2D Ruthenium-Chromium Oxide with Rich Grain Boundaries Boosts Acidic Oxygen Evolution Reaction Kinetics.

Ruthenium oxide is currently considered as the promising alternative to Ir-based catalysts employed for proton exchange membrane water electrolyzers but still faces the bottlenecks of limited durability and slow kinetics. Herein, a 2D amorphous/crystalline heterophase ac-Cr0.53Ru0.47O2-δ substitutional solid solution with pervasive grain boundaries (GBs) is developed to accelerate the kinetics of acidic oxygen evolution reaction (OER) and extend the long-term stability simultaneously. The ac-Cr0.53Ru0.47O2-δ shows a super stability with a slow degradation rate and a remarkable mass activity of 455 A gRu -1 at 1.6 V vs RHE, which is ≈3.6- and 5.9-fold higher than those of synthesized RuO2 and commercial RuO2, respectively. The strong interaction of Cr-O-Ru local units in synergy with the specific 2D structural characteristics of ac-Cr0.53Ru0.47O2-δ dominates its enhanced stability. Meanwhile, high-density GBs and the shortened Ru-O bonds tailored by amorphous/crystalline structure and Cr-O-Ru interaction regulate the adsorption and desorption rates of oxygen intermediates, thus accelerating the overall acidic OER kinetics.

Synergistic Effect of Grain Boundaries and Oxygen Vacancies on Enhanced Selectivity for Electrocatalytic CO2 Reduction.

Dual-engineering involved of grain boundaries (GBs) and oxygen vacancies (VO) efficiently engineers the material's catalytic performance by simultaneously introducing favorable electronic and chemical properties. Herein, a novel SnO2 nanoplate is reported with simultaneous oxygen vacancies and abundant grain boundaries (V,G-SnOx/C) for promoting the highly selective conversion of CO2 to value-added formic acid. Attributing to the synergistic effect of employed dual-engineering, the V,G-SnOx/C displays highly catalytic selectivity with a maximum Faradaic efficiency (FE) of 87% for HCOOH production at -1.2 V versus RHE and FEs > 95% for all C1 products (CO and HCOOH) within all applied potential range, outperforming current state-of-the-art electrodes and the amorphous SnOx/C. Theoretical calculations combined with advanced characterizations revealed that GB induces the formation of electron-enriched Sn site, which strengthens the adsorption of *HCOO intermediate. While GBs and VO synergistically lower the reaction energy barrier, thus dramatically enhancing the intrinsic activity and selectivity toward HCOOH.

The Role of Grain Boundaries on Ion Migration and Charge Recombination in Halide Perovskites.

Grain boundaries (GBs) have a significant role in polycrystalline perovskite solar cells (PSCs). However, there is ongoing debate regarding the impact of GBs on the performance and long-term stability of PSCs. Employing the first-principles molecular dynamics for perovskites, the iodine vacancy defect migrations both in bulk and at GBs are investigated. i) The positive iodine vacancy (VI +) is found that have both lower formation energy (1.4 eV) and activation energy (0.18 eV) than those of neutral iodine vacancy (VI), statistically. It indicated the VI + acts as the dominant migrated iodine vacancy rather than VI; ii) the iodine vacancy at GBs has ≈0.48 eV higher activation energy than those in bulk, which leads to the accumulation of iodine vacancy at GBs; iii) the presence of VI + result in a 3-fold increase in charge recombination ratio at GBs, compared to pristine PSCs. Based on quantum molecular dynamics statistical results, which are consistent with experimental measurements, insights into iodine vacancy migration both at GBs and in the bulk are gained. This understanding can be valuable for defects engineering related to ion migration, in order to improve the long-term stability and promote the performance of PSCs.

Epifluorescence microscopy study of a quadruple node of triple junctions of grain boundaries in a Eu2+-decorated highly textured composite of (Cl, Br)(K, Rb) and I(K, Rb) solid solutions.

The structural nature and geometry, as well as the lattice-relative orientation, of an arrangement of crystal defects in a highly textured Eu2+-doped composite of two alkali-halide solid solutions was studied by epifluorescence microscopy (EFM) using the doping ion as a fluorochrome. A three-dimensional reconstruction and a skeleton type model, as built from a sequence of EFM images of different optical cross-sections of this arrangement, are presented. Structurally, this arrangement is a quadruple node (QN) of triple junctions of grain boundaries. The QN core geometry is that of a tetragonal tristetrahedron (TTTH), centred at the QN site, whose tetrahedron vertices and edges are on the QN triple junctions and grain boundaries, respectively, whereas the tristetrahedron tetragonal axis is nearly parallel to the lattice [001]-axis. The measured values of the angles between triple junctions and between the grain boundaries forming them are reported. The distinct chemical compositions of the composite solid solutions are discussed to be responsible, in last instance, for the tristetrahedron departure from a cubic configuration. Collaterally, certain families of translationally periodic almost-parallel (TPAP)-wall-like regions which consist of TPAP-columns of TPAP-spindle-like singularities, as well as certain zigzag arrays of columns of this like, existing into the QN grains, are reported to be observed. Three-dimensional reconstructions of typical individuals of these families and arrays as well as of their constituent parts are presented and geometrically analysed. These families and arrays are discussed to be families of tilt subboundaries, whose constituent dislocations are decorated by cylindrical second-phase europium di-halide precipitates, and regularly faceted tilt subboundaries, respectively. Crystal growing and sample preparation, composite structural characterisation by powder and single-slab X-ray diffraction (PXRD and SSXRD, respectively), microscopy and fluorescence-cube unit optics, image processing, electronic three-dimensional reconstruction and measuring methodologies, are all described in detail.

Performance Degradation of a Double-Perovskite PrBaCo2O5+δ Cathode Operating under a CO2/H2O-Containing Atmosphere.

The electrochemical activity and stability of the PBCO electrode are investigated under the annealing processes in an atmosphere containing CO2/H2O for solid oxide fuel cells (SOFCs). The electrochemical impedance spectrum results unequivocally confirm the significant deterioration in PBCO cathode performance upon annealing under ambient air conditions, particularly when exposed to CO2/H2O atmospheres. Microstructure and surface chemical state analyses reveal the segregation of BaO on the PBCO surface, and the formation of insulating BaCO3 degraded the electrochemical performance. CO2 and H2O exhibit a significant induced effect on the segregation of Ba in PBCO to the surfaces, thereby causing a rapid decline in electrode performance. Additionally, the analysis of volume relaxation reveals that the presence of oxygen in the electrode environment can also influence the deposition process occurring on the surface of the electrode. However, this phenomenon is not observed in N2. This study emphasizes the impact of various gases present in the working atmosphere on surface-separated BaO, which consequently plays a pivotal role in the activity and long-term stability of PBCO electrodes.

The Importance of Sintering-Induced Grain Boundaries in Copper Catalysis to Improve Carbon-Carbon Coupling.

Syngas conversion serves as a gas-to-liquid technology to produce liquid fuels and valuable chemicals from coal, natural gas, or biomass. During syngas conversion, sintering is known to deactivate the catalyst owing to the loss of active surface area. However, the growth of nanoparticles might induce the formation of new active sites such as grain boundaries (GBs) which perform differently from the original nanoparticles. Herein, we reported a unique Cu-based catalyst, Cu nanoparticles with in situ generated GBs confined in zeolite Y (denoted as activated Cu/Y), which exhibited a high selectivity for C5+ hydrocarbons (65.3 C%) during syngas conversion. Such high selectivity for long-chain products distinguished activated Cu/Y from typical copper-based catalysts which mainly catalyze methanol synthesis. This unique performance was attributed to the GBs, while the zeolite assisted the stabilization through spatial confinement. Specifically, the GBs enabled H-assisted dissociation of CO and subsequent hydrogenation into CHx*. CHx* species not only serve as the initiator but also directly polymerize on Cu GBs, known as the carbide mechanism. Meanwhile, the synergy of GBs and their vicinal low-index facets led to the CO insertion where non-dissociative adsorbed CO on low-index facets migrated to GBs and inserted into the metal-alkyl bond for the chain growth.

Cold-Sintered ZnO Ceramic Composites Co-Doped with Polytetrafluoroethylene and Oxides.

Grain boundaries play a significant role in determining the performance of ceramic-based materials. The modulation of interfacial structures provides a promising approach to improve the physicochemical and electrical properties of ceramic materials. In this work, the grain boundary structures of ZnO-based ceramics were manipulated by incorporating polytetrafluoroethylene (PTFE) and metal oxides through the cold sintering process (CSP). It was found that the grain size of ZnO-based ceramics can be effectively reduced from 525.93 nm to 338.08 nm with an addition of PTFE and metal oxides of CoO and Mn2O3. Microstructural results show that most of the PTFE phase and metal oxides were distributed along the grain boundaries, which may lead to the increased grain boundary resistance from 1.59 × 106 ohm of pure ZnO to 6.21 × 1010 ohm of ZnO-based ceramics doped with PTFE and metal oxides, and enhanced Schottky barrier height from 0.32 eV to 0.59 eV. As a result, the breakdown field and nonlinear coefficient of the ZnO-based ceramics were improved to 3555.56 V/mm and 13.55, respectively. Therefore, this work indicates that CSP presents a feasible approach to design functional ceramic composites through the integration of polymer and metal oxides.

Effect and Regulation Mechanism of Post-deposition Annealing on the Ferroelectric Properties of AlScN Thin Films.

Integrating ferroelectric AlScN with III-N semiconductors to enhance the performance and tunability of nitride devices requires high-quality AlScN films. This work focuses on the effect and regulation mechanism of post-annealing in pure N2 on the crystal quality and ferroelectric properties of AlScN films. It is found that the crystal quality improves with increasing annealing temperatures. Remarkably, the leakage current of AlScN films caused by grain boundaries could be reduced by four orders of magnitude after annealing at 400 °C. The crystal growth dynamics simulations and band structure calculations indicate that the energy supplied by the temperature facilitates the evolution of abnormally oriented grains to have a better c-axis orientation, resulting in the defect states at the Fermi-level disappearing, which is mainly the reason for the leakage current decrease. More interestingly, the reduction of leakage current leads to the previously leaking region exhibiting ferroelectric properties, which is of great significance to improve the ferroelectricity of AlScN and ensure the uniformity of devices. Furthermore, annealing enhances the tensile strain on the film, which flattens the energy landscape of ferroelectric switching and reduces the coercive field. However, the risk of incorporation of oxygen will also be increased if the annealing temperatures are higher than 400 °C, which will not only reduce the relative displacement of metal atoms and nitrogen atoms in AlScN but also enhance the ferroelectric depolarization field, leading to the remnant polarization decreasing dramatically. These discoveries facilitate a deeper understanding of the influencing mechanism on the ferroelectric properties of AlScN films and provide a direction for obtaining high-quality AlScN.

Metastable grain boundaries: the roles of structural and chemical disorders in their energetics, non-equilibrium kinetic evolution, and mechanical behaviors.

Complex environments in advanced manufacturing usually involve ultrafast laser or ion irradiation which leads to rapid heating and cooling and drives grain boundaries (GBs) to non-equilibrium states, featuring distinct energetics and kinetic behaviors compared to conventional equilibrium or near-equilibrium GBs. In this topical review, we provide an overview of both recent experimental and computational studies on metastable GBs, i.e. their energetics, kinetic behaviors, and mechanical properties. In contrast to GBs at thermodynamic equilibrium, the inherent structure energy of metastable GBs exhibits a spectrum instead of single value for a particular misorientation, due to the existence of microstructural and chemical disorder. The potential energy landscape governs the energetic and kinetic behaviors of metastable GBs, including the ageing/rejuvenating mechanism and activation barrier distributions. The unique energetics and structural disorder of metastable GBs lead to unique mechanical properties and tunability of interface-rich nanocrystalline materials. We also discuss that, in addition to structural disorder, chemical complexity in multi-components alloys could also drive the GBs away from their ground states and, subsequently, significantly impact on the GBs-mediated deformation. And under some extreme conditions such as irradiation, structural disorders and chemical complexity may simultaneously present at interfaces, further enriching of metastability of GBs and their physical and mechanical behaviors. Finally, we discuss the machine learning techniques, which have been increasingly employed to predict and understand the complex behaviors of metastable GBs in recent years. We highlight the potential of data-driven approaches to revolutionize the study of disorder systems by efficiently extracting the relationship between structural features and material properties. We hope this topical review paper could shed light and stimulate the development of new GBs engineering strategies that allow more flexibility and tunability for the design of nano-structured materials.

Defects and Defect Engineering of Two-Dimensional Transition Metal Dichalcogenide (2D TMDC) Materials.

As layered materials, transition metal dichalcogenides (TMDCs) are promising two-dimensional (2D) materials. Interestingly, the characteristics of these materials are transformed from bulk to monolayer. The atomically thin TMDC materials can be a good alternative to group III-V and graphene because of their emerging tunable electrical, optical, and magnetic properties. Although 2D monolayers from natural TMDC materials exhibit the purest form, they have intrinsic defects that limit their application. However, the synthesis of TMDC materials using the existing fabrication tools and techniques is also not immune to defects. Additionally, it is difficult to synthesize wafer-scale TMDC materials for a multitude of factors influencing grain growth mechanisms. While defect engineering techniques may reduce the percentage of defects, the available methods have constraints for healing defects at the desired level. Thus, this holistic review of 2D TMDC materials encapsulates the fundamental structure of TMDC materials, including different types of defects, named zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D). Moreover, the existing defect engineering methods that relate to both formation of and reduction in defects have been discussed. Finally, an attempt has been made to correlate the impact of defects and the properties of these TMDC materials.

D-Band Engineering in Pd-Based Nanowire Networks for Further Enhancement in Ethanol Electrooxidation Reaction.

The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00 A mgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.

Strain-Assisted Phase Transformation in Two-Dimensional Transition-Metal Dichalcogenides.

Two-dimensional polymorphic transition-metal dichalcogenides have drawn attention for their diverse applications. This work explores the complex interplay between strain-induced phase transformation and crack growth behavior in annealed nanocrystalline MoS2. Employing molecular dynamics (MD) simulations, this research focuses on the effect of grain size, misorientation, and annealing on phase evolution and their effects on the mechanical behavior of MoS2. First, examining phase transformation in monocrystalline MoS2 under various stress states reveals distinct behaviors depending on the initial phase (1T or 2H) and crystallographic orientation with respect to loading directions. Notably, transformation from a layered hexagonal to a body-centered tetragonal structure is more noticeable when strain in a zigzag direction is applied to the 1T sample. As such, single crystalline MoS2 with a 1T phase exhibits a 16% lower fracture stress in the armchair direction compared to that with a 2H phase. On the other hand, the 1T phase shows a 5% higher phonon lifetime compared to the 2H phase with similar phonon group velocities. Next, the influence of thermal energy and mechanical stress on the phase transformation of nanocrystalline MoS2 is investigated through annealing and quenching cycles, uncovering 60 and 44% irreversibility of phase transformation for an average grain size of 3 and 11 nm, respectively. Besides, the evolution of nanocrystalline samples with different initial phases and grain sizes is studied under uniaxial and biaxial stress. This study shows an inverse pseudo-Hall-Petch effect with exponents of 0.11 and 0.09 for 2H and 1T, respectively. The study reveals that phase transformation can occur concurrently with crack initiation and propagation with the 1T phase exhibiting a 19% lower grain size sensitivity of fracture stress compared to the 2H phase.

Inorganic Composition Modulation of Solid Electrolyte Interphase for Fast Charging Lithium Metal Batteries.

The solid electrolyte interphase (SEI) with lithium fluoride (LiF) is critical to the performance of lithium metal batteries (LMBs) due to its high stability and mechanical properties. However, the low Li ion conductivity of LiF impedes the rapid diffusion of Li ions in the SEI, which leads to localized Li ion oversaturation dendritic deposition and hinders the practical applications of LMBs at high-current regions (>3 C). To address this issue, a fluorophosphated SEI rich with fast ion-diffusing inorganic grain boundaries (LiF/Li3P) is introduced. By utilizing a sol electrolyte that contains highly dispersed porous LiF nanoparticles modified with phosphorus-containing functional groups, a fluorophosphated SEI is constructed and the presence of electrochemically active Li within these fast ion-diffusing grain boundaries (GBs-Li) that are non-nucleated is demonstrated, ensuring the stability of the Li || NCM811 cell for over 1000 cycles at fast-charging rates of 5 C (11 mA cm-2). Additionally, a practical, long cycling, and intrinsically safe LMB pouch cell with high energy density (400 Wh kg-1) is fabricated. The work reveals how SEI components and structure design can enable fast-charging LMBs.

Ligand-Induced In Situ Epitaxial Growth of PbI2 Nanosheets/MAPbI3 Heterojunction Realizes High-Performance HTM-Free Carbon-Based MAPbI3 Solar Cells.

Hole-transporting layer-free carbon-based perovskite solar cells (HTL-free C-PSCs) hold great promise for photovoltaic applications due to their low cost and outstanding stability. However, the low power conversion efficiency (PCE) of HTL-free C-PSCs mainly results from grain boundaries (GBs). Here, epitaxial growth is proposed to rationally design a hybrid nanostructure of PbI2 nanosheets/perovskite with the desired photovoltaic properties. A post-treatment technique using tri(2,2,2-trifluoromethyl) phosphate (TFEP) to induce in situ epitaxial growth of PbI2 nanosheets at the GBs of perovskite films realizes high-performance HTL-free C-PSCs. The structure model and high-resolution transmission electron microscope unravel the epitaxial growth mechanism. The epitaxial growth of oriented PbI2 nanosheets generates the PbI2 /perovskite heterojunction, which not only passivates defects but forms type-I band alignment, avoiding carrier loss. Additionally, Fourier-transform infrared spectroscopy, 31 P NMR, and 1 H NMR spectra reveal the passivation effect and hydrogen bonding interaction between TFEP and perovskite. As a result, the VOC is remarkably boosted from 1.04 to 1.10 V, leading to a substantial gain in PCE from 14.97% to 17.78%. In addition, the unencapsulated PSC maintains the initial PCE of 80.1% for 1440 h under air ambient of 40% RH. The work offers a fresh perspective on the rational design of high-performance HTL-free C-PSCs.

Mechanism Analysis for the Enhancement of Low-Temperature Impact Toughness of Nodular Cast Iron by Heat Treatment.

The low-temperature impact toughness of nodular cast iron can be significantly enhanced by heat treatment, and thus meet the severe service requirements in the fields of high-speed rail and power generation, etc. In order to explore the enhancement mechanism, microstructure, hardness, composition and other characteristics of as-cast and heat-treated nodular cast iron is systematically tested and compared by optical microscopy, microhardness tester, EBSD, SEM, electron probe, and impact toughness testing machine in this study. The results show that heat treatment has little effect on the morphology and size of graphite in nodular cast iron, ignores the effect on the grain size, morphology, and distribution of ferritic matrix, and has little effect on the hardness and exchange of elements, while it is meaningful to find that heat treatment brings about significant decrease in high-angle grain boundaries (HAGB) between 59° and 60°, decreasing from 10% to 3%. Therefore, the significant enhancement of low-temperature impact toughness of nodular cast iron by heat treatment may result from the obvious decrease in HAGB between 59° and 60°, instead of other reasons. From this perspective, the study can provide novel ideas for optimizing the heat treatment process of nodular cast iron.

Investigation of Grain Boundary Effects in Sm0.2Ce0.8O2-x Thin Film Memristors.

Cerium-based materials (CeO2-x) are of significant interest in the development of vacancy-modulated resistive switching (RS) memory devices. However, the influence of grain boundaries on the performance of memristors is very limited. To fill this gap, this study explores the influence of grain boundaries in cerium-based thin film resistive random-access memory (RRAM) devices. Sm0.2Ce0.8O2-x (SDC20) thin films were deposited on (100)-oriented Nb-doped SrTiO3 (NSTO) and (110)-oriented NSTO substrates using pulsed laser deposition (PLD). Devices constructed with a Pt/SDC20/NSTO structure exhibited reversible and stable bipolar resistive switching (RS) behavior. The differences in conduction mechanisms between single-crystal and polycrystalline devices were confirmed, with single-crystal devices displaying a larger resistance window and higher stability. Combining the results of XPS and I-V curve fitting, it was confirmed that defects near the grain boundaries in the SDC-based memristors capture electrons, thereby affecting the overall performance of the RRAM devices.

Interfacial Rivet to Fill Structural Defects: A Spacer Engineering Gift for 3D Solar Cells.

The combination of 2D and 3D perovskites to passivate surfaces or interfaces with a high concentration of defects shows great promise for improving the efficiency of perovskite solar cells (PSCs). Constructing high-quality perovskite film systems by precisely modulating 2D perovskites with good morphologies and growth sites on 3D perovskite films remains a formidable challenge due to the complexity of spacer-engineered surface reactions. In this study, phase-pure 2D (HA)2(MA)n-1PbnI3n+1 perovskites with a controlled number of layers (n) are separated on a large scale and exploited as interface rivets to optimize 3D perovskite films, resulting in tunable film structural defects and grain boundaries. The optimized PSCs system benefits from a reduction in non-radiative recombination, resulting in improved optical performance, higher mobility, and lower trap density. The corresponding device achieves a champion power conversion efficiency (PCE) of more than 25%, especially for voltage (VOC) and fill factor (FF). The quality and uniformity of the perovskite films are further confirmed using large-area devices with an active area of 14 cm2, which exhibits a PCE of more than 21.24%. The high-quality thin-film system based on the 2D perovskites presented herein provides a new perspective for improving the efficiency and stability of PSCs.

Diffusion-reaction model of positron annihilation for complex defect pattern.

The increasing structural complexity in modern material science is often associated with grain sizes in theµm- and the sub-µm-regime. Therefore, when positron annihilation is applied for studying free-volume type defects in such materials, positron trapping at grain boundaries (GBs) cannot be neglected, even when other defect types are in the primary focus. For this purpose, the available diffusion-reaction model for positron trapping and annihilation at GBs is extended to competitive trapping at two different types of intragranular defects. Closed-form expressions for the mean positron lifetime and the relative intensities of the defect-specific positron lifetime components are given. The model is presented for cylindrical-shaped crystallites, but is valid in the general sense for spherical symmetry as well with appropriate replacements. The model yields the basis for properly determining defect concentrations, even for the inconvenient but common case that one intragranular defect type exhibits a lifetime component similar to that in GBs. It turns out, that positron trapping at GBs matters even forµm-sized crystallites and should not be neglected for precise studies of intragranular defects.