatalytic behavior of the heterogeneous structures could be ascribed to i) the type II-heterojunction between 2D CN and 3D STO; and ii) the creation of the Schottky contacts between semiconductors and Pt NPs. The configuration of the type-II heterojunction formed by the two semiconductors of 2D g-C3N4 and 3D STO contributes to improved light absorption ability, and rapid separation and transfer of photoinduced charges. At the same time, the close junction of Pt establishes the Schottky barrier to facilitate efficient electron transfer in the ternary nanostructures, impeding the quick recombination of photoexcited charge carriers, and offering abundant reactive sites, contributing multiple electron pathways for the photoreaction strategy. Increased photocurrent density from the LSV measurement and a declined in PL intensity confirmed the enhanced interfacial charge separation in the tertiary photocatalyst. Furthermore, the CN/STO@Pt-3 ternary heterostructure presents outstanding photocatalytic performance after five cycles, indicating good stability and reusability. This work gives a valuable modification pathway for the establishing multi-channel charge carrier transport for energy conversion and environmental remediation processes.

High-speed independent polarization modulation based on dual channel 2DEG anisotropic terahertz metasurfaces.

In communication and imaging systems, anisotropic metasurfaces bring new degrees of freedom for the independent control of electromagnetic waves with different polarizations. This paper proposes a dual-polarization modulation metasurface (DPMM) operating in the terahertz (THz) frequency range, which can effectively and independently modulate two orthogonally linearly polarized electromagnetic waves. The metasurface unit adopts an anisotropic structure, and by integrating multiple GaN-based high electron mobility transistors (GaN-HEMTs) into the anisotropic structure, independent control of the two-dimension electron gas (2DEG) carrier concentration in the dual-polarization channel is achieved, enabling selective modulation of x-polarization and y-polarization waves. Simulation and static experimental results demonstrate the excellent modulation isolation performance of the DPMM, with a maximum isolation exceeding 45 dB. Dynamic experiments further highlight the high-speed modulation effect, with modulation speeds exceeding 1 GHz for a single channel and an overall modulation speed of 2 GHz for dual polarization, highlighting its potential for enhancing channel capacity and information throughput in THz communication and imaging systems.

Multiple interaction electron beam powder bed fusion for controlling melt pool dynamics and improving surface quality

Low surface quality of fabricated parts and long processing times are two commonly stated reasons against a more wide-spread adoption of electron beam powder bed fusion (PBF-EB) as a commercially viable manufacturing technique. Aside from the large particle size distribution (45–150 µm) of processed powders, the surface roughness, limited structural resolution and process instabilities are attributed to unwanted dynamics of the melt pool, like spattering, balling, evaporation and melt pool displacement. As a result, a contouring step using slow but stable melting parameters is usually added to the process to improve surface quality, leading to increased processing times.In this study, we demonstrate how the surface quality can be improved by supplying the energy for melt pool formation over multiple, timely separated interactions. To investigate the effect of this multiple interaction processing (MIP), series of single line melt structures with increasing number of interactions were fabricated, characterized and corresponding thermal diffusion simulations performed. The experimental results show how MIP allows to lower surface roughness of melted structures through a reduction of spattering, balling and melt pool displacement during processing, while our simulation model identifies these benefits to be caused by a significant reduction in surface temperature and thus evaporation, with increasing number of interactions for melt pool formation. Our model further demonstrates, how a relatively simple, computationally inexpensive and thus scalable thermal diffusion model is capable of providing valuable information about thermal conditions during melt pool formation. Lastly, we introduce a few simple equations to calculate appropriate MIP parameters for any kind of scan strategy.

Periodic Adjacent Pd‐Fe Pair Sites for Enhanced Nitrate Electroreduction to Ammonia via Accelerating Proton Relay

AbstractRecently, bimetallic nanoparticles (NPs) are promising for driving nitrate (NO3 −) reduction reaction (NO3RR) to produce ammonia (NH3) due to their multiple active sites and electron redistribution via strong metal–metal interaction. However, the quantitatively determining the atomic configuration of the active sites and revealing their respective roles in NO3RR process are still challenged. Herein, the configuration of atomically ordered PdFe3 L12 intermetallic NPs into mesoporous carbon nanofibers (O‐PdFe3‐mCNFs) is reported as an efficient NO3RR catalyst for NH3 synthesis. Compared to the face‐centered cubic one, the O‐PdFe3‐mCNFs demonstrate a high NO3− removal of 98.3% within 270 min with a large NH3 yield rate of 1014.2 µmol h−1 cm−2. The detailed in situ and theoretical analysis reveals that the high performance of O‐PdFe3‐mCNFs is attributed to the synergetic effect from the periodic adjacent Pd‐Fe pair sites at the ordered (110) facet via accelerating proton relay, where the Fe sites show preferable stabilization of nitrogen−oxygen (*NO) intermediates while Pd sites serve as proton reservoir for *NO hydrogenation. Moreover, the strong d‐d orbital hybridization tunes d‐band center of the alloy NPs and effectively modulates the adsorption energy of *NO3− and *NO. This synergetic electrocatalyst design offers a new avenue for developing highly efficient multifunctional NO3RR catalysts.

Negative-Ion Electron Capture Dissociation of MALDI-Generated Peptide Anions.

Negative-ion electron capture dissociation (niECD) is an anion MS/MS technique that provides fragmentation analogous to conventional ECD, including high peptide sequence coverage and retention of labile post-translational modifications (PTMs). niECD has been proposed to be the most efficient for salt-bridged zwitterionic precursor ion structures. Several important PTMs, e.g., sulfation and phosphorylation, are acidic and can, therefore, be challenging to characterize in the positive-ion mode. Furthermore, PTM-friendly techniques, such as ECD, require multiple precursor ion-positive charges. By contrast, singly charged ions, refractory to ECD, are most compatible with niECD. Because electrospray ionization (ESI) typically yields multiply charged ions, we sought to explore matrix-assisted laser desorption/ionization (MALDI) in combination with niECD. However, the requirement for zwitterionic gaseous structures may preclude efficient niECD of MALDI-generated anions. Unexpectedly, we found that niECD of anions from MALDI is not only possible but proceeds with similar or higher efficiency compared with ESI-generated anions. Matrix selection did not appear to have a major effect. With MALDI, niECD is demonstrated up to m/z ∼4300. For such larger analytes, multiple electron captures are observed, resulting in triply charged fragments from singly charged precursor ions. Such charge-increased fragments show improved detectability. Furthermore, significantly improved (∼20-fold signal-to-noise increase) niECD spectral quality is achieved with equivalent sample amounts from MALDI vs ESI. Overall, the reported combination with MALDI significantly boosts the analytical utility of niECD.

Facile Fabrication of Large-Area CuO Flakes for Sodium-Ion Energy Storage Applications.

CuO is recognized as a promising anode material for sodium-ion batteries because of its impressive theoretical capacity of 674 mAh g-1, derived from its multiple electron transfer capabilities. However, its practical application is hindered by slow reaction kinetics and rapid capacity loss caused by side reactions during discharge/charge cycles. In this work, we introduce an innovative approach to fabricating large-area CuO and CuO@Al2O3 flakes through a combination of magnetron sputtering, thermal oxidation, and atomic layer deposition techniques. The resultant 2D CuO flakes demonstrate excellent electrochemical properties with a high initial reversible specific capacity of 487 mAh g-1 and good cycling stability, which are attributable to their unique architectures and superior structural durability. Furthermore, when these CuO flakes are coated with an ultrathin Al2O3 layer, the integration of the 2D structures with outer nanocoating leads to significantly enhanced electrochemical properties. Notably, even after 70 rate testing cycles, the CuO@Al2O3 materials maintain a high capacity of 525 mAh g-1 at a current density of 50 mA g-1. Remarkably, at a higher current density of 2000 mA g-1, these materials still achieve a capacity of 220 mAh g-1. Moreover, after 200 cycles at a current density of 200 mA g-1, a high charge capacity of 319 mAh g-1 is sustained. In addition, a full cell consisting of a CuO@Al2O3 anode and a NaNi1/3Fe1/3Mn1/3O2 cathode is investigated, showcasing remarkable cycling performance. Our findings underscore the potential of these innovative flake-like architectures as electrode materials in high-performance sodium-ion batteries, paving the way for advancements in energy storage technologies.