Superhard and Superconducting Bilayer Borophene.

Two-dimensional superconductors, especially the covalent metals such as borophene, have received significant attention due to their new fundamental physics, as well as potential applications. Furthermore, the bilayer borophene has recently ignited interest due to its high stability and versatile properties. Here, the mechanical and superconducting properties of bilayer-δ6 borophene are explored by means of first-principles computations and anisotropic Migdal-Eliashberg analytics. We find that the coexistence of strong covalent bonds and delocalized metallic bonds endows this structure with remarkable mechanical properties (maximum 2D-Young's modulus of ~570 N/m) and superconductivity with a critical temperature of ~20 K. Moreover, the superconducting critical temperature of this structure can be further boosted to ~46 K by applied strain, which is the highest value known among all borophenes or two-dimensional elemental materials.

Synthesis Landscapes for Ammonia Borane Chemical Vapor Deposition of h-BN and BNNT: Unraveling Reactions and Intermediates from First-Principles.

Planar hexagonal boron nitride (h-BN) and tubular BN nanotube (BNNT), known for their superior mechanical and thermal properties, as well as wide electronic band gap, hold great potential for nanoelectronic and optoelectronic devices. Chemical vapor deposition has demonstrated the best way to scalable synthesis of high-quality BN nanomaterials. Yet, the atomistic understanding of reactions from precursors to product-material remains elusive, posing challenges for experimental design. Here, performing first-principles calculations and ab initio molecular simulations, we explore pyrolytic decomposition pathways of the most used precursor ammonia borane (H3BNH3, AB) to BN, in gas-phase and on Ni(111) or amorphous boron (for BNNT growth) surfaces, for comparison. It reveals that in the gas phase, a pair of AB molecules cooperate to form intermediate NH3 and ammonia diborane, which further dissociates into H2BNH2, accompanied by critical BH4- and NH4+ ions. These ions act as H scavengers facilitating H2BNH2 dehydrogenation into HBNH. The consequent HBNH directly feeds BN flake growth by reacting with the crystal edge, while the addition of H2BNH2 to the edge is prohibited at 1500 K. In contrast, on Ni and boron surfaces, AB monomer dehydrogenates stepwise, deeper, yielding BNH and BN dimer as the primary building unit. Our study maps out three typical experimental conditions regarding the dissociation of AB-precursor, providing insights into the underlying reaction mechanisms of gas-phase precursors, to help as guidelines for the experimental growth of BN nanomaterials.

Kinetically Controlled Synthesis of Metallic Glass Nanoparticles with Expanded Composition Space.

Nanoscale metallic glasses offer opportunities for investigating fundamental properties of amorphous solids and technological applications in biomedicine, microengineering, and catalysis. However, their top-down fabrication is limited by bulk counterpart availability, and bottom-up synthesis remains underexplored due to strict formation conditions. Here, a kinetically controlled flash carbothermic reaction is developed, featuring ultrafast heating (>105 K s-1) and cooling rates (>104 K s-1), for synthesizing metallic glass nanoparticles within milliseconds. Nine compositional permutations of noble metals, base metals, and metalloid (M1─M2─P, M1 = Pt/Pd, M2 = Cu/Ni/Fe/Co/Sn) are synthesized with widely tunable particle sizes and substrates. Through combinatorial development, a substantially expanded composition space for nanoscale metallic glass is discovered compared to bulk counterpart, revealing that the nanosize effect enhances glass forming ability. Leveraging this, several nanoscale metallic glasses are synthesized with composition that have never, to the knowledge, been synthesized in bulk. The metallic glass nanoparticles exhibit high activity in heterogeneous catalysis, outperforming crystalline metal alloy nanoparticles.

Creating chirality in the nearly two dimensions.

Structural chirality, defined as the lack of mirror symmetry in materials' atomic structure, is only meaningful in three-dimensional space. Yet two-dimensional (2D) materials, despite their small thickness, can show chirality that enables prominent asymmetric optical, electrical and magnetic properties. In this Perspective, we first discuss the possible definition and mathematical description of '2D chiral materials', and the intriguing physics enabled by structural chirality in van der Waals 2D homobilayers and heterostructures, such as circular dichroism, chiral plasmons and the nonlinear Hall effect. We then summarize the recent experimental progress and approaches to induce and control structural chirality in 2D materials from monolayers to superlattices. Finally, we postulate a few unique opportunities offered by 2D chiral materials, the synthesis and new properties of which can potentially lead to chiral optoelectronic devices and possibly materials for enantioselective photochemistry.

A Global Perspective on Oral Vaccination of Wildlife against Rabies.

The long-term mitigation of human-domestic animal-wildlife conflicts is complex and difficult. Over the last 50 yr, the primary biomedical concepts and actualized collaborative global field applications of oral rabies vaccination to wildlife serve as one dramatic example that revolutionized the field of infectious disease management of free-ranging animals. Oral vaccination of wildlife occurred in diverse locales within Africa, Eurasia, the Middle East, and North America. Although rabies is not a candidate for eradication, over a billion doses of vaccine-laden baits distributed strategically by hand, at baiting stations, or via aircraft, resulted in widespread disease prevention, control, or local disease elimination among mesocarnivores. Pure, potent, safe, and efficacious vaccines consisted of either modified-live, highly attenuated, or recombinant viruses contained within attractive, edible baits. Since the late 1970s, major free-ranging target species have included coyotes (Canis latrans), foxes (Urocyon cinereoargenteus; Vulpes vulpes), jackals (Canis aureus; Lupulella mesomelas), raccoons (Procyon lotor), raccoon dogs (Nyctereutes procyonoides), and skunks (Mephitis mephitis). Operational progress has occurred in all but the latter species. Programmatic evaluations of oral rabies vaccination success have included: demonstration of biomarkers incorporated within vaccine-laden baits in target species as representative of bait contact; serological measurement of the induction of specific rabies virus neutralizing antibodies, indicative of an immune response to vaccine; and most importantly, the decreasing detection of rabies virus antigens in the brains of collected animals via enhanced laboratory-based surveillance, as evidence of management impact. Although often conceived mistakenly as a panacea, such cost-effective technology applied to free-ranging wildlife represents a real-world, One Health application benefiting agriculture, conservation biology, and public health. Based upon lessons learned with oral rabies vaccination of mesocarnivores, opportunities for future extension to other taxa and additional diseases will have far-reaching, transdisciplinary benefits.

Persistence of Anti-Rabies Antibody Response in Horses Following Vaccination.

Rabies is a fatal zoonotic disease affecting all mammalian species. It is caused by the rabies virus and is prevalent worldwide. Horses are not commonly infected with rabies but their vaccination is recommended due to the potential zoonotic risk. This study aimed to evaluate the duration of immunity following rabies vaccination in horses. A total of 126 serum samples were collected from 93 horses, vaccinated 6 to 91 months before sampling. Rabies-virus-neutralizing antibody (RVNA) levels were evaluated using the Rabies Fluorescent Focus Inhibition Test (RFFIT). A protective RVNA titer of above 0.5 IU/mL was found in 112 (88.9%) of the samples and 84 (90.3%) of the horses. Antibody titers declined over time (rho = -0.271, p = 0.002); however, there was no significant difference in antibody titers or the prevalence of unprotected horses between the time intervals following vaccination. Purebred horses had lower antibody titers (p = 0.024). The response to booster vaccination was inspected in ten horses, and increased antibody titers were found in eight of them. The results of this study demonstrate the prolonged persistence of protective immunity in horses following rabies vaccination, in some cases, for up to eight years. Therefore, the current annual vaccination strategy should be re-evaluated. A rate of 9.7% of poor responders should be considered from an epidemiological perspective in order to minimize the risk of emergence of the disease.

Enhanced As-COF nanochannels as a high-capacity anode for K and Ca-ion batteries.

Covalent organic frameworks can be used for next-generation rechargeable metal-ion batteries due to their controllable spatial and chemical architectures and plentiful elemental reserves. In this study, the arsenic-based covalent organic framework (As-COF) is designed by employing the geometrical symmetry of a semiconducting phosphazene-based covalent organic framework that uses p-phenylenediamine as a linker and hexachorocyclotriphosphazene as an As-containing monomer in a C3-like spatial configuration. The As-COF with engineered nanochannels demonstrates exceptional anodic behavior for potassium (K) and calcium (Ca) ion batteries. It exhibits a high storage capacity of about 914(2039) mA h g-1, low diffusion barriers of 0.12(0.26) eV, low open circuit voltage of 0.23(0.18) V, and a minimal volume expansion of 2.41(2.32)% for K (Ca) ions. These attributes collectively suggest that As-COF could significantly advance high-capacity rechargeable batteries.

Large effective magnetic fields from chiral phonons in rare-earth halides.

Time-reversal symmetry (TRS) is pivotal for materials' optical, magnetic, topological, and transport properties. Chiral phonons, characterized by atoms rotating unidirectionally around their equilibrium positions, generate dynamic lattice structures that break TRS. Here, we report that coherent chiral phonons, driven by circularly polarized terahertz light pulses, polarize the paramagnetic spins in cerium fluoride in a manner similar to that of a quasi-static magnetic field on the order of 1 tesla. Through time-resolved Faraday rotation and Kerr ellipticity, we found that the transient magnetization is only excited by pulses resonant with phonons, proportional to the angular momentum of the phonons, and growing with magnetic susceptibility at cryogenic temperatures. The observation quantitatively agrees with our spin-phonon coupling model and may enable new routes to investigating ultrafast magnetism, energy-efficient spintronics, and nonequilibrium phases of matter with broken TRS.

Accelerating multielectron reduction at CuxO nanograins interfaces with controlled local electric field.

Regulating electron transport rate and ion concentrations in the local microenvironment of active site can overcome the slow kinetics and unfavorable thermodynamics of CO2 electroreduction. However, simultaneous optimization of both kinetics and thermodynamics is hindered by synthetic constraints and poor mechanistic understanding. Here we leverage laser-assisted manufacturing for synthesizing CuxO bipyramids with controlled tip angles and abundant nanograins, and elucidate the mechanism of the relationship between electron transport/ion concentrations and electrocatalytic performance. Potassium/OH- adsorption tests and finite element simulations corroborate the contributions from strong electric field at the sharp tip. In situ Fourier transform infrared spectrometry and differential electrochemical mass spectrometry unveil the dynamic evolution of critical *CO/*OCCOH intermediates and product profiles, complemented with theoretical calculations that elucidate the thermodynamic contributions from improved coupling at the Cu+/Cu2+ interfaces. Through modulating the electron transport and ion concentrations, we achieve high Faradaic efficiency of 81% at ~900 mA cm-2 for C2+ products via CO2RR. Similar enhancement is also observed for nitrate reduction reaction (NITRR), achieving 81.83 mg h-1 ammonia yield rate per milligram catalyst. Coupling the CO2RR and NITRR systems demonstrates the potential for valorizing flue gases and nitrate wastes, which suggests a practical approach for carbon-nitrogen cycling.

Controlled Growth of Single-Crystal Graphene Wafers on Twin-Boundary-Free Cu(111) Substrates.

Single-crystal graphene (SCG) wafers are needed to enable mass-electronics and optoelectronics owing to their excellent properties and compatibility with silicon-based technology. Controlled synthesis of high-quality SCG wafers can be done exploiting single-crystal Cu(111) substrates as epitaxial growth substrates recently. However, current Cu(111) films prepared by magnetron sputtering on single-crystal sapphire wafers still suffer from in-plane twin boundaries, which degrade the SCG chemical vapor deposition. Here, it is shown how to eliminate twin boundaries on Cu and achieve 4 in. Cu(111) wafers with ≈95% crystallinity. The introduction of a temperature gradient on Cu films with designed texture during annealing drives abnormal grain growth across the whole Cu wafer. In-plane twin boundaries are eliminated via migration of out-of-plane grain boundaries. SCG wafers grown on the resulting single-crystal Cu(111) substrates exhibit improved crystallinity with >97% aligned graphene domains. As-synthesized SCG wafers exhibit an average carrier mobility up to 7284 cm2 V-1 s-1 at room temperature from 103 devices and a uniform sheet resistance with only 5% deviation in 4 in. region.

Electronic Properties of Zn2V(1-x)NbxN3 Alloys to Model Novel Materials for Light-Emitting Diodes.

We propose the Zn2V(1-x)NbxN3 alloy as a new promising material for optoelectronic applications, in particular for light-emitting diodes (LEDs). We perform accurate electronic-structure calculations of the alloy for several concentrations x using density-functional theory with meta-GGA exchange-correlation functional TB09. The band gap is found to vary between 2.2 and 2.9 eV with varying V/Nb concentration. This range is suitable for developing bright LEDs with tunable band gap as potential replacements for the more expensive Ga(1-x)In(x)N systems. Effects of configurational disorder are taken into account by explicitly considering all possible distributions of the metal ions within the metal sublattice for the chosen supercells. We have evaluated the band gap's nonlinear behavior (bowing) with variation of V/Nb concentration for two possible scenarios: (i) only the structure with the lowest total energy is present at each concentration and (ii) the structure with minimum band gap is present at each concentration, which corresponds to experimental conditions when also metastable structures are presents. We found that the bowing is about twice larger in the latter case. However, in both cases, the bowing parameter is found to be lower than 1 eV, which is about twice smaller than that in the widely used Ga(1-x)In(x)N alloy. Furthermore, we found that both crystal volume changes due to alloying and local effects (atomic relaxation and the V-N/Nb-N bonding difference) have important contributions to the band gap bowing in Zn2V(1-x)NbxN3.

Battery metal recycling by flash Joule heating.

The staggering accumulation of end-of-life lithium-ion batteries (LIBs) and the growing scarcity of battery metal sources have triggered an urgent call for an effective recycling strategy. However, it is challenging to reclaim these metals with both high efficiency and low environmental footprint. We use here a pulsed dc flash Joule heating (FJH) strategy that heats the black mass, the combined anode and cathode, to >2100 kelvin within seconds, leading to ~1000-fold increase in subsequent leaching kinetics. There are high recovery yields of all the battery metals, regardless of their chemistries, using even diluted acids like 0.01 M HCl, thereby lessening the secondary waste stream. The ultrafast high temperature achieves thermal decomposition of the passivated solid electrolyte interphase and valence state reduction of the hard-to-dissolve metal compounds while mitigating diffusional loss of volatile metals. Life cycle analysis versus present recycling methods shows that FJH significantly reduces the environmental footprint of spent LIB processing while turning it into an economically attractive process.

Synthesis of Clean Hydrogen Gas from Waste Plastic at Zero Net Cost.

Hydrogen gas (H2 ) is the primary storable fuel for pollution-free energy production, with over 90 million tonnes used globally per year. More than 95% of H2 is synthesized through metal-catalyzed steam methane reforming that produces 11 tonnes of carbon dioxide (CO2 ) per tonne H2 . "Green H2 " from water electrolysis using renewable energy evolves no CO2 , but costs 2-3× more, making it presently economically unviable. Here catalyst-free conversion of waste plastic into clean H2 along with high purity graphene is reported. The scalable procedure evolves no CO2 when deconstructing polyolefins and produces H2 in purities up to 94% at high mass yields. The sale of graphene byproduct at just 5% of its current value yields H2 production at a negative cost. Life-cycle assessment demonstrates a 39-84% reduction in emissions compared to other H2 production methods, suggesting the flash H2 process to be an economically viable, clean H2 production route.

Growth Instability of 2D Materials on Non-Euclidean Surfaces.

Chemical growth of two-dimensional (2D) materials with controlled morphology is critical to bring their tantalizing properties to fruition. However, the growth must be on a substrate, which involves either intrinsic or intentionally introduced undulation, at a scale significantly larger than the materials thickness. Recent theory and experiments showed that 2D materials grown on a curved feature on substrates can incur a variety of topological defects and grain boundaries. Using a Monte Carlo method, we herein show that 2D materials growing on periodically undulated substrates with nonzero Gaussian curvature of practical relevance follow three distinct modes: defect-free conformal, defect-free suspension and defective conformal modes. The growth on the non-Euclidean surface can accumulate tensile stress that gradually lifts the materials from substrates and progressively turns the conformal mode into a suspension mode with increasing the undulation amplitude. Further enhancing the undulation can trigger Asaro-Tiller-Grinfield growth instability in the materials, manifested as discretely distributed topological defects due to strong stress concentration. We rationalize these results by model analyses and establish a "phase" diagram for guiding the control of growth morphology via substrate patterning. The undulation-induced suspension of 2D materials can help understand the formation of overlapping grain boundaries, spotted quite often in experiments, and guide how to avoid them.

Floating Fe Catalyst Formation and Effects of Hydrogen Environment in the Growth of Carbon Nanotubes.

Hydrocarbon conversion to advanced carbon nanomaterials with concurrent hydrogen production holds promise for clean energy technologies. This has been largely enabled by the floating catalyst chemical vapor deposition (FCCVD) growth of carbon nanotubes (CNTs), where commonly catalytic iron nanoparticles are formed from ferrocene decomposition. However, the catalyst formation mechanism and the effect of the chemical environment, especially hydrogen, remain elusive. Here, by employing atomistic simulations, we demonstrate how (i) hydrogen accelerates the ferrocene decomposition and (ii) prevents catalyst encapsulation. A subsequent catalytic dehydrogenation of methane on a liquid Fe nanoparticle showed that carbon dimers tend to be the dominant on-surface species. Such atomistic insights help us better understand the catalyst formation and CNT nucleation in the early stages of the FCCVD growth process and optimize it for potential scaleup.

Electronic Properties of Functionalized Diamanes for Field-Emission Displays.

Ultrathin diamond films, or diamanes, are promising quasi-2D materials that are characterized by high stiffness, extreme wear resistance, high thermal conductivity, and chemical stability. Surface functionalization of multilayer graphene with different stackings of layers could be an interesting opportunity to induce proper electronic properties into diamanes. Combination of these electronic properties together with extraordinary mechanical ones will lead to their applications as field-emission displays substituting original devices with light-emitting diodes or organic light-emitting diodes. In the present study, we focus on the electronic properties of fluorinated and hydrogenated diamanes with (111), (110), (0001), (101̅0), and (2̅110) crystallographic orientations of surfaces of various thicknesses by using first-principles calculations and Bader analysis of electron density. We see that fluorine induces an occupied surface electronic state, while hydrogen modifies the occupied bulk state and also induces unoccupied surface states. Furthermore, a lower number of layers is necessary for hydrogenated diamanes to achieve the convergence of the work function in comparison with fluorinated diamanes, with the exception of fluorinated (110) and (2̅110) films that achieve rapid convergence and have the same behavior as other hydrogenated surfaces. This induces a modification of the work function with an increase of the number of layers that makes hydrogenated (2̅110) diamanes the most suitable surface for field-emission displays, better than the fluorinated counterparts. In addition, a quasi-quantitative descriptor of surface dipole moment based on the Tantardini-Oganov electronegativity scale is introduced as the average of bond dipole moments between the surface atoms. This new fundamental descriptor is capable of predicting a priori the bond dipole moment and may be considered as a new useful feature for crystal structure prediction based on artificial intelligence.

Theory of sigma bond resonance in flat boron materials.

In chemistry, theory of aromaticity or π bond resonance plays a central role in intuitively understanding the stability and properties of organic molecules. Here we present an analogue theory for σ bond resonance in flat boron materials, which allows us to determine the distribution of two-center two-electron and three-center two-electron bonds without quantum calculations. Based on this theory, three rules are proposed to draw the Kekulé-like bonding configurations for flat boron materials and to explore their properties intuitively. As an application of the theory, a simple explanation of why neutral borophene with ~1/9 hole has the highest stability and the effect of charge doping on borophene's optimal hole concentration is provided with the assumption of σ and π orbital occupation balance. Like the aromaticity theory for carbon materials, this theory greatly deepens our understanding on boron materials and paves the way for the rational design of various boron-based materials.

Single-Photon Emission from Two-Dimensional Materials, to a Brighter Future.

Single photons, often called flying qubits, have enormous promise to realize scalable quantum technologies ranging from an unhackable communication network to quantum computers. However, finding an ideal single-photon emitter (SPE) is a great challenge. Recently, two-dimensional (2D) materials have shown great potential as hosts for SPEs that are bright and operate under ambient conditions. This Perspective enumerates the metrics required for an SPE source and highlights that 2D materials, because of reduced dimensionality, exhibit interesting physical effects and satisfy several metrics, making them excellent candidates to host SPEs. The performance of SPE candidates discovered in 2D materials, hexagonal boron nitride and transition metal dichalcogenides, will be assessed based on the metrics, and the remaining challenges will be highlighted. Lastly, strategies to mitigate such challenges by developing design rules to deterministically create SPE sources will be presented.

Evidence for Topological Magnon-Phonon Hybridization in a 2D Antiferromagnet down to the Monolayer Limit.

Topological phonons and magnons potentially enable low-loss, quantum coherent, and chiral transport of information and energy at the atomic scale. Van der Waals magnetic materials are promising to realize such states due to their recently discovered strong interactions among the electronic, spin, and lattice degrees of freedom. Here, we report the first observation of coherent hybridization of magnons and phonons in monolayer antiferromagnet FePSe3 by cavity-enhanced magneto-Raman spectroscopy. The robust magnon-phonon cooperativity in the 2D limit occurs even in zero magnetic field, which enables nontrivial band inversion between longitudinal and transverse optical phonons caused by the strong coupling with magnons. The spin and lattice symmetry theoretically guarantee magnetic-field-controlled topological phase transition, verified by nonzero Chern numbers calculated from the coupled spin-lattice model. The 2D topological magnon-phonon hybridization potentially offers a new route toward quantum phononics and magnonics with an ultrasmall footprint.

Flexo-Ferroelectricity and a Work Cycle of a Two-Dimensional-Monolayer Actuator.

Well recognized mechanical flexibility of two-dimensional (2D) materials is shown to bring about unexpected behaviors to the recently discovered monolayer ferroelectrics, especially those displaying normal, off-plane polarization. A "ferro-flexo" coupling term is introduced into the energy expression, to account for the connection of ferroelectricity and bending (strain gradient) of the layer, to predict and quantify its spontaneous curvature and how it affects the phase transitions. With InP as a chemically specific representative example, the first-principles calculations indeed reveal strong coupling ∼P·Ï° between the ferroelectric polarization (P) and the curvature of the layer (Ï° ≡ 1/r), having profound consequences for both mechanics and ferroelectricity of the material. Due to flexural relaxation, the spontaneous polarization and the transition barrier rise significantly, leading to large changes in the Curie temperature, coercive field, and domain wall width and energy, based on Monte Carlo simulations. On the other hand, the polarization switching, characteristic to ferroelectrics, does induce an overall layer bending, enabling a conversion of electrical signal to movement as an actuator; its possible work-cycles and maximum work-efficiency are briefly discussed.