Integrated Structural Modulation Inducing Fast Charge Transfer in Aqueous Zinc-Ion Batteries.

Aqueous Zn-ion batteries (AZIBs) are promising energy-storage devices owing to their exceptional safety, long cycle life, simple production, and high storage capacity. Manganese oxides are considered potential cathode materials for AZIBs, primarily because of their safety, low cost, simple synthesis, and high storage capacity. However, MnO2-based cathodes tend to deteriorate structurally during long-term cycling, which reduces their reversible capacity. In this study, an advanced α-MnO2@SnO2 nanocomposite via facile hydrothermal synthesis is developed. The synergistic effects of lattice disorder and increased electron conductivity in the α-MnO2@SnO2 nanocomposite mitigate structural degradation and enhance the overall electrochemical performance. The nanocomposite exhibits a high reversible capacity of 347 mAh g-1 at a current density of 100 mA g-1 after 50 cycles. Furthermore, it exhibits excellent rate performance and stable capacity even after 1000 cycles, maintaining a capacity of 78 mAh g-1 at a high current density of 5 A g-1. This excellent electrochemical performance is attributed to the reversible Zn intercalation in α-MnO2@SnO2 nanocomposites due to the increased structural stability and fast ion/electron exchange caused by the distortion of the tunnel structure, on the basis of various ex situ experiments, density functional theory calculations, and electrochemical characterizations.

Potassium fluoride-induced FeOOH formation in NiFe oxalate for improved oxygen evolution performance.

Our study introduces a facile synthetic route for the in situ formation of nickel (Ni)-iron (Fe) oxyhydroxide from NiFe oxalate. By adding potassium fluoride (KF) to the synthetic solution, we achieved a predominant surface distribution of Fe (>80 at%) while limiting its bulk incorporation compared to solutions without KF. Operando Raman spectroscopy analysis confirms that the enriched Fe predominantly exists as FeOOH. Our optimized catalyst demonstrates significant efficiency, achieving a current density of 10 mA cm-2 at a notably low overpotential of 226 mV.

Synthesis and electrochemical evaluation of nickel hydroxide nanosheets with phase transition to nickel oxide.

Transition metal hydroxides are commonly used to develop nanostructures with desired functionalities by controlling their size, morphology, and structure. In this study, nickel hydroxide nanosheets with a hexagonal island shape are synthesized via a surfactant-assisted method. Using this method, nickel hydroxide nanosheets can be easily achieved in a quick manner. The synthesized nanosheets are 3-6 nm thick and exhibit a curly and wrinkled morphology with increasing surfactant concentration. These nanosheets demonstrate superior catalytic properties for the oxygen evolution reaction activity compared to nickel oxide sheets obtained via a simple heat treatment. Furthermore, we conduct surface enhanced Raman scattering analysis to confirm that the nickel hydroxide nanosheets serve as active species for NiOOH during the oxygen evolution reaction, and we propose an electrochemical mechanism for this system. This study not only presents the detailed synthesis process but also proposes a straightforward approach, offering valuable insights into the structural and electrochemical properties of the resulting nanosheets.

Morphologically Controlled Synthesis of Reduced-Dimensional ZnO/Zn(OH)2 Nanosheets.

Conventional two-dimensional materials either have natural layered structures or are produced, with large surface areas, via physical or chemical synthesis. However, to form a two-dimensional material from a non-layered material, a method different from the existing ones is required. In this study, a surfactant-assisted method was utilized to synthesize Zn(OH)2 (a nonlayered transition metal oxide) nanosheets. This study described the synthesis of Zn(OH)2 nanosheets using an anionic sulfate layer and demonstrated a method of controlling the thickness and shape of the synthesized nanosheets by varying the surfactant concentration. Further, the characteristics of oxygen evolution reaction using ZnO/Zn(OH)2 nanosheets, obtained by annealing the synthesized sheets, as catalysts were studied.

Correction: Thermally driven phase transition of cobalt hydroxide sheets via cobalt oxides to cobalt nanoparticles.

Correction for 'Thermally driven phase transition of cobalt hydroxide sheets via cobalt oxides to cobalt nanoparticles' by Aram Yoon et al., Nanoscale Horiz., 2022, https://doi.org/10.1039/d2nh00218c.

In-situ formation of co particles encapsulated by graphene layers.

The process of encapsulating cobalt nanoparticles using a graphene layer is mainly direct pyrolysis. The encapsulation structure of hybrids prepared in this way improves the catalyst stability, which greatly reduces the leaching of non-metals and prevents metal nanoparticles from growing beyond a certain size. In this study, cobalt particles surrounded by graphene layers were formed by increasing the temperature in a transmission electron microscope, and they were analyzed using scanning transmission electron microscopy (STEM). Synthesized cobalt hydroxide nanosheets were used to obtain cobalt particles using an in-situ heating holder inside a TEM column. The cobalt nanoparticles are surrounded by layers of graphene, and the number of layers increases as the temperature increases. The interlayer spacing of the graphene layers was also investigated using atomic imaging. The success achieved in the encapsulation of metallic nanoparticles in graphene layers paves the way for the design of highly active and reusable heterogeneous catalysts for more challenging molecules.

Atomic Structure of Dislocations and Grain Boundaries in Two-Dimensional PtSe2.

Each 2D material has a distinct structure for its grain boundary and dislocation cores, which is dictated by both the crystal lattice geometry and the elements that participate in bonding. For the class of noble metal dichalcogenides, this has yet to be thoroughly investigated at the atomic scale. Here, we examine the atomic structure of the dislocations and grain boundaries (GBs) in two-dimensional PtSe2, using atomic-resolution annular dark field scanning transmission electron microscopy, combined with density functional theory and empirical force field calculations. The PtSe2 we study adopts the 1T phase in large-area polycrystalline films with numerous planar tilt GB distinct dislocations, including 5|7+Se and 4|4|8+Se polygons, in tilt-angle monolayer GBs, with features sharply distinguished from those in 2H-phase TMDs. On the basis of dislocation cores, the GB structures are investigated in terms of pathways of dislocation chain arrangement, dislocation core distributions in different misorientation angles, and 2D strain fields induced. Based on the Frank-Bilby equation, the deduced Burgers vector magnitude is close to the lattice constant of 1T-PtSe2, building the quantitative relationship of dislocation spacings and small GB angles. The 30° GBs are most frequently formed as a stitched interface between the armchair and zigzag lattices, constructed by a string of 5|7+Se dislocations asymmetrically with a small deviation angle. Another special angle GB, mirror twin 60° GB, is also mapped linearly by metal-condensed asymmetric or Se-rich symmetric dislocations. This report gives atomic-level insights into the GBs and dislocations in 1T-phase noble metal TMD PtSe2, which is a promising material to underpin extending properties of 2D materials by local structure engineering.

Atomistic Mechanics of Torn Back Folded Edges of Triangular Voids in Monolayer WS2.

Triangular nanovoids in 2D materials transition metal dichalcogenides have vertex points that cause stress concentration and lead to sharp crack propagation and failure. Here, the atomistic mechanics of back folding around triangular nanovoids in monolayer WS2 sheets is examined. Combining atomic-resolution images from annular dark-field scanning transmission electron microscopy with reactive molecular modelling, it is revealed that the folding edge formation has statistical preferences under geometric conditions based on the orientation mismatch. It is further investigated how loading directions and strong interlayer friction, interplay with WS2 lattice's crack preference, govern the deformation and fracture pattern around folding edges. These results provide fundamental insights into the combination of fracture and folding in flexible monolayer crystals and the resultant Moiré lattices.

Atomic Arrangements of Graphene-like ZnO.

ZnO, which can exist in various dimensions such as bulk, thin films, nanorods, and quantum dots, has interesting physical properties depending on its dimensional structures. When a typical bulk wurtzite ZnO structure is thinned to an atomic level, it is converted into a hexagonal ZnO layer such as layered graphene. In this study, we report the atomic arrangement and structural merging behavior of graphene-like ZnO nanosheets transferred onto a monolayer graphene using aberration-corrected TEM. In the region to which an electron beam is continuously irradiated, it is confirmed that there is a directional tendency, which is that small-patched ZnO flakes are not only merging but also forming atomic migration of Zn and O atoms. This study suggests atomic alignments and rearrangements of the graphene-like ZnO, which are not considered in the wurtzite ZnO structure. In addition, this study also presents a new perspective on the atomic behavior when a bulk crystal structure, which is not an original layered structure, is converted into an atomic-thick layered two-dimensional structure.

OH molecule-involved formation of point defects in monolayer graphene.

Point defects in freestanding graphene monolayers such as monovacancies (MVs) and divacancies have been investigated at atomic scale with aberration-corrected transmission electron microscopy and theoretical calculations. In general, these defects can be formed simply by the absence of individual carbon atoms and carbon bond reconstructions in the graphene lattice under electron and ion irradiation. However, in this study, we found that oxygen and hydrogen atoms can be involved in the formation of these point defects caused by the simultaneous detachment of oxygen-carbon atoms. Here we report the effect of the oxygen and hydrogen atoms on the graphene surface forming the point defects under electron beam irradiation, and their role of stabilizing other MVs when composed of 13-5 ring pairs. In addition, theoretical analysis using density functional theory calculations demonstrates that the participating atoms can form the point defects in the intermediate states and stabilize 13-5 ring pairs under electron beam irradiation.

Sequential conversion from line defects to atomic clusters in monolayer WS2.

Transition metal dichalcogenides (TMD), which is composed of a transition metal atom and chalcogen ion atoms, usually form vacancies based on the knock-on threshold of each atom. In particular, when electron beam is irradiated on a monolayer TMD such as MoS2 and WS2, S vacancies are formed preferentially, and they are aligned linearly to constitute line defects. And then, a hole is formed at the point where the successively formed line defects collide, and metal clusters are also formed at the edge of the hole. This study reports a process in which the line defects formed in a monolayer WS2 sheet expends into holes. Here, the process in which the W cluster, which always occurs at the edge of the formed hole, goes through a uniform intermediate phase is explained based on the line defects and the formation behavior of the hole. Further investigation confirms the atomic structure of the intermediate phase using annular dark field scanning transition electron microscopy (ADF-STEM) and image simulation.

Spatially Bandgap-Graded MoS2(1-x)Se2x Homojunctions for Self-Powered Visible-Near-Infrared Phototransistors.

Ternary transition metal dichalcogenide alloys with spatially graded bandgaps are an emerging class of two-dimensional materials with unique features, which opens up new potential for device applications. Here, visible-near-infrared and self-powered phototransistors based on spatially bandgap-graded MoS2(1-x)Se2x alloys, synthesized by a simple and controllable chemical solution deposition method, are reported. The graded bandgaps, arising from the spatial grading of Se composition and thickness within a single domain, are tuned from 1.83 to 1.73 eV, leading to the formation of a homojunction with a built-in electric field. Consequently, a strong and sensitive gate-modulated photovoltaic effect is demonstrated, enabling the homojunction phototransistors at zero bias to deliver a photoresponsivity of 311 mA W-1, a specific detectivity up to ~ 1011 Jones, and an on/off ratio up to ~ 104. Remarkably, when illuminated by the lights ranging from 405 to 808 nm, the biased devices yield a champion photoresponsivity of 191.5 A W-1, a specific detectivity up to ~ 1012 Jones, a photoconductive gain of 106-107, and a photoresponsive time in the order of ~ 50 ms. These results provide a simple and competitive solution to the bandgap engineering of two-dimensional materials for device applications without the need for p-n junctions.

Spatially Controlled Fabrication and Mechanisms of Atomically Thin Nanowell Patterns in Bilayer WS2 Using in Situ High Temperature Electron Microscopy.

We show controlled production of atomically thin nanowells in bilayer WS2 using an in situ heating holder combined with a focused electron beam in a scanning transmission electron microscope (STEM). We systematically study the formation and evolvement mechanism involved in removing a single layer of WS2 within a bilayer region with 2 nm accuracy in location and without punching through to the other layer to create a hole. Best results are found when using a high temperature of 800 °C, because it enables thermally activated atomic migration and eliminates the interference from surface carbon contamination. We demonstrate precise control over spatial distributions with 5 nm accuracy of patterning and the width of nanowells adjustable by dose-dependent parameters. The mechanism of removing a monolayer of WS2 within a bilayer region is different than removing equivalent sections in a monolayer film due to the van der Waals interaction of the underlying remaining layer in the bilayer system that stabilizes the excess W atom stoichiometry within the edges of the nanowell structure and facilitates expansion. This study offers insights for the nanoengineering of nanowells in two-dimensional (2D) transitional metal dichalcogenides (TMDs), which could hold potential as selective traps to localize 2D reactions in molecules and ions, underpinning the broader utilization of 2D material membranes.

Striated 2D Lattice with Sub-nm 1D Etch Channels by Controlled Thermally Induced Phase Transformations of PdSe2.

2D crystals are typically uniform and periodic in-plane with stacked sheet-like structure in the out-of-plane direction. Breaking the in-plane 2D symmetry by creating unique lattice structures offers anisotropic electronic and optical responses that have potential in nanoelectronics. However, creating nanoscale-modulated anisotropic 2D lattices is challenging and is mostly done using top-down lithographic methods with ≈10 nm resolution. A phase transformation mechanism for creating 2D striated lattice systems is revealed, where controlled thermal annealing induces Se loss in few-layered PdSe2 and leads to 1D sub-nm etched channels in Pd2 Se3 bilayers. These striated 2D crystals cannot be described by a typical unit cells of 1-2 Å for crystals, but rather long range nanoscale periodicity in each three directions. The 1D channels give rise to localized conduction states, which have no bulk layered counterpart or monolayer form. These results show how the known family of 2D crystals can be extended beyond those that exist as bulk layered van der Waals crystals by exploiting phase transformations by elemental depletion in binary systems.

Atomically Sharp Dual Grain Boundaries in 2D WS2 Bilayers.

It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS2 can be atomically sharp, where top and bottom layer GBs are located within sub-nanometer distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic-resolution annular dark-field scanning transmission electron microscopy (ADF-STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA' stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF-STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS2 layer, but the second WS2 layer has different dislocation structures not seen in freestanding monolayers, which have metal-rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.

Atomic Structure and Dynamics of Defects and Grain Boundaries in 2D Pd2Se3 Monolayers.

We study the atomic structure and dynamics of defects and grain boundaries in monolayer Pd2Se3 using annular dark field scanning transmission electron microscopy. The Pd2Se3 monolayers are reproducibly created by thermally induced phase transformation of few-layered PdSe2 films in an in situ heating holder in the TEM to promote Se loss. A variety of point vacancies, one-dimensional defects, grain boundaries (GBs), and defect ring complexes are directly observed in monolayer Pd2Se3, which show a series of dynamics triggered by electron beam irradiation. High mobility of vacancies leads to self-healing of point vacancies by migration to the edge and subsequent edge etching under beam irradiation. Specific defects for Pd2Se3 are stabilized by the formation of Se-Se bonds, which can shift in a staggered way to buffer strain, forming a wave-like one-dimensional defect. Bond rotations are also observed and play an important role in defect and grain boundary dynamics in Pd2Se3 during vacancy production. The GBs form in a meandering pathway and migrate by a sequence of Se-Se bond rotations without large-scale vacancy formation. In the GB corners and tilted GBs, other highly symmetric vacancy defects also occur to adapt to the orientation change. These results give atomic level insights into the defects and grain boundaries in Pd2Se3 2D monolayers.

Postgrowth Substitutional Tin Doping of 2D WS2 Crystals Using Chemical Vapor Deposition.

Doping of two-dimensional materials provides them tunable physical properties and widens their applications. Here, we demonstrate the postgrowth doping strategy in monolayer and bilayer tungsten disulfide (WS2) crystals, which utilizes a metal exchange mechanism, whereby Sn atoms become substitutional dopants in the W sites by energetically favorable replacement. We achieve this using chemical vapor deposition techniques, where high-quality grown WS2 single crystals are first grown and then subsequently reacted with a SnS precursor. Thermal control of the exchange doping mechanism is revealed, indicating that a sufficiently high enough temperature is required to create the S vacancies that are the initial binding sites for the SnS precursor and metal exchange occurrence. This results in a better control of dopant distribution compared to the tradition all-in-one approach, where dopants are added during the growth phase. The Sn dopants exhibit an n-type doping behavior in the WS2 layers based on the decreased threshold voltage obtained from transistor device measurements. Annular dark-field scanning transmission electron microscopy shows that in bilayer WS2 the Sn doping occurs only in the top layer, creating vertical heterostructures with atomic layer doping precision. This postgrowth modification opens up ways to selectively dope one layer at a time and construct mixed stoichiometry vertical heterojunctions in bilayer crystals.

Atomic structural catalogue of defects and vertical stacking in 2H/3R mixed polytype multilayer WS2 pyramids.

We examine the atomic structure of chemical vapour deposition grown multilayer WS2 pyramids using aberration corrected annular dark field scanning transmission electron microscopy coupled with an in situ heating holder. The stacking orders and specific types of defects after partial degradation by S and W atomic loss at high temperature are resolved layer-by-layer. Our study of an individual WS2 pyramid with at least six layers, reveals a mixed 2H and 3R polytype stacking. Etching occurred both top and bottom of the WS2 pyramid, which aids in determining the exact vertical layer stacking configurations in the thicker regions. We provide an extensive catalogue of the contrast profiles associated with defects in WS2 as a function of layer number and stacking type, as imaged using ADF-STEM. These results provide extensive details about the identification of a wide range of defects in S2 layers, and the unique ADF-STEM contrast patterns that arise from complex multilayer stacking.

In situ high temperature atomic level dynamics of large inversion domain formations in monolayer MoS2.

Here we study the high-temperature formation and dynamics of large inversion domains (IDs) that form in monolayer MoS2 using atomic-resolution annular dark-field scanning transmission electron microscopy (ADF-STEM) with an in situ heating stage. We use temperatures above 700 °C to thermally activate rapid S vacancy migration and this leads to a formation mechanism of IDs that differs from the one at room temperature, where S vacancy migration is limited. We show that at high temperatures the formation of IDs occurs from intersected networks of long S vacancy line defects, whose strain fields are non-orthogonal and trigger large scale atomic reconstructions. Once formed, the IDs are influenced by the dynamic behaviour of nearby line defects and voids. With Mo and S atoms undergoing movement, the two types of ID grain boundaries can shift to allow further expansion of the ID area along the adjoining line defects. We reveal that IDs serve as metastable configurations between line defect rearrangements and eventual void formation under electron beam irradiation during heating. The formation of voids near to the IDs causes them to revert back to pristine lattice, which has the effect of restricting the ID domain size to a certain range (e.g. 3-5 nm in our observation) instead of continuously enlarging. This study provides insights into how the MoS2 IDs form and evolve at high temperature and can benefit the tailoring of electronic properties of two dimensional materials by structural manipulation.

Atomic Structure and Dynamics of Self-Limiting Sub-Nanometer Pores in Monolayer WS2.

We reveal a self-limiting mechanism during the formation of a specific type of circular nanopore in monolayer WS2 that limits its diameter to sub-nm. A single W atom vacancy (triangular nanopore) is transformed into the self-limiting nanopore (SLNP) through the atomic restructuring of S atoms around the area, reducing the number of dangling bonds at the nanopore edge by shifting them further in-plane with W-W bonding instead. Bond rotations in WS2 help accommodate the electron beam induced atomic loss and ensure the stability of the SLNP. The SLNP shows significant improvement in diameter stability during electron beam irradiation compared to other triangular nanopores in WS2 that typically continue to expand in diameter during atom loss. The atomic structure of these SLNPs is studied using aberration-corrected scanning transmission electron microscopy with an in situ heating holder, revealing that the SLNPs are mostly formed at a temperature of ∼500 °C, which is a balance between thermally activated S vacancy diffusion and sufficient S vacancy density to initiate local atomic reconstruction. At higher temperatures ( i. e., 1000 °C), S vacancies quickly migrate away into long line vacancies, resulting in low S vacancy density and rapidly expanding holes generated at the edges of the line vacancies. At room temperature, S vacancy migration is low and vacancy density is very high, which limits atomic reconstruction, and instead many small holes open up. These results provide insights into the factors that lead to uniform sized nanopores in the sub-nm range in transition-metal dichalcogenides.