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Two-dimensional transition metal dichalcogenides (2D TMDs) are a promising class of functional materials for fundamental physics explorations and applications in next-generation electronics, catalysis, quantum technologies, and energy-related fields. Theory and simulations have played a pivotal role in recent advancements, from understanding physical properties and discovering new materials to elucidating synthesis processes and designing novel devices. The key has been developments in ab initio theory, deep learning, molecular dynamics, high-throughput computations, and multiscale methods. This review focuses on how theory and simulations have contributed to recent progress in 2D TMDs research, particularly in understanding properties of twisted moiré-based TMDs, predicting exotic quantum phases in TMD monolayers and heterostructures, understanding nucleation and growth processes in TMD synthesis, and comprehending electron transport and characteristics of different contacts in potential devices based on TMD heterostructures. The notable achievements provided by theory and simulations are highlighted, along with the challenges that need to be addressed. Although 2D TMDs have demonstrated potential and prototype devices have been created, we conclude by highlighting research areas that demand the most attention and how theory and simulation might address them and aid in attaining the true potential of 2D TMDs toward commercial device realizations.

Lithium iron phosphate (LiFePO 4 , LFP) batteries are widely used in electric vehicles and energy storage systems due to their excellent cycling stability, affordability and safety. However, the rate performance of LFP remains limited due to its low intrinsic electronic and ionic conductivities. In this work, an ex situ flash carbon coating method is developed to enhance the interfacial properties for fast charging. A continuous, amorphous carbon layer is achieved by rapidly decomposing the precursors and depositing carbon species in a confined space within 10 s. Simultaneously, different heteroatoms can be introduced into the surface carbon matrix, which regulates the irregular growth of cathode-electrolyte interphase (CEI) and selectively facilitates the inorganic region formation. The inorganic-rich, hybrid conductive CEI not only promotes electron and ion transport but also restricts parasitic side reactions. Consequently, LFP cathodes with fluorinated carbon coatings exhibited the highest capacity of 151 mAh g -1 at 0.2 C and 96 mAh g -1 at 10 C, indicating their excellent rate capability over commercial LFP (58 mAh g -1 at 10 C). This solvent-free, versatile surface modification is shown for other electrode materials, providing an efficient platform for electrode-electrolyte interphase engineering through a surface post-treatment., (© 2024 Wiley‐VCH GmbH.)

Recent advances in low-dimensional materials have enabled the synthesis of single-walled carbon nanotubes encapsulated in hexagonal boron nitride (BN) nanotubes (SWCNT@BNNT), creating one-dimensional van der Waals (vdW) heterostructures. However, controlling the quality and crystallinity of BNNT on the surface of SWCNTs using chemical vapor deposition (CVD) remains a challenge. To better understand the growth mechanism of the BNNT in SWCNT@BNNT, we conducted molecular dynamics (MD) simulations using empirical potentials. The simulation results suggest that spontaneous BN nucleation is unlikely to occur on the outer surface of the SWCNT when we assume only vdW interaction between the BN and SWCNT layers. However, we observe the elongation of the BNNT when a short BNNT is provided as a seed nucleus on the SWCNT. This grown BNNT structure, with its sharply cut edges, aligns with experimental observations made using transmission electron microscopy (TEM). Moreover, the edge-reconstruction process favors zigzag B edges, which exhibit low edge energy according to the ReaxFF potential. Our simulation successfully provides insights into the catalyst-free growth process of this one-dimensional vdW heterostructure.

The switching dynamics of a Au∥V S 2 @MoS 2 atomristor is explored by first-principles computations of the atomic-configuration energy and electron transport. It is found that external bias can reduce the energy barrier between the two (high- and low-) conduction states, to achieve nonvolatile resistive switching. We find that the force acting on the switching atom is a combination of electrostatic force (while its charge is induced both electrostatically and chemically) and also by electron-wind, whose effect may hinder the writing process at larger bias. The analysis uncovers how the writing and reading processes of the atomristor depend on several factors: (i) atomic structure details of the Au tip; (ii) the space-gap distance between the tip and MoS 2 layer; and (iii) tip metal choice. The fundamental understanding of switching events provides useful guidance for memristor design and possible limitations.

Catalysis is crucial for clean energy, green chemistry, and environmental remediation, but traditional methods rely on expensive and scarce precious metals. This review addresses this challenge by highlighting the promise of earth-abundant catalysts and the recent advancements in their rational design. Innovative strategies such as physics-inspired descriptors, high-throughput computational techniques, and artificial intelligence (AI)-assisted design with machine learning (ML) are explored, moving beyond time-consuming trial-and-error approaches. Additionally, biomimicry, inspired by efficient enzymes in nature, offers valuable insights. This review systematically analyses these design strategies, providing a roadmap for developing high-performance catalysts from abundant elements. Clean energy applications (water splitting, fuel cells, batteries) and green chemistry (ammonia synthesis, CO 2 reduction) are targeted while delving into the fundamental principles, biomimetic approaches, and current challenges in this field. The way to a more sustainable future is paved by overcoming catalyst scarcity through rational design., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Among C 60 's diverse functionalities, its potential application in CO 2 sequestration has gained increasing interest. However, the processes involved are sensitive to the molecule's electronic structure, aspects of which remain debated and require greater precision. To address this, we performed structural optimization of fullerene C 60 using the QM MP2/6-31G* method. The nonplanarity of the optimized icosahedron is characterized by two types of dihedral angles: 138° and 143°. The 120 dihedrals of 138° occur between two hexagons intersecting at C-C bonds of 1.42 Å, while the 60 dihedrals of 143° are observed between hexagons and pentagons at C-C bonds of 1.47 Å. NBO analysis reveals less pyramidal sp 1.78 hybridization for carbons at the 1.42 Å bonds and more pyramidal sp 2.13 hybridization for the 1.47 Å bonds. Electrostatic potential charges range from -0.04 a.u. to 0.04 a.u. on the carbon atoms. Second-order perturbation analysis indicates that delocalization interactions in the C-C bonds of 1.42 Å (143.70 kcal/mol) and 1.47 Å (34.98 kcal/mol) are 22% and 38% higher, respectively, than those in benzene. MP2/Def2SVP calculations yield a correlation energy of 13.49 kcal/mol per electron for C 60 , slightly higher than the 11.68 kcal/mol for benzene. However, the results from HOMO-LUMO calculations should be interpreted with caution. This study may assist in the rational design of fullerene C 60 derivatives for CO 2 reduction systems.

The successful synthesis of borophene beyond the monolayer limit has expanded the family of two-dimensional boron nanomaterials. While atomic-resolution topographic imaging has been previously reported, vibrational mapping has the potential to reveal deeper insight into the chemical bonding and electronic properties of bilayer borophene. Herein, inelastic electron tunneling spectroscopy (IETS) is used to resolve the low-energy vibrational and electronic properties of bilayer-α (BL-α) borophene on Ag(111) at the atomic scale. Using a carbon monoxide (CO)-functionalized scanning tunneling microscopy tip, the BL-α borophene IETS spectra reveal unique features compared to single-layer borophene and typical CO vibrations on metal surfaces. Distinct vibrational spectra are further observed for hollow and filled boron hexagons within the BL-α borophene unit cell, providing evidence for interlayer bonding between the constituent borophene layers. These experimental results are compared with density functional theory calculations to elucidate the interplay between the vibrational modes and electronic states in bilayer borophene.

Photochromic molecular motors hold promise for a multitude of potential applications in fields ranging from medicine to communications and structural repair. Yet, it is still a challenge to predict their mechanical efficiency. Here, azobenzene is explored as a representative light-driven nanomotor and estimate its quantum yield of photoisomerization and maximum mechanical efficiency. This is based on first-principles mapping of the 3D potential energy surfaces for the ground and excited states of the trans and cis configurations and identifying the minimum energy pathway for isomerization. A work cycle is devised and identifies force constant as the parameter that resembles temperature in the Carnot heat engine, but with very different efficiencies. The results show that the optomechanical efficiency of azobenzene at constant load is about 5% albeit under ideal conditions. To test the hypothesis, the study also explores the optomechanical efficiency of stilbene and 2-butene and shows that their efficiency does not exceed 5%., (© 2024 Wiley‐VCH GmbH.)

Effective recycling of end-of-life Li-ion batteries (LIBs) is essential due to continuous accumulation of battery waste and gradual depletion of battery metal resources. The present closed-loop solutions include destructive conversion to metal compounds, by destroying the entire three-dimensional morphology of the cathode through continuous thermal treatment or harsh wet extraction methods, and direct regeneration by lithium replenishment. Here, we report a solvent- and water-free flash Joule heating (FJH) method combined with magnetic separation to restore fresh cathodes from waste cathodes, followed by solid-state relithiation. The entire process is called flash recycling. This FJH method exhibits the merits of milliseconds of duration and high battery metal recovery yields of ~98%. After FJH, the cathodes reveal intact core structures with hierarchical features, implying the feasibility of their reconstituting into new cathodes. Relithiated cathodes are further used in LIBs, and show good electrochemical performance, comparable to new commercial counterparts. Life-cycle-analysis highlights that flash recycling has higher environmental and economic benefits over traditional destructive recycling processes., (© 2024. The Author(s).)

Per- and polyfluoroalkyl substances (PFAS) are persistent and bioaccumulative pollutants that can easily accumulate in soil, posing a threat to environment and human health. Current PFAS degradation processes often suffer from low efficiency, high energy and water consumption, or lack of generality. Here, we develop a rapid electrothermal mineralization (REM) process to remediate PFAS-contaminated soil. With environmentally compatible biochar as the conductive additive, the soil temperature increases to >1000 °C within seconds by current pulse input, converting PFAS to calcium fluoride with inherent calcium compounds in soil. This process is applicable for remediating various PFAS contaminants in soil, with high removal efficiencies ( >99%) and mineralization ratios ( >90%). While retaining soil particle size, composition, water infiltration rate, and cation exchange capacity, REM facilitates an increase of exchangeable nutrient supply and arthropod survival in soil, rendering it superior to the time-consuming calcination approach that severely degrades soil properties. REM is scaled up to remediate soil at two kilograms per batch and promising for large-scale, on-site soil remediation. Life-cycle assessment and techno-economic analysis demonstrate REM as an environmentally friendly and economic process, with a significant reduction of energy consumption, greenhouse gas emission, water consumption, and operation cost, when compared to existing soil remediation practices., (© 2024. The Author(s).)

Flash Joule heating has emerged as an ultrafast, scalable, and versatile synthesis method for nanomaterials, such as graphene. Here, we experimentally and theoretically deconvolute the contributions of thermal and electrical processes to the synthesis of graphene by flash Joule heating. While traditional methods of graphene synthesis involve purely chemical or thermal driving forces, our results show that the presence of charge and the resulting electric field in a graphene precursor catalyze the formation of graphene. Furthermore, modulation of the current or the pulse width affords the ability to control the three-step phase transition of the material from amorphous carbon to turbostratic graphene and finally to ordered (AB and ABC-stacked) graphene and graphite. Finally, density functional theory simulations reveal that the presence of a charge- and current-induced electric field inside the graphene precursor facilitates phase transition by lowering the activation energy of the reaction. These results demonstrate that the passage of electrical current through a solid sample can directly drive nanocrystal nucleation in flash Joule heating, an insight that may inform future Joule heating or other electrical synthesis strategies.

Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF 2 ) crystals into atomically thin two-dimensional fluoritene (2D CaF 2 ) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF 2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF 2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm -2 . Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF 2 and its potential applicability.

Most modern catalysts are based on precious metals and rear-earth elements, making some of organic synthesis reactions economically insolvent. Density functional theory calculations are used here to describe several differently oriented surfaces of the higher tungsten boride WB 5-x , together with their catalytic activity for the CO oxidation reaction. Based on our findings, WB 5-x appears to be an efficient alternative catalyst for CO oxidation. Calculated surface energies allow the use of the Wulff construction to determine the equilibrium shape of WB 5-x particles. It is found that the (010) and (101) facets terminated by boron and tungsten, respectively, are the most exposed surfaces for which the adsorption of different gaseous agents (CO, CO 2 , H 2 , N 2 , O 2 , NO, NO 2 , H 2 O, NH 3 , SO 2 ) is evaluated to reveal promising prospects for applications. CO oxidation on B-rich (010) and W-rich (101) surfaces is further investigated by analyzing the charge redistribution during the adsorption of CO and O 2 molecules. It is found that CO oxidation has relatively low energy barriers. The implications of the present results, the effects of WB 5-x on CO oxidation and potential application in the automotive, chemical, and mining industries are discussed., (© 2024. The Author(s).)

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.

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 (H 3 BNH 3 , 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 NH 3 and ammonia diborane, which further dissociates into H 2 BNH 2 , accompanied by critical BH 4 - and NH 4 + ions. These ions act as H scavengers facilitating H 2 BNH 2 dehydrogenation into HBNH. The consequent HBNH directly feeds BN flake growth by reacting with the crystal edge, while the addition of H 2 BNH 2 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.

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 cm 2 V -1 s -1 at room temperature from 103 devices and a uniform sheet resistance with only 5% deviation in 4 in. region., (© 2023 Wiley‐VCH GmbH.)

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 (>10 5 K s -1 ) and cooling rates (>10 4 K s -1 ), for synthesizing metallic glass nanoparticles within milliseconds. Nine compositional permutations of noble metals, base metals, and metalloid (M 1 ─M 2 ─P, M 1 = Pt/Pd, M 2 = 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., (© 2024 Wiley‐VCH GmbH.)

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., (© 2024. Springer Nature Limited.)

Regulating electron transport rate and ion concentrations in the local microenvironment of active site can overcome the slow kinetics and unfavorable thermodynamics of CO 2 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 Cu x O 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 + /Cu 2+ interfaces. Through modulating the electron transport and ion concentrations, we achieve high Faradaic efficiency of 81% at ~900 mA cm -2 for C 2+ products via CO 2 RR. Similar enhancement is also observed for nitrate reduction reaction (NITRR), achieving 81.83 mg h -1 ammonia yield rate per milligram catalyst. Coupling the CO 2 RR and NITRR systems demonstrates the potential for valorizing flue gases and nitrate wastes, which suggests a practical approach for carbon-nitrogen cycling., (© 2023. The Author(s).)

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.

Hydrogen gas (H 2 ) is the primary storable fuel for pollution-free energy production, with over 90 million tonnes used globally per year. More than 95% of H 2 is synthesized through metal-catalyzed steam methane reforming that produces 11 tonnes of carbon dioxide (CO 2 ) per tonne H 2 . "Green H 2 " from water electrolysis using renewable energy evolves no CO 2 , but costs 2-3× more, making it presently economically unviable. Here catalyst-free conversion of waste plastic into clean H 2 along with high purity graphene is reported. The scalable procedure evolves no CO 2 when deconstructing polyolefins and produces H 2 in purities up to 94% at high mass yields. The sale of graphene byproduct at just 5% of its current value yields H 2 production at a negative cost. Life-cycle assessment demonstrates a 39-84% reduction in emissions compared to other H 2 production methods, suggesting the flash H 2 process to be an economically viable, clean H 2 production route., (© 2023 Wiley-VCH GmbH.)

We propose the Zn 2 V (1- x ) Nb x N 3 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 Zn 2 V (1- x ) Nb x N 3 .

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.

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.

Ammonia is an indispensable commodity in the agricultural and pharmaceutical industries. Direct nitrate-to-ammonia electroreduction is a decentralized route yet challenged by competing side reactions. Most catalysts are metal-based, and metal-free catalysts with high nitrate-to-ammonia conversion activity are rarely reported. Herein, it is shown that amorphous graphene synthesized by laser induction and comprising strained and disordered pentagons, hexagons, and heptagons can electrocatalyze the eight-electron reduction of NO 3 - to NH 3 with a Faradaic efficiency of ≈100% and an ammonia production rate of 2859 µg cm -2 h -1 at -0.93 V versus reversible hydrogen electrode. X-ray pair-distribution function analysis and electron microscopy reveal the unique molecular features of amorphous graphene that facilitate NO 3 - reduction. In situ Fourier transform infrared spectroscopy and theoretical calculations establish the critical role of these features in stabilizing the reaction intermediates via structural relaxation. The enhanced catalytic activity enables the implementation of flow electrolysis for the on-demand synthesis and release of ammonia with >70% selectivity, resulting in significantly increased yields and survival rates when applied to plant cultivation. The results of this study show significant promise for remediating nitrate-polluted water and completing the NO x cycle., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

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.

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.

Graphitic 1D and hybrid nanomaterials represent a powerful solution in composite and electronic applications due to exceptional properties, but large-scale synthesis of hybrid materials has yet to be realized. Here, a rapid, scalable method to produce graphitic 1D materials from polymers using flash Joule heating (FJH) is reported. This avoids lengthy chemical vapor deposition and uses no solvent or water. The flash 1D materials (F1DM), synthesized using a variety of earth-abundant catalysts, have controllable diameters and morphologies by parameter tuning. Furthermore, the process can be modified to form hybrid materials, with F1DM bonded to turbostratic graphene. In nanocomposites, F1DM outperform commercially available carbon nanotubes. Compared to current 1D material synthetic strategies using life cycle assessment, FJH synthesis represents an 86-92% decrease in cumulative energy demand and 92-94% decrease in global-warming potential. This work suggests that FJH affords a cost-effective and sustainable route to upcycle waste plastic into valuable 1D and hybrid nanomaterials., (© 2023 Wiley-VCH GmbH.)

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., (© 2023. The Author(s).)

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.

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 ·ϰ between the ferroelectric polarization ( P ) and the curvature of the layer (ϰ ≡ 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.

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 FePSe 3 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.

Next-generation structural materials are expected to be lightweight, high-strength and tough composites with embedded functionalities to sense, adapt, self-repair, morph and restore. This Review highlights recent developments and concepts in bioinspired nanocomposites, emphasizing tailoring of the architecture, interphases and confinement to achieve dynamic and synergetic responses. We highlight cornerstone examples from natural materials with unique mechanical property combinations based on relatively simple building blocks produced in aqueous environments under ambient conditions. A particular focus is on structural hierarchies across multiple length scales to achieve multifunctionality and robustness. We further discuss recent advances, trends and emerging opportunities for combining biological and synthetic components, state-of-the-art characterization and modelling approaches to assess the physical principles underlying nature-inspired design and mechanical responses at multiple length scales. These multidisciplinary approaches promote the synergetic enhancement of individual materials properties and an improved predictive and prescriptive design of the next era of structural materials at multilength scales for a wide range of applications., (© 2022. Springer Nature Limited.)

Bringing to fruition the tantalizing properties, foreseen since the discovery of carbon nanotubes, has been hindered by the challenge to produce a desired helical symmetry type, single chirality. Despite progress in postsynthesis separation or somewhat sporadic success in selective growth, obtaining one chiral type at will remains elusive. The kinetics analysis here shows how a local yet moving reaction zone (the gas feedstock or elevated temperature) can entice the tubes to follow, so that, remotely akin to proverbial Lamarck giraffes, only the fastest survive. Reversing the reaction to dissolution would further eliminate the too fast-reactive types so that a desired chirality is singled out in production.

The equilibrium shape of crystals is a fundamental property of both aesthetic appeal and practical importance: the shape and its facets control the catalytic, light-emitting, sensing, magnetic and plasmonic behaviors. It is also a visible macro-manifestation of the underlying atomic-scale forces and chemical makeup, most conspicuous in two-dimensional (2D) materials of keen current interest. If the crystal surface/edge energy is known for different directions, its shape can be obtained by the geometric Wulff construction, a tenet of crystal physics; however, if symmetry is lacking, the crystal edge energy cannot be defined or calculated and thus its shape becomes elusive, presenting an insurmountable problem for theory. Here we show how one can proceed with auxiliary edge energies towards a constructive prediction, through well-planned computations, of a unique crystal shape. We demonstrate it for challenging materials such as SnSe, which is of C 2v symmetry, and even AgNO 2 of C 1 , which has no symmetry at all., (© 2022. The Author(s).)

Carbon and hydrogen bonding constitute the backbone of life; in the form of graphene, possibly functionalized by DNA nucleobases, these hold promise for the programmable assembly of graphene-based nanoelectronic devices. It is still unknown how hydrogen-bonded junctions inherent in such devices will perform as electron transport media. Here, we design nucleobase-bonded graphene nanoribbons and quantify their quantum transport characteristics using first-principles calculations. Pronounced rectifying behavior and negative differential resistance are found, as well as high conductance of certain structures, with the guanine-cytosine junction in general being superior to the adenine-thymine junction. The identified sensitivity of the conductance to atomic details of the interfaces offers initial hints and guidance for experimental realization. The dependence of current on electrostatic gate doping, with an on/off ratio of ∼10 2 , shows the potential of the junction as a field effect transistor.

The incorporation of charged functional groups is effective to modulate the activity of molecular complexes for the CO 2 reduction reaction (CO 2 RR), yet long-term heterogeneous electrolysis is often hampered by catalyst leaching. Herein, an electrocatalyst of atomically thin, cobalt-porphyrin-based, ionic-covalent organic nanosheets (CoTAP-iCONs) is synthesized via a post-synthetic modification strategy for high-performance CO 2 -to-CO conversion. The cationic quaternary ammonium groups not only enable the formation of monolayer nanosheets due to steric hindrance and electrostatic repulsion, but also facilitate the formation of a *COOH intermediate, as suggested by theoretical calculations. Consequently, CoTAP-iCONs exhibit higher CO 2 RR activity than other cobalt-porphyrin-based structures: an 870% and 480% improvement of CO current densities compared to the monomer and neutral nanosheets, respectively. Additionally, the iCONs structure can accommodate the cationic moieties. In a flow cell, CoTAP-iCONs attain a very small onset overpotential of 40 mV and a stable total current density of 212 mA cm -2 with CO Faradaic efficiency of >95% at -0.6 V for 11 h. Further coupling the flow electrolyzer with commercial solar cells yields a solar-to-CO conversion efficiency of 13.89%. This work indicates that atom-thin, ionic nanosheets represent a promising structure for achieving both tailored activity and high stability., (© 2022 Wiley-VCH GmbH.)

High-surface-area α-Al 2 O 3 nanoparticles are used in high-strength ceramics and stable catalyst supports. The production of α-Al 2 O 3 by phase transformation from γ-Al 2 O 3 is hampered by a high activation energy barrier, which usually requires extended high-temperature annealing (~1500 K, > 10 h) and suffers from aggregation. Here, we report the synthesis of dehydrated α-Al 2 O 3 nanoparticles (phase purity ~100%, particle size ~23 nm, surface area ~65 m 2 g -1 ) by a pulsed direct current Joule heating of γ-Al 2 O 3 . The phase transformation is completed at a reduced bulk temperature and duration (~573 K, < 1 s) via an intermediate δ'-Al 2 O 3 phase. Numerical simulations reveal the resistive hotspot-induced local heating in the pulsed current process enables the rapid transformation. Theoretical calculations show the topotactic transition (from γ- to δ'- to α-Al 2 O 3 ) is driven by their surface energy differences. The α-Al 2 O 3 nanoparticles are sintered to nanograined ceramics with hardness superior to commercial alumina and approaching that of sapphire., (© 2022. The Author(s).)

The sensitivity of covalent organic frameworks (COFs) to pore collapse during activation processes is generally termed activation stability, and activation stability is important for achieving and maintaining COF crystallinity and porosity which are relevant to a variety of applications. However, current understanding of COF stability during activation is insufficient, and prior studies have focused primarily on thermal stability or on the activation stability of other porous materials, such as metal-organic frameworks (MOFs). In this work, we demonstrate and implement a versatile experimental approach to quantify activation stability of COFs and use this to establish a number of relationships between their pore size, the type of pore substituents, pore architecture, and structural robustness. Additionally, density functional theory calculations reveal the impact on both inter-and intra-layer interactions, which govern activation stability, and we demonstrate that activation stability can be systematically tuned using a multivariate synthesis approach involving mixtures of functionalized and unfunctionalized COF building blocks. Our findings provide novel fundamental insights into the activation stability of COFs and offer guidance for the design of more robust COFs., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

Two-dimensional (2D) bilayers, twisted to particular angles to display electronic flat bands, are being extensively explored for physics of strongly correlated 2D systems. However, the similar rich physics of one-dimensional (1D) strongly correlated systems remains elusive as it is largely inaccessible by twists. Here, a distinctive way to create 1D flat bands is proposed, by either stamping or growing a 2D monolayer on a non-Euclidean topography-patterned surface. Using boron nitride (hBN) as an example, our analysis employing elastic plate theory, density-functional and coarse-grained tight-binding method reveals that hBN's bi-periodic sinusoidal deformation creates pseudo- electric and magnetic fields with unexpected spatial dependence. A combination of these fields leads to anisotropic confinement and 1D flat bands. Moreover, changing the periodic undulations can tune the bandwidth, to drive the system to different strongly correlated regimes such as density waves, Luttinger liquid, and Mott insulator. The 1D nature of these states differs from those obtained in twisted materials and can be exploited to study the exciting physics of 1D quantum systems., (© 2022. The Author(s).)

Two-dimensional transition metal dichalcogenides (TMD), such as molybdenum disulfide (MoS 2 ), have aroused substantial research interest in recent years, motivating the quest for new synthetic strategies. Recently, halide salts have been reported to promote the chemical vapor deposition (CVD) growth of a wide range of TMD. Nevertheless, the underlying promoting mechanisms and reactions are largely unknown. Here, we employ first-principles calculations and ab initio molecular dynamics (AIMD) simulations in order to investigate the detailed molecular mechanisms during the salt-assisted CVD growth of MoS 2 monolayers. The sulfurization of molybdenum oxyhalides MoO 2 X 2 (X = F, Cl, Br, and I)─the form of Mo-feedstock dominating in salt-assisted synthesis─has been explored and displays much lower activation barriers than that of molybdenum oxide present during conventional "saltless" growth of MoS 2 . Furthermore, the rate-limiting barriers appear to depend linearly on the electronegativity of the halogen element, with oxyiodide having the lowest barrier. Our study reveals the promoting mechanisms of halides and allows growth parameter optimization to achieve even faster growth of MoS 2 monolayers in the CVD synthesis.

Electron optics is the systematic use of electromagnetic (EM) fields to control electron motions. In graphene, strain induces pseudo-electromagnetic fields to guide electron motion. Here we demonstrate the use of substrate topography to impart desirable strain on graphene to induce static pseudo-EM fields. We derive the quasi-classical equation of motion for Dirac Fermions in a pseudo-EM field in graphene and establish the correspondence between the quasi-classical and quantum mechanical snake states. Based on the trajectory analysis, we design sculpted substrates to realize various "optical devices" such as a converging lens or a collimator, and further propose a setup to achieve valley Hall effect solely through substrate patterning, without any external fields, to be used in valleytronics applications. Finally, we discuss how the predicted strain/pseudo-EM field patterns can be experimentally sustained by typical substrates and generalized to other 2D materials.

The electrochemical dinitrogen (N 2 ) reduction reaction (NRR) under ambient conditions has gained significant interest as an environmentally friendly alternative to the traditional Haber-Bosch process for the synthesis of ammonia (NH 3 ). However, up to now, most of the reported NRR electrocatalysts with satisfactory catalytic activities have been hindered by the large overpotential in N 2 activation. The preparation of highly efficient Mo-based NRR electrocatalyst in acidic electrolytes under ambient conditions is demonstrated here, consisting of stabilized single Mo atoms anchored on holey nitrogen-doped graphene synthesized through a convenient potassium-salt-assisted activation method. At -0.05 V versus a reversible hydrogen electrode (RHE), an electrode consisting of the resultant electrocatalyst immobilized on carbon fiber paper can attain an exceptional Faradaic efficiency of 50.2% and a NH 3 yield rate of 3.6 µg h -1 mg cat -1 with low overpotentials. Density functional theory calculations further unveil that compared to the original graphene without holes, the edge coordinated Mo atoms and the existence of vacancies on holey graphene lower the overpotential of N 2 reduction, thereby promoting the NRR catalytic activity. This work could provide new guidelines for future designs in single-atom catalysis that would be beneficial to ambient N 2 fixation, and replacement of classical synthesis processes that are very energy-intensive., (© 2022 Wiley-VCH GmbH.)

Two-dimensional boron (i.e. borophene) holds promise for a variety of emerging nanoelectronic and quantum technologies. Since borophene is synthesized under ultrahigh vacuum (UHV) conditions, it is critical that the chemical stability and structural integrity of borophene in oxidizing environments are understood for practical borophene-based applications. In this work, we assess the mechanism of borophene oxidation upon controlled exposure to air and molecular oxygen in UHV via scanning tunneling microscopy andspectroscopy, x-ray photoelectron spectroscopy, and density functional theory calculations. While borophene catastrophically degrades almost instantaneously upon exposure to air, borophene undergoes considerably more controlled oxidation when exposed to molecular oxygen in UHV. In particular, UHV molecular oxygen dosing results in single-atom covalent modification of the borophene basal plane in addition to disordered borophene edge oxidation that shows altered electronic characteristics. By comparing these experimental observations with density functional theory calculations, further atomistic insight is gained including pathways for molecular oxygen dissociation, surface diffusion, and chemisorption to borophene. Overall, this study provides an atomic-scale perspective of borophene oxidation that will inform ongoing efforts to passivate and utilize borophene in ambient conditions., (© 2022 IOP Publishing Ltd.)

Hydrogenated borophenes─borophanes─have recently been synthesized as a new platform for studying low-dimensional borides, but most of their lattice structures remain unknown. Here, we determine the structures of borophane polymorphs on Ag(111) by performing extensive structural search using the cluster expansion method augmented with first-principles calculations. Our results reveal rich borophane polymorphs whose stability depends on hydrogen pressure. At relatively low hydrogen pressures, borophane structures with rhombic patterns of two-center-two-electron B-H bonds are energetically preferred, in excellent agreement with two experimentally observed phases. In a wider range of hydrogen pressures, the structure with a combination of two-center-two-electron B-H and three-center-two-electron B-H-B bonds is a deep global minimum, rationalizing its experimental prevalence. For all these borophane polymorphs, their hydrogen "skin" raises the energy barriers for oxidation above 1.1 eV, while their work functions can be reduced by more than 0.5 eV through varying the hydrogen coverage.

Two-dimensional metals offer intriguing possibilities to explore the metallic and other related properties in systems with reduced dimensionality. Here, following recent experimental reports of synthesis of two-dimensional metallic gallium (gallenene) on insulating substrates, we conduct a computational search of gallenene structures using the Particle Swarm Optimization algorithm, and identify stable low energy structures. Our calculations of the critical temperature for conventional superconductivity yield values of ∼7 K for gallenene. We also emulate the presence of the substrate by introducing the external confining potential and test its effect on the structures with unstable phonons., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1 s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, Cr 2 C 3 , MoC, and W 2 C) and covalent carbides (B 4 C and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including β-Mo 2 C and metastable α-MoC 1-x and η-MoC 1-x are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000 K coupled with kinetically controlled ultrafast cooling (>10 4  K s -1 ). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with β-Mo 2 C showing the best performance., (© 2022. The Author(s).)