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Many computational models have been developed to predict the rates of atomic displacements in two-dimensional (2D) materials under electron beam irradiation. However, these models often drastically underestimate the displacement rates in 2D insulators, in which beam-induced electronic excitations can reduce the binding energies of the irradiated atoms. This bond softening leads to a qualitative disagreement between theory and experiment, in that substantial sputtering is experimentally observed at beam energies deemed far too small to drive atomic dislocation by many current models. To address these theoretical shortcomings, this paper develops a first-principles method to calculate the probability of beam-induced electronic excitations by coupling quantum electrodynamics (QED) scattering amplitudes to density functional theory (DFT) single-particle orbitals. The presented theory then explicitly considers the effect of these electronic excitations on the sputtering cross section. Applying this method to 2D hexagonal BN and MoS

In many applications, amorphous particles bond together through a phenomenon known as sintering to minimize their surface energy. Water is a plasticizer for many food and pharmaceutical powders and the strong reduction in viscosity induced by moisture absorption can accelerate strongly particle sintering [1]. Numerical simulations of particle sintering usually neglect the coupling with moisture transfer, considering a uniform viscosity throughout the particle. In this study, a novel approach based on solving Navier-Stokes equation using an Arbitrary Lagrangian-Eulerian (ALE) approach is proposed to model the dynamics of particle sintering coupled with moisture transfer. Maltodextrin DE21 is considered as an industrially relevant example of amorphous particles. Due to moisture uptake, strong gradients of viscosity can exist in the particles undergoing sintering. FEM simulations consider accurately the forces acting on the contact area between the particles, leading to slower dynamics than commonly used approximate analytical models. This study highlights that FEM simulations considering a homogeneous moisture and viscosity within the particles are in many cases sufficiently accurate and identifies the limits of validity of this assumption. In the conditions considered in this study, the intraparticle gradients were found to condition significantly the sintering dynamics only when particle diameter is above 1.5 mm. The particle size affects strongly both the dynamics of sintering and of moisture transfer. Moreover, higher external relative humidity leads to a lower viscosity and a faster sintering kinetics. The initial water content was found to have a lower impact in the conditions studied. This coupled simulation approach can be used to identify conditions reducing the risk of caking during the storage of amorphous powders or to master sintering during powder structuration processes. Furthermore this study helps identifying when simpler simulation approaches considering homogeneous particles can be safely used and shows the limitations of simplified analytical models.

Metal-to-semiconducting transition in the naphthylene-β 2D lattice induced by a spin-polarized state.

Y.A.K. acknowledges the financial support from the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No. 2021R1I1A305628711). A.B. gratefully acknowledges the Centre National de la Recherche Scientifique (CNRS) and the International Center for Frontier Research in Chemistry (icFRC) (Strasbourg, France). J.M.D.T. acknowledges joint partial funding from Gobierno del Principado de Asturias and European Regional Development Fund (ERDF/FEDER) (grant IDI/2021/000037). Y.C. acknowledges the financial support from the Australian Research Council under the ARC research hub for safe and reliable energy (IH200100035).

Electron transport through iron porphyrin (FeP) molecules self-assembled on a gold (Au) substrate was investigated using conductive atomic force microscopy (AFM) to measure current–voltage (I–V) ch...

The on-surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. Herein, Raman spectroscopy is used to characterize different types of GNRs on their growth substrate and track their quality upon substrate transfer. A Raman-optimized (RO) device substrate and an optimized mapping approach are presented that allow for the acquisition of high-resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substrates. This approach is well suited to routinely monitor the geometry-dependent low-frequency modes of GNRs. In particular, the radial breathing-like mode (RBLM) and the shear-like mode (SLM) for 5-, 7-, and 9-atom-wide armchair GNRs (AGNRs) are tracked and their frequencies are compared with first-principles calculations.

The adsorption and activation of CO2 molecules on the surface of photocatalysts are critical steps to realize efficient solar energy-induced CO2 conversion to valuable chemicals. In this work, a defect engineering approach of a high-valence cation Nb-doping into TiO2 was developed, which effectively enhanced the adsorption and activation of CO2 molecules on the Nb-doped TiO2 surface. A highly ordered Nb-doped TiO2 nanotube array was prepared by anodization of the Ti-Nb alloy foil and subsequent annealing at 550 °C in air for 2 h for its crystallization. Our sample showed a superior photocatalytic CO2 reduction performance under simulated solar illumination. The main CO2 reduction product was a higher-energy compound of acetaldehyde, which could be easily transported and stored and used to produce various key chemicals as intermediates. The acetaldehyde production rate was over ∼500 μmol·g-1·h-1 with good stability for repeated long-time uses, and it also demonstrated a superior product selectivity to acetaldehyde of over 99%. Our work reveals that the Nb-doped TiO2 nanotube array could be a promising candidate with high efficiency and good product selectivity for the photocatalytic CO2 reduction with solar energy.

The search for targeted modifications of graphene to tune its electronic properties has stimulated the proposal of several new allotropic variations of carbon with s p and s p 2 hybridizations. In this study, a class of 2-dimensional carbon nanostructures with mixed s p 2 − s p 3 hybridization is theoretically investigated. These structures contain hexagonal and tetragonal cycles and are shown to exhibit metallic or semiconducting behaviors depending on structural parameters. The key for the manipulation of the physical properties is the extent of the system’s graphene-like section. Remarkable properties emerge, such as Dirac cones, which are allowed by the coupling between different sectors of the system as mediated by tetrahedrally-coordinated carbon atoms. In addition to fundamental properties, we also point aspects suggesting the experimental feasibility of these systems.

The experimental identification of structural transitions in layered black phosphorus (BP) under mechanical stress is essential to extend its application in microelectromechanical (MEMS) devices under harsh conditions. High-pressure Raman spectroscopic analysis of BP flakes suggests a transition pressure at ∼4.2 GPa, where the BP's crystal structure progressively transforms from an orthorhombic to a rhombohedral symmetry (blue phosphorus, bP). The phase transition has been identified by observing a transition from blueshift to redshift of the in-plane characteristic Raman modes (B

Hotspot engineering has the potential to transform the field of surface-enhanced Raman spectroscopy (SERS) by enabling ultrasensitive and reproducible detection of analytes. However, the ability to controllably generate SERS hotspots, with desired location and geometry, over large-area substrates, has remained elusive. In this study, we sculpt artificial edges in monolayer molybdenum disulfide (MoS2) by low-power focused laser-cutting. We find that when gold nanoparticles (AuNPs) are deposited on MoS2 by drop-casting, the AuNPs tend to accumulate predominantly along the artificial edges. First-principles density functional theory (DFT) calculations indicate strong binding of AuNPs with the artificial edges due to dangling bonds that are ubiquitous on the unpassivated (laser-cut) edges. The dense accumulation of AuNPs along the artificial edges intensifies plasmonic effects in these regions, creating hotspots exclusively along the artificial edges. DFT further indicates that adsorption of AuNPs along the artificial edges prompts a transition from semiconducting to metallic behavior, which can further intensify the plasmonic effect along the artificial edges. These effects are observed exclusively for the sculpted (i.e., cut) edges and not observed for the MoS2 surface (away from the cut edges) or along the natural (passivated) edges of the MoS2 sheet. To demonstrate the practical utility of this concept, we use our substrate to detect Rhodamine B (RhB) with a large SERS enhancement (∼104) at the hotspots for RhB concentrations as low as ∼10-10 M. The single-step laser-etching process reported here can be used to controllably generate arrays of SERS hotspots. As such, this concept offers several advantages over previously reported SERS substrates that rely on electrochemical deposition, e-beam lithography, nanoimprinting, or photolithography. Whereas we have focused our study on MoS2, this concept could, in principle, be extended to a variety of 2D material platforms.

Two-dimensional semiconductors, including transition metal dichalcogenides, are of interest in electronics and photonics but remain nonmagnetic in their intrinsic form. Previous efforts to form two-dimensional dilute magnetic semiconductors utilized extrinsic doping techniques or bulk crystal growth, detrimentally affecting uniformity, scalability, or Curie temperature. Here, we demonstrate an in situ substitutional doping of Fe atoms into MoS2 monolayers in the chemical vapor deposition growth. The iron atoms substitute molybdenum sites in MoS2 crystals, as confirmed by transmission electron microscopy and Raman signatures. We uncover an Fe-related spectral transition of Fe:MoS2 monolayers that appears at 2.28 eV above the pristine bandgap and displays pronounced ferromagnetic hysteresis. The microscopic origin is further corroborated by density functional theory calculations of dipole-allowed transitions in Fe:MoS2. Using spatially integrating magnetization measurements and spatially resolving nitrogen-vacancy center magnetometry, we show that Fe:MoS2 monolayers remain magnetized even at ambient conditions, manifesting ferromagnetism at room temperature. Ferromagnetism with a Curie temperature above room temperature in 2D materials is highly desirable for practical spintronics applications. Here, the authors demonstrate such phenomenon in monolayer MoS2 via in situ iron-doping and measured local magnetic field strength up to 0.5 ± 0.1 mT.

Selective two-electron oxygen reduction reaction (ORR) offers a promising route for hydrogen peroxide synthesis, and defective sp2 carbon-based materials are attractive, low-cost electrocatalysts for this process. However, due to a wide range of possible defect structures formed during material synthesis, identification and fabrication of precise active sites remain a challenge. Here, we report a graphene edgebased electrocatalyst for two-electron ORR - nanowire-templated three-dimensional fuzzy graphene (NT3DFG). NT-3DFG exhibits excellent efficiency (onset potential of 0.79 $\pm$ 0.01 V versus RHE), selectivity (93 $\pm$ 3 % H2O2), and tunable ORR activity as a function of graphene edge site density. Using spectroscopic surface characterization and density functional theory calculations, we find that NT-3DFG edge sites are readily functionalized by carbonyl (C=O) and hydroxyl (C-OH) groups under alkaline ORR conditions. Our calculations indicate that multiple site configurations at both armchair and zigzag edges may achieve a local coordination environment that allows selective, two-electron ORR. We derive a general geometric descriptor based on the local coordination environment that provides activity predictions of graphene surface sites within ~0.1 V of computed values. Herein we combine synthesis, spectroscopy, and simulations to improve active site characterization and accelerate carbon-based electrocatalyst discovery., 33 pages, 36 pages of Supporting Information

Freeze-drying is generally used to achieve high quality products and preserve thermal sensitive components; however, it is also considered as a high energy and costly process. Modeling of the process can help to optimize the process to reduce these drawbacks. In this work, a mathematical model is presented to predict the heat and mass transfer behavior for freeze-drying of porous frozen food particles during freeze-drying to optimize the process. For the mass transfer, a comparison between Knudsen diffusion and the more complex dusty-gas approach is performed. Simulation results of a single particle are validated by experiments of single-layer drying to extend the usage of this model from a single particle to a particle bed. For the moisture transfer, adaption parameters are introduced and evaluated. A comparison shows a good agreement of the model with experimental results. The results furthermore suggest a strong correlation of the drying kinetics with pore size and particle porosity. An increase in the pore diameter strongly improves the overall mass transfer rates and hence is a suitable parameter for an effective increase of the drying rates in freeze-drying. Freeze-drying is generally used to achieve high quality products and preserve thermal sensitive components; however, it is also considered as a high energy and costly process. Modeling of the process can help to optimize the process to reduce these drawbacks. In this work, a mathematical model is presented to predict the heat and mass transfer behavior for freeze-drying of porous frozen food particles during freeze-drying to optimize the process. For the mass transfer, a comparison between Knudsen diffusion and the more complex dusty-gas approach is performed. Simulation results of a single particle are validated by experiments of single-layer drying to extend the usage of this model from a single particle to a particle bed. For the moisture transfer, adaption parameters are introduced and evaluated. A comparison shows a good agreement of the model with experimental results. The results furthermore suggest a strong correlation of the drying kinetics with pore size and particle porosity. An increase in the pore diameter strongly improves the overall mass transfer rates and hence is a suitable parameter for an effective increase of the drying rates in freeze-drying.

The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultrahigh vacuum conditions from Br- and I-substituted precursors. It is shown that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed the integration of 5-AGNRs into devices and the realization of the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

Two-dimensional (2D) materials, owing to their extremely low thickness, are ideal materials for nanopores with optimal detection sensitivity and resolution. Among 2D materials, molybdenum disulfide (MoS

Density functional theory based calculations and experimental analysis on a limited number of real samples are performed to study how the presence of silver intercalated in the van der Waals gap of few-layer MoS2 affects the low-frequency Raman active modes of this material. Silver is found to predominantly affect the breathing-like and shear-like vibrational modes of MoS2. These modes correspond to quasi-rigid movements of each individual layer with a restoring force (and, in turn, frequency) that is determined by modulations in the weak interlayer interactions. Noticeable red-shifts with increasing Ag concentration are found for all low-frequency modes. This finding indicates the potential for low-frequency vibrations as useful gauges for practical determination of silver concentration using low-frequency Raman spectroscopy. This work also describes a semi-classical linear chain model that allows to extrapolate results to a large number of layers. Further, first-principles calculations show how Raman spectroscopy can be used to characterize the quality of the two-dimensional interface between MoS2 and a silver substrate.

Reconstitution of dairy powders is strongly influenced by the presence and physical state of fat on the particle surface. The present study investigates the effect of a micronized lactose coating on the physical state of the fat and the reconstitution kinetics of whole milk powder at four different temperatures (4/21/40/60 °C) and two stirring rates (400/800 rpm). For this purpose, two types of micronized lactose were used as coating materials: crystalline and amorphous.\ud \ud \ud \ud At 4 °C and 21 °C, the coated powders sink and are reconstituted faster than pure whole milk powder, regardless of the stirring rate applied. At 40/60 °C and 400 rpm, although the amorphous micronized lactose coating leads to a significant decrease in the reconstitution time, the crystalline coating has the opposite effect (or no effect). This discrepancy is related to the large differences in terms of dissolution enthalpy between the two micronized lactose physical states. It is posited that the dissolution of the coating material causes a temperature shift at the powder-water interface which could hamper the complete melting of surface fat and influence its viscosity, thereby affecting wetting and sinking. These differences are overcome at a high stirring rate (800 rpm) or if agglomerated whole milk powder is used as the host material.

This study reports on the accuracy of the GW approximation for the treatment of the Hubbard model compared to exact diagonalization (ED) results. We consider not only global quantities, such as the total energy and the density of states, but also the spatial and spin symmetry of wavefunctions via the analysis of the local density of states. GW is part of the more general Green’s function approach used to develop many-body approximations. We show that, for small linear chains, the GW approximation corrects the mean-field (MF) approach by reducing the total energy and the magnetization obtained from the MF approximation. The GW energy gap is in better agreement with ED, especially in systems of an even number of atoms where, in contrast to the MF approximation, no plateau is observed below the artificial predicted phase transition. In terms of density of states, the GW approximation induces quasi-particles and side satellite peaks via a splitting process of MF peaks. At the same time, GW slightly modifies the localization (e.g., edges or center) of states. We also use the GW approximation results in the context of Löwdin’s symmetry dilemma and show that GW predicts an artificial paramagnetic–antiferromagnetic phase transition at a higher Hubbard parameter than MF does.

Spray-dried milk powders are characterized by an underrepresentation of hydrophilic compounds on the particle surface compared to the bulk, which renders reconstitution unfavourable. To overcome this issue, in the present study we instigated the coating of whole milk powder with two types of micronized lactose: crystalline and amorphous.\ud \ud \ud \ud We demonstrate that deposition of micronized lactose on the surface of whole milk powder leads to an increase in the reconstitution rate at 21 °C, correlated with a decrease in the apparent contact angle of the material. We also show that the physical solid state of micronized lactose is an important factor influencing the reconstitution performance of coated whole milk powder; If micronized lactose is amorphous, increasing the coating concentration beyond a certain point has little or no further effect on the reconstitution kinetics, which could be explained by viscosity build-up effects that hamper capillary penetration and sinking.

Several bottom-up chemical routes have been developed in the last few years to find ways to grow new forms of nanocarbon by devising a strategical selection of molecular precursors. Here, theoretical calculations are performed on 2D nanocarbon allotropes obtained from the fusion of triphenylene-like units through tetragonal rings. This 2D triphenylene structure has a metallic character in a closed shell configuration, but it also features a spin-polarized semiconducting state. The behavior of the electronic properties of the system is investigated when the structure is cast into nanoribbon forms. It is found that to be metallic in the nonpolarized case, the ribbons must be sufficiently wide while narrow 1D systems are semiconducting. A lower threshold width is also needed for the emergence of a spin-polarized semiconducting configuration in these nanoribbons. These behaviors are robust as they do not depend on edge geometry and chirality, thus offering opportunities for their possible applications in nanoscale devices.

Heterostructures made from topological and magnetic insulators promise to form excellent platforms for new electronic and spintronic functionalities mediated by interfacial effects. We report the results of a first-principles density functional theory study of the geometric, electronic structure, and magnetic properties of the $\mathrm{EuS}(111)/{\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ interface, including van der Waals and relativistic spin-orbit effects. In contrast to previous theoretical studies, we find no appreciable magnetic anisotropy in such a heterostructure. We also do not see additional induced magnetization at the interface or the magnetic proximity effect on the topological states. This is due to the localized nature of Eu moments and because of a partial charge transfer of $\ensuremath{\sim}0.5$ electron from Eu to Se. The formation of the surface dipole shifts the Dirac cone about 0.4 eV below the chemical potential, and the associated electrostatic screening moves the topological state from the first to the second quintuple layer of ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$.

We propose two kinds of 2D carbon allotropes with a naphthyl-like group used as structural unit. We name them naphthylenes of the α, and β kinds, and study their atomic and electronic structure using density functional theory. We also investigate a set of nanoribbons cut out of naphthylenes. We show that these systems are usually metallic, with frontier states spread inside the structure, rather than at their edges. This results in a type of nanomaterials featuring controlled properties that can be tuned for targeted applications in nanoelectronics.

The realization of on-chip quantum networks requires tunable quantum states to encode information carriers on them. We show that Cr2Ge2Te6 (CGT) as a van der Waals ferromagnet can enable magnetic proximity coupling to site-controlled quantum emitters in WSe2, giving rise to ultrahigh exciton g factors up to 20 ± 1. By comparing the same site-controlled quantum emitter before and after ferromagnetic proximity coupling, we also demonstrate a technique to directly measure the resulting magnetic exchange field (MEF) strength. Experimentally determined values of MEF up to 1.2 ± 0.2 meV in the saturation regime approach the theoretical limit of 2.1 meV that was determined from density functional theory calculations of the CGT/WSe2 heterostructure. Our work extends the on-chip control of magneto-optical properties of excitons via van der Waals heterostructures to solid-state quantum emitters.