Size-Dependent Electrochemical Performance Mediated by Stress-Induced Cracking in Zn2SnO4 Electrodes.

Correlating the microscopic structural characteristics with the macroscopic electrochemical performance in electrode materials is critical for developing excellent-performance lithium-ion batteries, which however remains largely unexplored. Here, we show that the Zn2SnO4 (ZTO) nanowires (NWs) with smaller diameters (d < 5 nm) exhibit slower capacity fade rate and better cycling stability, as compared with the NWs with larger diameters ranging from tens to hundreds of nanometers. By applying in situ transmission electron microscopy (TEM), we discover a strong correlation of cracking behavior with the NW diameter. Upon the first lithiation, there exists a critical diameter of ∼80 nm, below which the NWs neither crack nor fracture, and above which the cracks could easily nucleate and propagate along the specific planes, resulting in the deteriorated cycling stability in larger sized electrodes. Further theoretical calculations based on the finite element model and the climbing image nudged elastic band method faithfully predict the size-dependent cracking behaviors, which may result from the synergistic effect of axial stress evolution as well as preferential Li-ion migration directions during the first lithiation. This work provides a real-time tracking of the tempo-spatial structural evolution of a single ZTO NW, which facilitates a fundamental understanding of how the sample size affects the electrochemical behavior and thus offers a reference for future battery design and application strategy.

Unexpected Two-Dimensional Polarons Induced by Oxygen Vacancies in Layered Structure MoO3-x.

Unveiling the effects of oxygen vacancies on the structural stability of layered α-MoO3 is critical for optimizing its physical and chemical properties. Herein, we present experimental evidence regarding the phase stability of α-MoO3 with ∼2% oxygen vacancy concentrations. Interestingly, we report a previously ignored oxygen-deficient orthorhombic MoO3-x phase in space group Cmcm. Further density functional theory calculations reveal a detailed phase transition mechanism from α-MoO3 to MoO3-x. More importantly, we demonstrate that two-dimensional (2D) large polarons must exist to stabilize the MoO3-x crystal structure. 2D large polarons are suspected to exist in numerous quasi-2D systems but have never been found in layered α-MoO3 or other molybdenum oxides. Our work contributes to a basic understanding of the polaronic behavior in MoO3-x and may broaden the application realm of molybdenum oxides.

Study of the growth mechanism of a self-assembled and ordered multi-dimensional heterojunction at atomic resolution.

Multi-dimensional heterojunction materials have attracted much attention due to their intriguing properties, such as high efficiency, wide band gap regulation, low dimensional limitation, versatility and scalability. To further improve the performance of materials, researchers have combined materials with various dimensions using a wide variety of techniques. However, research on growth mechanism of such composite materials is still lacking. In this paper, the growth mechanism of multi-dimensional heterojunction composite material is studied using quasi-two-dimensional (quasi-2D) antimonene and quasi-one-dimensional (quasi-1D) antimony sulfide as examples. These are synthesized by a simple thermal injection method. It is observed that the consequent nanorods are oriented along six-fold symmetric directions on the nanoplate, forming ordered quasi-1D/quasi-2D heterostructures. Comprehensive transmission electron microscopy (TEM) characterizations confirm the chemical information and reveal orientational relationship between Sb2S3 nanorods and the Sb nanoplate as substrate. Further density functional theory calculations indicate that interfacial binding energy is the primary deciding factor for the self-assembly of ordered structures. These details may fill the gaps in the research on multi-dimensional composite materials with ordered structures, and promote their future versatile applications.

Probing the Atomistic Reaction Pathways in CuO/C Catalysts.

CuOx/C catalysts have been used in the selective catalytic reduction of NOx because of the exceptional low-temperature denitration (de-NOx) activity. A fundamental understanding of the reaction between CuO and C is critical for controlling the component of CuOx/C and thus optimizing the catalytic performance. In this study, a transmission electron microscope equipped with an in situ heating device was utilized to investigate the atomic-scale reaction between CuO and C. We report two reaction mechanisms relying on the volume ratio between C and CuO: (1) The reduction from CuO to Cu2O (when the ratio is < ∼31%); (2) the reduction of CuO into polycrystalline Cu (when the ratio is > ∼34%). The atomistic reduction pathway can be well interpreted by considering the diffusion of O vacancy through the first-principle calculations. The atomic-scale exploration of CuO/C offers ample prospects for the design of industrial de-NOx catalysts in the future.

Size-Dependent Phase Transition in Ultrathin Ga2O3 Nanowires.

Gallium oxide (Ga2O3) has attracted extensive attention as a potential candidate for low-dimensional metal-oxide-semiconductor field-effect transistors (MOSFETs) due to its wide bandgap, controllable doping, and low cost. The structural stability of nanoscale Ga2O3 is the key parameter for designing and constructing a MOSFET, which however remains unexplored. Using in situ transmission electron microscopy, we reveal the size-dependent phase transition of sub-2 nm Ga2O3 nanowires. Based on theoretical calculations, the transformation pathways from the initial monoclinic ß-phase to an intermediate cubic γ-phase and then back to the ß-phase have been mapped and identified as a sequence of Ga cation migrations. Our results provide fundamental insights into the Ga2O3 phase stability within the nanoscale, which is crucial for advancing the miniaturization, light weight, and integration of wide-bandgap semiconductor devices.

Strong interlayer coupling and unusual antisite defect-mediated p-type conductivity in GePx (x = 1, 2).

As an emerging candidate for anisotropic two-dimensional materials, the group IV-V family (e.g. GeP, GeP2) has appealing applications in photoelectronics. However, their intrinsic point defect properties, which largely determine the device performance and optimization, are still poorly explored. In our study, through density functional theory (DFT) calculations, antisite defects were affirmed to be dominant with the lowest formation energies in 2D GePx semiconductors because of the similar atomic size and electronegativity of elemental components, which is in contrast to previous calculations and experimental speculation. These antisite defects could introduce relatively shallow states within the bandgap in bulk cases. The transition energy levels and electronic structures of defects reveal that GeP and PGe antisites act as dominant acceptors and donors, respectively. Strong interlayer coupling between anions results in a significant upshift of the valence band maximum (VBM) and shallower acceptor behaviors of GePx. Together with the dominant GeP antisite defect, the large upshift of the VBM in GeP leads to a remarkable transition of conductivity from intrinsic in the monolayer to p-type in the bulk. Such a synergistic effect in GeP2 is rather weak due to the strong inherent intralayer coupling of anions. Our research provides deep insights into the strong anion coupling effects on the electronic structures and defect properties of GeP and GeP2, which sheds light on defect engineering and electronic applications of GePx based semiconductors.

Understanding Alkaline Hydrogen Oxidation Reaction on PdNiRuIrRh High-Entropy-Alloy by Machine Learning Potential.

High-entropy alloy (HEA) catalysts have been widely studied in electrocatalysis. However, identifying atomic structure of HEA with complex atomic arrangement is challenging, which seriously hinders the fundamental understanding of catalytic mechanism. Here, we report a HEA-PdNiRuIrRh catalyst with remarkable mass activity of 3.25 mA µg-1 for alkaline hydrogen oxidation reaction (HOR), which is 8-fold enhancement compared to that of commercial Pt/C. Through machine learning potential-based Monte Carlo simulation, we reveal that the dominant Pd-Pd-Ni/Pd-Pd-Pd bonding environments and Ni/Ru oxophilic sites on HEA surface are beneficial to the optimized adsorption/desorption of *H and enhanced *OH adsorption, contributing to the excellent HOR activity and stability. This work provides significant insights into atomic structure and catalytic mechanism for HEA and offers novel prospects for developing advanced HOR electrocatalysts.

Na+ Migration Mediated Phase Transitions Induced by Electric Field in the Framework Structured Tungsten Bronze.

Framework structured tungsten bronzes serve as promising candidates for electrode materials in sodium-ion batteries (SIBs). However, the tungsten bronze framework structure changes drastically as mediated by the sodium ion concentration at high temperatures. While the three-dimensional ion channels facilitate fast ion storage and transport capabilities, the structural instability induced by Na+ migration is a big concern regarding the battery performance and safety, which unfortunately remains elusive. Here, we show the real-time experimental evidence of the phase transitions in framework structured Na0.36WO3.14 (triclinic phase) by applying different external voltages. The Na+-rich (Na0.48WO3, tetragonal phase) or -deficient (NaxWO3, x < 0.36, hexagonal phase) phase nucleates under the positive or negative bias, respectively. Combined with the theoretical calculations, the atomistic phase transition mechanisms associated with the Na+ migration are directly uncovered. Our work sheds light on the phase instability in sodium tungsten bronzes and paves the way for designing advanced SIBs with high-stability.

Pseudo-Elasticity and Variable Electro-Conductivity Mediated by Size-Dependent Deformation Twinning in Molybdenum Nanocrystals.

Deformation twinning merits attention because of its intrinsic importance as a mode of energy dissipation in solids. Herein, through the atomistic electron microscopy observations, the size-dependent twinning mechanisms in refractory body-centered cubic molybdenum nanocrystals (NCs) under tensile loading are shown. Two distinct twinning mechanisms involving the nucleation of coherent and inclined twin boundaries (TBs) are uncovered in NCs with smaller (diameter < ≈5 nm) and larger (diameter > ≈5 nm) diameters, respectively. Interestingly, the ultrahigh pseudo-elastic strain of ≈41% in sub-5 nm-sized crystals is achieved through the reversible twinning mechanism. A typical TB cross-transition mechanism is found to accommodate the NC re-orientation during the pseudo-elastic deformation. More importantly, the effects of different types of TBs on the electrical conductivity based on the repeatable experimental measurements and first-principles calculations are quantified. These size-dependent mechanical and electrical properties may prove essential in advancing the design of next-generation flexible nanoelectronics.

Synergistic passivation and stepped-dimensional perovskite analogs enable high-efficiency near-infrared light-emitting diodes.

Formamidinium lead iodide (FAPbI3) perovskites are promising emitters for near-infrared light-emitting diodes. However, their performance is still limited by defect-assisted nonradiative recombination and band offset-induced carrier aggregation at the interface. Herein, we introduce a couple of cadmium salts with acetate or halide anion into the FAPbI3 perovskite precursors to synergistically passivate the material defects and optimize the device band structure. Particularly, the perovskite analogs, containing zero-dimensional formamidinium cadmium iodide, one-dimensional δ-FAPbI3, two-dimensional FA2FAn-1PbnI3n+1, and three-dimensional α-FAPbI3, can be obtained in one pot and play a pivotal and positive role in energy transfer in the formamidinium iodide-rich lead-based perovskite films. As a result, the near-infrared FAPbI3-based devices deliver a maximum external quantum efficiency of 24.1% together with substantially improved operational stability. Combining our findings on defect passivation and energy transfer, we also achieve near-infrared light communication with device twins of light emitting and unprecedented self-driven detection.

Oxygen-Inserted Top-Surface Layers of Ni for Boosting Alkaline Hydrogen Oxidation Electrocatalysis.

Precisely tailoring the electronic structures of electrocatalysts to achieve an optimum hydroxide binding energy (OHBE) is vital to the alkaline hydrogen oxidation reaction (HOR). As a promising alternative to the Pt-group metals, considerable efforts have been devoted to exploring highly efficient Ni-based catalysts for alkaline HOR. However, their performances still lack practical competitiveness. Herein, based on insights from the molecular orbital theory and the Hammer-Nørskov d-band model, we propose an ingenious surface oxygen insertion strategy to precisely tailor the electronic structures of Ni electrocatalysts, simultaneously increasing the degree of energy-level alignment between the adsorbed hydroxide (*OH) states and surface Ni d-band and decreasing the degree of anti-bonding filling, which leads to an optimal OHBE. Through the pyrolysis procedure mediated by a metal-organic framework at a low temperature under a reducing atmosphere, the obtained oxygen-inserted two atomic-layer Ni shell-modified Ni metal core nanoparticle (Ni@Oi-Ni) exhibits a remarkable alkaline HOR performance with a record mass activity of 85.63 mA mg-1, which is 40-fold higher than that of the freshly synthesized Ni catalyst. Combining CO stripping experiments with ab initio calculations, we further reveal a linear relationship between the OHBE and the content of inserted oxygen, which thus results in a volcano-type correlation between the OH binding strength and alkaline HOR activity. This work indicates that the oxygen insertion into the top-surface layers is an efficient strategy to regulate the coordination environment and electronic structure of Ni catalysts and identifies the dominate role of OH binding strength in alkaline HOR.

General synthesis of 2D rare-earth oxide single crystals with tailorable facets.

Two-dimensional (2D) rare-earth oxides (REOs) are a large family of materials with various intriguing applications and precise facet control is essential for investigating new properties in the 2D limit. However, a bottleneck remains with regard to obtaining their 2D single crystals with specific facets because of the intrinsic non-layered structure and disparate thermodynamic stability of different facets. Herein, for the first time, we achieve the synthesis of a wide variety of high-quality 2D REO single crystals with tailorable facets via designing a hard-soft-acid-base couple for controlling the 2D nucleation of the predetermined facets and adjusting the growth mode and direction of crystals. Also, the facet-related magnetic properties of 2D REO single crystals were revealed. Our approach provides a foundation for further exploring other facet-dependent properties and various applications of 2D REO, as well as inspiration for the precise growth of other non-layered 2D materials.

Self-Limiting Synthesis of Ultrathin Ge(110) Single Crystal via Liquid Metal.

Germanium, the prime applied semiconductor, is widely used in solid-state electronics and photoelectronics. Unfortunately, since the 3D diamond-like structure with strong covalent bonds impedes the 2D anisotropic growth, only the examples of ultrathin Ge along the (111) plane have been investigated, much less to the controllable synthesis along another crystal surface. Meanwhile, Ge(111) flakes are limited in semiconductor applications because of their gapless property. Here, ultrathin Ge(110) single crystal is synthesized with semiconductive property via gallium-associated self-limiting growth. The obtained ultrathin Ge(110) single crystal exhibits anisotropic honeycomb structure, uniformly incremental lattice, wide tunable direct-bandgap, blue-shifted photoluminescence emission, and unique phonon modes, which are consistent with the previous theoretical predictions. It also confirms excellent second harmonic generation and high hole mobility of 724 cm2 V-1 s-1 . The realization of ultrathin Ge(110) single crystal will provide an excellent candidate for application in electronics and optoelectronics.

Cation Defect Mediated Phase Transition in Potassium Tungsten Bronze.

Applying in situ transmission electron microscopy, the phase instability in potassium tungsten bronze (KxWO3, 0.18 < x < 0.57) induced by heating was investigated. The atomistic phase transition pathway of monoclinic K0.20WO3 → hexagonal KmWO3 (0.18 < m < 0.20) → cubic WO3 induced by cationic defects (K and W vacancies) was directly revealed. Unexpectedly, a K+-rich tetragonal KnWO3 (0.40 < n < 0.57) phase would nucleate as well, which may result from the blockage of K+ diffusion at the grain boundaries. Our results point out the critical role of the cationic defects in mediating the crystal structures in KxWO3, which provide reference to rational structural design for extensive high-temperature applications.

Room-temperature oxygen vacancy migration induced reversible phase transformation during the anelastic deformation in CuO.

From the mechanical perspectives, the influence of point defects is generally considered at high temperature, especially when the creep deformation dominates. Here, we show the stress-induced reversible oxygen vacancy migration in CuO nanowires at room temperature, causing the unanticipated anelastic deformation. The anelastic strain is associated with the nucleation of oxygen-deficient CuOx phase, which gradually transforms back to CuO after stress releasing, leading to the gradual recovery of the nanowire shape. Detailed analysis reveals an oxygen deficient metastable CuOx phase that has been overlooked in the literatures. Both theoretical and experimental investigations faithfully predict the oxygen vacancy diffusion pathways in CuO. Our finding facilitates a better understanding of the complicated mechanical behaviors in materials, which could also be relevant across multiple scientific disciplines, such as high-temperature superconductivity and solid-state chemistry in Cu-O compounds, etc.

Atomistic Observation of Desodiation-Induced Phase Transition in Sodium Tungsten Bronze.

The phase instability in layered-structure Na0.5WO3.25 induced by the extraction of Na ions was investigated by applying transmission electron microscopy. Real-time atomic-scale observation reveals the phase transition pathway: Na0.5WO3.25 (triclinic) → NaxWO3 (cubic) → WO3 (monoclinic) with specific orientation relationships. The dynamic evolution of Na0.5WO3.25/NaxWO3 phase boundaries shows that Na0.5WO3.25 will cleave along the (100)T and (010)T and recrystallize as (101)C and (010)C of NaxWO3, respectively. The phase transition pathway can be well-explained according to the structural characteristics in the three phases. By better understanding of the phase instability induced by the extraction of Na ions in possible layered-structure cathode materials, this work provides a reference for the design of sophisticated strategies toward high-performance Na-ion batteries.

Study of the Growth Mechanism of Solution-Synthesized Symmetric Tellurium Nanoflakes at Atomic Resolution.

As a new member of 2D materials, 2D tellurium (Te) has recently attracted much attention due to its intriguing properties. Through hydrothermal processing, 2D Te with tunable thickness and size has been realized, and its growth mechanism has also been studied. However, the tailored growth of 2D Te nanoflakes with symmetrical morphologies and interfacial moiré fringes has never been reported. Here, 2D Te nanoflakes have been prepared using the hydrothermal method, and mirror-symmetrical shapes (including "V-shape," "heart-shape," and "paper airplane-shape") with obvious moiré fringes in the middle of the nanoflakes are observed. Comprehensive transmission electron microscopy (TEM) techniques are utilized for structural characterization of these nanoflakes, especially the moiré fringes in the symmetry axis region of the nanoflakes. The systematic analyses of the moiré fringes and the observation of obvious overlapping edges of the composing nanoflakes from the cross-sectional samples reveal the possible mechanism of morphological evolution for these symmetrical nanoflakes. These details may fill the research gap in the controllable growth of 2D Te nanomaterials, pave the way for the fabrication of 2D Te moiré superlattices and in-plane homojunctions, and promote their future versatile applications.

Author Correction: Activation of subnanometric Pt on Cu-modified CeO2 via redox-coupled atomic layer deposition for CO oxidation.

A Correction to this paper has been published: https://doi.org/10.1038/s41467-020-19663-3 .

Activation of subnanometric Pt on Cu-modified CeO2 via redox-coupled atomic layer deposition for CO oxidation.

Improving the low-temperature activity (below 100 °C) and noble-metal efficiency of automotive exhaust catalysts has been a continuous effort to eliminate cold-start emissions, yet great challenges remain. Here we report a strategy to activate the low-temperature performance of Pt catalysts on Cu-modified CeO2 supports based on redox-coupled atomic layer deposition. The interfacial reducibility and structure of composite catalysts have been precisely tuned by oxide doping and accurate control of Pt size. Cu-modified CeO2-supported Pt sub-nanoclusters demonstrate a remarkable performance with an onset of CO oxidation reactivity below room temperature, which is one order of magnitude more active than atomically-dispersed Pt catalysts. The Cu-O-Ce site with activated lattice oxygen anchors deposited Pt sub-nanoclusters, leading to a moderate CO adsorption strength at the interface that facilitates the low-temperature CO oxidation performance.

Ultrathin high-κ antimony oxide single crystals.

Ultrathin oxides have been reported to possess excellent properties in electronic, magnetic, optical, and catalytic fields. However, the current and primary approaches toward the preparation of ultrathin oxides are only applicable to amorphous or polycrystalline oxide nanosheets or films. Here, we successfully synthesize high-quality ultrathin antimony oxide single crystals via a substrate-buffer-controlled chemical vapor deposition strategy. The as-obtained ultrathin antimony oxide single crystals exhibit high dielectric constant (~100) and large breakdown voltage (~5.7 GV m-1). Such a strategy can also be utilized to fabricate other ultrathin oxides, opening up an avenue in broadening the applicaitons of ultrathin oxides in many emerging fields.