Atomic Scale Research Articles

Atomic Engineering of 3D Self‐Supported Bifunctional Oxygen Electrodes for Rechargeable Zinc‐Air Batteries and Fuel Cell Applications

AbstractThe oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are cornerstone half reactions involved in many renewable energy technologies. High‐density single‐atom catalysts maximize the atom utilization and isolated active sites. Furthermore, introduction of pyri‐N into the carbon‐based nanostructures as an oxygen electrocatalyst creates an abundance of active sites. Here, an innovative strategy is reported based on atomic scale dispersion of Co atoms into the pyri‐N enriched carbon nanotube encapsulated Ni nanoparticles grown on 3D electrospun carbon nanofiber nano‐assemblies. Notably, the CoSANi‐NCNT/CNF electrocatalyst exhibited excellent OER and ORR activity in terms of low overpotentials and higher half‐wave potentials. The atomically distributed Co allows the maximum exposure of active sites on the pyri‐N dominated multidimensional carbon skeleton, and synergistic effects with Ni nanoparticles greatly reduced the delocalization around the metal centers and provided an ideal environment for interactions with oxygen intermediates, thus facilitating the 4e− pathway, as evidenced by the DFT calculations. Moreover, Zn‐air batteries using a CoSANi‐NCNT/CNF air cathode exhibited a high‐power density and admirable specific capacity. This studies may provide an avenue for the rational modulation of single‐atom catalysts and cost‐effective, large‐scale synthesis of bifunctional oxygen electrocatalysts for rechargeable Zn‐air batteries and anion exchange membrane fuel cell.

AtomTex: texture characterization software for atomic configurations

Abstract A software named AtomTex has been developed for characterizing texture/orientation of atomic configurations. The software currently can generate orientation distribution functions, Miller indices, pole figures, inverse pole figures and angle-axis pairs between grains. Utilizing AtomTex, one can explicitly trace orientation evolution of a given atom, resembling an in-situ probe with atomic scale resolution, which is expected to significantly deepen understanding how microstructure evolves upon various thermomechanical treatments.

Light-induced electron dynamics of molecules in cavities: comparison of model Hamiltonians

The rapidly expanding field of polaritonic chemistry requires accurate theoretical simulations to understand new phenomena at the atomic scale. Computing the optoelectronic properties of molecules using established electronic structure methods is a careful balance of accuracy and computational expense, and expanding these methods to quantum electrodynamics to describe coupled cavity-molecule systems is an active topic of development. Key to these methods are the Hamiltonian operators representing the photon cavity modes. The recently introduced quantum electrodynamics time-dependent configuration interaction (QED-TDCI) method allows for the combination of electron dynamics simulations with quantum electrodynamics, enabling the simulation of time-dependent optoelectronic properties of cavity-molecule systems. Using this method, a comparison of two many-state QED Hamiltonians—the Pauli-Fierz and quantum Rabi model Hamiltonians—is presented, with a particular focus on time-dependent properties in applied electric fields.

A Cable-Stayed Honeycomb Superstructure to Improve the Stability of Li-Rich Materials via Inhibiting Interlaminar Lattice Strain.

In layered Li-rich materials, over stoichiometric Li forms an ordered occupation of LiTM6 in TM layer, showing a honeycomb superstructure along [001] direction. At the atomic scale, the instability of the superstructure at high voltage is the root cause of problems such as capacity/voltage decay of Li-rich materials. Here we report a Li-rich material with a high Li/Ni disorder, these interlayer Ni atoms locate above the honeycomb superstructure and share adjacent O coordination with honeycomb TM. These Ni-O bonds act as cable-stayed bridge to the honeycomb plane, and improve the high-voltage stability. The cable-stayed honeycomb superstructure is confirmed by in-situ X-ray diffraction to have a unique cell evolution mechanism that it can alleviate interlaminar lattice strain by promoting in-plane expansion along a-axis and inhibiting c-axis stretching. Electrochemical tests also demonstrate significantly improved long cycle performance after 500 cycles (86% for Li-rich/Li half cell and 82% for Li-rich/Si-C full cell) and reduced irreversible oxygen release. This work proves the feasibility of achieving outstanding stability of lithium-rich materials through superstructure regulation and provides new insights for the development of the next-generation high-energy-density cathodes. This article is protected by copyright. All rights reserved.

Computational analysis of device-to-device variability in resistive switching through single-layer hexagonal boron nitride and graphene vertical heterostructure model

Abstract We quantify the device-to-device variations in resistive switching by considering a single-layer hexagonal boron nitride and graphene junction as a model. Then, we mimic the variations in the surface of a two-dimensional material in terms of defects and interface states by changing the distance between single-layer hexagonal boron nitride and graphene. We use density functional theory as a methodology to perform simulations at the atomic scale. The results show that the distance affects the current–voltage characterization results and that creating ultra uniform structures is important to reduce the device-to-device variability. These results are crucial to understand the reliability and accuracy of device-to-device variations in memory devices and mimic the neural dynamics beyond the synaptic cleft.

Temperature and pressure-induced excitation-dependent emissions in zero-dimensional hybrid metal halides with mixed halogens.

Zero-dimensional (0D) hybrid metal halides (HMHs) have emerged as a promising platform for exploring excitation-dependent multicolor luminescent materials owing to their diverse crystal structures and chemical compositions. Nevertheless, understanding the mechanism behind excitation-dependent emissions (EDEs) in 0D HMHs and achieving precise modulation remains challenging. In this work, the delicate regulations on the EDE of 0D (DMEDABr)4SnBr3I3 (DMEDA: N, N'-dimethylethylenediamine) with mixed halogens are achieved under low temperature and high pressure, respectively. The inhomogeneous halogen occupation at the atomic scale leads to the formation of Br-rich and I-rich SnX6 (X = Br, I) octahedra, which act as distinct luminescent centers upon photoexcitation. At low temperatures, the narrowed photoluminescence spectra could distinguish the individual emissions from different luminescent centers, resulting in a pronounced EDE of (DMEDABr)4SnBr3I3. In addition, the contraction and distortion of the luminescent SnX6 (X = Br, I) centers at high pressure further result in different degrees of emission shifts, giving rise to the gradual emergence and disappearance of EDE. This work elucidates the underlying mechanism of EDE in 0D HMHs and highlights the crucial role of halogens in determining the optical properties of metal halides.

Scanning Probe Microscopies for Characterizations of 2D Materials.

2D materials are intriguing due to their remarkably thin and flat structure. This unique configuration allows the majority of their constituent atoms to be accessible on the surface, facilitating easier electron tunneling while generating weak surface forces. To decipher the subtle signals inherent in these materials, the application of techniques that offer atomic resolution (horizontal) and sub-Angstrom (z-height vertical) sensitivity is crucial. Scanning probe microscopy (SPM) emerges as the quintessential tool in this regard, owing to its atomic-level spatial precision, ability to detect unitary charges, responsiveness to pico-newton-scale forces, and capability to discern pico-ampere currents. Furthermore, the versatility of SPM to operate under varying environmental conditions, such as different temperatures and in the presence of various gases or liquids, opens up the possibility of studying the stability and reactivity of 2D materials in situ. The characteristic flatness, surface accessibility, ultra-thinness, and weak signal strengths of 2D materials align perfectly with the capabilities of SPM technologies, enabling researchers to uncover the nuanced behaviors and properties of these advanced materials at the nanoscale and even the atomic scale.

In Operando X-ray Spectroscopic and DFT Studies Revealing Improved H2 Evolution by the Synergistic Ni-Co Electron Effect in the Alkaline Condition.

The different electrolyte conditions, e.g., pH value, for driving efficient HER and OER are one of the major issues hindering the aim for electrocatalytic water splitting in a high efficiency. In this regard, seeking durable and active HER electrocatalysts to align the alkaline conditions of the OER is a promising solution. However, the success in this strategy will depend on a fundamental understanding about the HER mechanism at the atomic scale. In this work, we have provided thorough understanding for the electrochemical HER mechanisms in KOH over Ni- and Co-based hollow pyrite microspheres by in operando X-ray spectroscopies and DFT calculations, including NiS2, CoS2, and Ni0.5Co0.5S2. We discovered that the Ni sites in hollow NiS2 microspheres were very stable and inert, while the Co sites in hollow CoS2 microspheres underwent reduction and generated Co metallic crystal domains under HER. The generation of Co metallic sites would further deactivate H2 evolution due to the large hydrogen desorption free energy (-1.73 eV). In contrast, the neighboring Ni and Co sites in hollow Ni0.5Co0.5S2 microspheres exhibited the electronic interaction to elevate the reactivity of Ni and facilitate the stability of Co without structure or surface degradation. The energy barrier in H2O adsorption/dissociation was only 0.73 eV, followed by 0.06 eV for hydrogen desorption over the Ni0.5Co0.5S2 surface, revealing Ni0.5Co0.5S2 as a HER electrocatalyst with higher durability and activity than NiS2 and CoS2 in the alkaline medium due to the synergy of neighboring Ni and Co sites. We believe that the findings in our work offer a guidance toward future catalyst design.

Unveiling the Potential Scope of Nanoparticles in the Current Era of Crop Productivity

Nanotechnology, a revolutionary field encompassing the manipulation of matter on an atomic or molecular scale, holds immense potential for upgrading wide areas, including agriculture. Understanding the scope of nanotechnology, researchers have directed their focus towards addressing the challenges in agriculture and enhancing crop productivity. Nanoparticles offer unique properties, including high surface area and reactivity, that can be harnessed to optimize nutrient delivery, mitigate soil toxicity, and enhance plant growth. Various studies have demonstrated the effectiveness of nanoparticles in increasing crop yields, improving nutrient uptake efficiency, and reducing environmental impacts associated with conventional agricultural practices with sustainable agriculture. Nanotechnology overcomes various challenges encountered in traditional agricultural practices including limited availability of nutrients in the soil, inefficient nutrient uptake by plants, soil degradation, and environmental pollution by providing targeted nutrient delivery, improving nutrient absorption, and mitigating environmental impacts. Also, nanoparticle interactions with plants and microbes and strengthening symbiotic relationships by providing active nutrient supplies to microbes. Furthermore, nanoparticles can improve soil structure and fertility by reducing compaction, increasing water retention, and enhancing soil aggregation. These improvements in soil quality not only benefit crop growth but also contribute to sustainable land management practices.This review paper provides an overview of the current research landscape in the application of nanoparticles in agriculture, highlighting key findings, challenges, and future prospects. By leveraging the principles of nanotechnology, agricultural scientists and practitioners aim to revolutionize crop production, meet the needs of farmers, and ensure food security in the face of evolving environmental and socio-economic challenges.

Unit‐Cell‐Thickness Electron Confinement by Geometrically Constrained Antipolar Ordering

AbstractAchieving precise electron or spin confinement is essential for the progress of oxide electronics and emerging quantum information processing. While 2D electron confinement is commonly achieved with bare surfaces, heteroepitaxial interfaces, and charged domain walls, its practical application poses challenges, notably by diverse confinement widths, limited material selection, and the lack of freedom of positioning to a desired location within a given material system. Here, with scrutinizing a novel defect structure, the study suggests a new strategy with compelling evidence to trigger electron confinement down to single unit‐cell‐thickness, through geometrically constrained antipolar ordering facilitated by superlattice‐like periodic planar faults in metallic SrFeO3. Employing atomic resolution electron microscopy and density functional theory, the results demonstrate that electrons are confined two‐dimensionally to screen the positive bound charges on head‐to‐head antipolar state boundary, meanwhile oxygen vacancies segregated in the planar faults compensate the negative bound charges on the tail‐to‐tail one, leading to the stabilization of the antipolar ordering. Additionally, distinguished from traditional methods, this approach offers a potential programing capability for achieving precise charge and spin control by regulating planar fault structure at atomic scale.

Assessment of the potential structure and nucleation efficacy of multi-component heterogeneous substrate

In recent years, nucleation of multi-component heterogeneous interface structures has attracted increasing attention due to their excellent grain refinement and anti-poisoning capabilities in Al-Si alloy. In this research, a general methodology was proposed to predict the surface structure and meanwhile evaluate the grain refinement efficacy of the multi-component boride nucleants based on a comprehensive experimental and theoretical study of a novel Al-Si alloy refiner, i.e., Al-3.5Nb-1V-1B. By using high-resolution electron microscopy, the (Nb, V)B2 particle with a characteristic “core-shell” surface structure was observed, attributed to V adsorption driven by interfacial energy minimization, validated by ab initio calculations. A general interfacial energy-based model was then proposed which predicts the multi-component boride substrate structure, well consistent with the experimental findings. The nucleation potency of different substrates was analyzed in atomic scale and only if the interfacial atomic vibration was considered together with the nucleation-influencing factors (i.e., the lattice mismatch and the anti Si-poisoning effect), the predicted nucleation potency order can agree well with the experimental results. A thermodynamics-kinetics combined analytic model was summarized by coupling the lattice mismatch parameter, the interfacial Si adsorption energy and the interfacial atomic vibration amplitude, which accurately evaluates the multi-component boride grain refiners for the Al-Si alloys.

Role of threshold stress in creep of IN740H, a γ′-lean Ni-based superalloy

IN740H, a Ni-based superalloy comprising a low-volume fraction of γ′, is a candidate material to be used over long periods at high temperatures and stresses, as conditions prevalent in advanced ultra-supercritical (AUSC) power plants. In this study, IN740H has been tested at temperatures above 700 °C to gain mechanistic insights into its high-temperature creep behavior. The material showed classic signatures of the presence of threshold stress, marked by observation of a high apparent creep stress exponent, n, (e.g., 10 at 750 °C) and a high apparent activation energy for creep, Qc (e.g., ∼545 kJ/mol), along with a rapid increase in n at lower stresses. Accounting for the threshold stress led to a decrease in the values of n and Qc to 4 and 280 kJ/mol, respectively. Furthermore, the transmission electron microscopy and atomic scale compositional analysis reveal the pinning of dislocations at γ-γ′ interface and segregation of Co, Cr and Mo atoms in the regions of γ-γ′ interface rich in dislocations. The above combination of n and Qc and the observation of dislocation pinning at the γ-γ′ interface indicate the dislocation climb over γ′ as the dominant creep mechanism in this γ′-lean Ni-based superalloy, with the detachment of dislocations from the γ-γ′ interface, augmented by the segregation of Co, Cr and Mo, as the mechanism responsible for the realization of the threshold stress. This work, thus, provides a new impetus to research on the long-term structural integrity of γ′-lean Ni-based superalloys exposed to extreme service conditions.

Irradiation multi-scale damage and interface effects of 3D braided carbon fiber/epoxy composites subjected to high dose γ-rays

The serious damage caused to 3D braided carbon fiber (CF)/epoxy (EP) composites in high-energy irradiation environments is a pressing research topic that has not yet been reported. This study analyzed the γ-irradiation multi-scale damage of the matrix, interfaces, and near-interface regions in 3D braided CF/EP composites with three different braiding angles (18°, 28°, 38°) at atomic, microscopic, and macroscopic scales. The molecular structure and atomic charge information alterations of epoxy matrix were characterized using soft X-ray absorption spectroscopy (sXAS). When the irradiation dose reached 1000 KGy, the compressive strength of composites decreased by 20.88 %, 18.07 %, and 16.60 %, respectively, with an increase in the braiding angle. Micro-CT observation, along with statistical computing, confirmed that irradiation causes interface damage and increases the defect volume of 3D braided composites. Nanoindentation was used to compare the modulus of carbon fiber, interface, near-interface regions and matrix in irradiated composites and the function of CF/resin interface as an irradiation defect capture site in the irradiation resistance of resin-matrix composites has been newly established. In addition, the mechanism behind the effect of braiding angle on macroscopic properties was also analyzed.

Enhancing surface strength of tungsten by gradient nano-grained structure

A gradient nano-grained (GNG) structure demonstrates satisfactory surface strength. However, the underlying mechanism responsible for its strengthening lacks sufficient research. To explain how gradient nano-grained structures improve surface strength in detail, large-scale parallel molecular dynamics simulations are utilized in this study to investigate the mechanical deformation behavior of BCC tungsten with varying grain sizes during spherical nanoindentation. The findings suggest that a well-designed gradient structure can promote rational plasticity and an appropriate distribution of internal atomic stress. The critical point of maximum stress and hardness is observed when the initial grain size is 4.5 nm, with an average grain size of 7.1 nm. The interaction between grain boundary slip and migration in small grains, along with the enhanced activity of grain boundary dislocations in large grains, collectively contributes to the enhancement of the strength and hardness of the GNG structure. Compared with a homogeneous nano-grained structure, the gradient nano-grained structure exhibits a more rational distribution of dislocations and stress relaxation effects to enhance strength. The present work utilizes the molecular dynamics nanoindentation method to study GNG materials, providing a methodology for investigating the surface strengthening effects of GNG structures at the atomic scale and effectively revealing potential mechanisms for resisting surface deformation in GNG structures.

2D Janus Polarization Functioned by Mechanical Force.

2Dpolarization materials have emerged as promising candidates for meeting the demands of device miniaturization, attributed to their unique electronic configurations and transport characteristics. Although the existing inherent and sliding mechanisms are increasingly investigated in recent years, strategies for inducing 2D polarization with innovative mechanisms remain rare. This study introduces a novel 2D Janus state by modulating the puckered structure. Combining scanning probe microscopy, transmission electron microscopy, and density functional theory calculations, this work realizes force-triggered out-of-plane and in-plane dipoles with distorted smaller warping in GeSe. The Janus state is preserved after removing the external mechanical perturbation, which could be switched by modulating the sliding direction. This work offers a versatile method to break the space inversion symmetry in a 2D system to trigger polarization in the atomic scale, which may open an innovative insight into configuring novel 2D polarization materials.

Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8GHz, RLmin = -46dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

Calculating Binding Free Energies in Model Host-Guest Systems with Unrestrained Advanced Sampling.

Host-guest interactions are important to the design of pharmaceuticals and, more broadly, to soft materials as they can enable targeted, strong, and specific interactions between molecules. The binding process between the host and guest may be classified as a "rare event" when viewing the system at atomic scales, such as those explored in molecular dynamics simulations. To obtain equilibrium binding conformations and dissociation constants from these simulations, it is essential to resolve these rare events. Advanced sampling methods such as the adaptive biasing force (ABF) promote the occurrence of less probable configurations in a system, therefore facilitating the sampling of essential collective variables that characterize the host-guest interactions. Here, we present the application of ABF to a rod-cavitand coarse-grained model of host-guest systems to acquire the potential of mean force. We show that the employment of ABF enables the computation of the configurational and thermodynamic properties of bound and unbound states, including the free energy landscape. Moreover, we identify important dynamic bottlenecks that limit sampling and discuss how these may be addressed in more general systems.

In Situ Self‐Assembled Active and Stable Ir@MnOx/La0.7Sr0.3Cr0.9Ir0.1O3‐δ Interfaces for CO2 Electrolysis

Solid oxide electrolysis cells are prospective approaches for CO2 utilization but face significant challenges due to the sluggish reaction kinetics and poor stability of the fuel electrodes. Herein, we strategically addressed the long‐standing trade‐off phenomenon between enhanced exsolution and improved structural stability via topotactic ion exchange. The surface dynamic reconstruction of the MnOx/La0.7Sr0.3Cr0.9Ir0.1O3‐δ (LSCIr) catalyst was visualized at the atomic scale. Compared with the Ir@LSCIr interface, the in situ self‐assembled Ir@MnOx/LSCIr interface exhibited greater CO2 activation and easily removable carbonate intermediates, thus reached a 42% improvement in CO2 electrolysis performance at 1.6 V. Furthermore, an improved CO2 electrolysis stability was achieved due to the uniformly wrapped MnOx shell of the Ir@MnOx/LSCIr cathode. Our approach enables a detailed understanding of the dynamic microstructure evolution at active interfaces and provides a roadmap for the rational design and evaluation of efficient metal/oxide catalysts for CO2 electrolysis.

In Situ Self-Assembled Active and Stable Ir@MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ Interfaces for CO2 Electrolysis.

Solid oxide electrolysis cells are prospective approaches for CO2 utilization but face significant challenges due to the sluggish reaction kinetics and poor stability of the fuel electrodes. Herein, we strategically addressed the long-standing trade-off phenomenon between enhanced exsolution and improved structural stability via topotactic ion exchange. The surface dynamic reconstruction of the MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ (LSCIr) catalyst was visualized at the atomic scale. Compared with the Ir@LSCIr interface, the in situ self-assembled Ir@MnOx/LSCIr interface exhibited greater CO2 activation and easily removable carbonate intermediates, thus reached a 42% improvement in CO2 electrolysis performance at 1.6 V. Furthermore, an improved CO2 electrolysis stability was achieved due to the uniformly wrapped MnOx shell of the Ir@MnOx/LSCIr cathode. Our approach enables a detailed understanding of the dynamic microstructure evolution at active interfaces and provides a roadmap for the rational design and evaluation of efficient metal/oxide catalysts for CO2 electrolysis.

Atomic-Scale Tracking Topological Phase Transition Dynamics of Polar Vortex-Antivortex Pairs.

Non-trivial topological structures, such as vortex-antivortex (V-AV) pairs, have garnered significant attention in the field of condensed matter physics. However, the detailed topological phase transition dynamics of V-AV pairs, encompassing behaviors like self-annihilation, motion, and dissociation, have remained elusive in real space. Here, we employ polar V-AV pairs as a model system and track their transition pathways with atomic-scale resolution, facilitated by in situ (scanning) transmission electron microscopy and phase field simulations. Our investigation reveals that polar vortices and antivortices can stably coexist as bound pairs at room temperature, and their polarization decreases with heating. No dissociation behavior is observed between the V-AV phase at room temperature and the paraelectric phase at high temperature. However, the application of electric fields can promote the approach of vortex and antivortex cores, ultimately leading to their annihilation near the interface. Revealing the transition process mediated by polar V-AV pairs at the atomic scale, particularly the role of polar antivortex, provides us new insights into understanding the topological phases of matter and their topological phase transitions. Moreover, the detailed exploration of the dynamics of polar V-AV pairs under thermal and electrical fields lays a solid foundation for their potential applications in electronic devices. This article is protected by copyright. All rights reserved.