Single-Crystal P2-Na0.67Mn0.67Ni0.33O2 Cathode Material with Improved Cycling Stability for Sodium-Ion Batteries.

Layered oxides constitute one of the most promising cathode materials classes for large-scale sodium-ion batteries because of their high specific capacity, scalable synthesis, and low cost. However, their practical use is limited by their low energy density, physicochemical instability, and poor cycling stability. Aiming to mitigate these shortcomings, in this work, we synthesized polycrystalline (PC) and single-crystal (SC) P2-type Na0.67-δMn0.67Ni0.33O2 (NMNO) cathode materials through a solid-state route and evaluated their physicochemical and electrochemical performance. The SC-NMNO cathode with a large mean primary particle size (D50) of 12.7 µm was found to exhibit high cycling stability leading to 47% higher capacity retention than PC-NMNO after 175 cycles at 1C rate in the potential window 4.2-1.5 V. This could be attributed to the effective mitigation of parasitic side reactions at the electrode-electrolyte interface and suppressed intergranular cracking induced by anisotropic volume changes. This is confirmed by the lower volume variation of SC-NMNO (ΔV ∼ 1.0%) compared to PC-NMNO (ΔV ∼ 1.4%) upon charging to 4.2 V. Additionally, the SC-NMNO cathode displayed slightly higher thermal stability compared to PC-NMNO. Both cathodes exhibited good chemical stability against air and water exposure, thus enabling material storage/handling in the ambient atmosphere as well as making them suitable for aqueous processing. In this regard, PC-NMNO was investigated with two low-cost aqueous binders, carboxymethyl cellulose, and sodium trimetaphosphate, which exhibited higher binding strength and displayed excellent electrochemical performance compared to PVDF, which could potentially lead to significant cost reduction in electrode manufacturing.

Simultaneous Inside and Outside Functionalization of Single-Walled Carbon Nanotubes.

Functionalizing single-walled carbon nanotubes (SWCNTs) in a robust way that does not affect the sp2 carbon framework is a considerable research challenge. Here we describe how triiodide salts of positively charged macrocycles can be used not only to functionalize SWCNTs from the outside, but simultaneously from the inside. We employed disulfide exchange in aqueous solvent to maximize the solvophobic effect and therefore achieve a high degree of macrocycle immobilization. Characterization by Raman spectroscopy, EDX-STEM and HR-TEM clearly showed that serendipitously this wet-chemical functionalization procedure also led to the encapsulation of polyiodide chains inside the nanotubes. The resulting three-shell composite materials are redox-active and experience an intriguing interplay of electrostatic, solvophobic and mechanical effects that could be of interest for applications in energy storage.

An Efficient Electron Ptychography Method for Retrieving the Object Spectrum from Only a Few Iterations.

We present an efficient approach for electron ptychography based on a mathematical relationship that differs from that underlying the established algorithms of the ptychography iterative engine or the noniterative algorithms like the Wigner-distribution-deconvolution or the single-side-band method. Three variables are handled in this method-the transfer function of the objective lens, the object spectrum, and the diffraction wave whose phase is unknown. In the case of an aberration-corrected electron microscope, one is able to obtain a well-estimated transfer function of the lens. After reducing the number of three variables down to two, we construct an iterative loop between the object spectrum and the diffraction wave, which retrieves the object spectrum within a small number of iterations. We tested this object spectrum retrieval method on both a calculated and an experimental 4D-STEM datasets. By applying this method, we explore the influence of sampling, dose, and the size of illumination aperture on the reconstructed phase images.

Atomic-Scale Time-Resolved Imaging of Krypton Dimers, Chains and Transition to a One-Dimensional Gas.

Single-atom dynamics of noble-gas elements have been investigated using time-resolved transmission electron microscopy (TEM), with direct observation providing for a deeper understanding of chemical bonding, reactivity, and states of matter at the nanoscale. We report on a nanoscale system consisting of endohedral fullerenes encapsulated within single-walled carbon nanotubes ((Kr@C60)@SWCNT), capable of the delivery and release of krypton atoms on-demand, via coalescence of host fullerene cages under the action of the electron beam (in situ) or heat (ex situ). The state and dynamics of Kr atoms were investigated by energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS). Kr atom positions were measured precisely using aberration-corrected high-resolution TEM (AC-HRTEM), aberration-corrected scanning TEM (AC-STEM), and single-atom spectroscopic imaging (STEM-EELS). The electron beam drove the formation of 2Kr@C120 capsules, in which van der Waals Kr2 and transient covalent [Kr2]+ bonding states were identified. Thermal coalescence led to the formation of longer coalesced nested nanotubes containing more loosely bound Krn chains (n = 3-6). In some instances, delocalization of Kr atomic positions was confirmed by STEM analysis as the transition to a one-dimensional (1D) gas, as Kr atoms were constrained to only one degree of translational freedom within long, well-annealed, nested nanotubes. Such nested nanotube structures were investigated by Raman spectroscopy. This material represents a highly compressed and dimensionally constrained 1D gas stable under ambient conditions. Direct atomic-scale imaging has revealed elusive bonding states and a previously unseen 1D gaseous state of matter of this noble gas element, demonstrating TEM to be a powerful tool in the discovery of chemistry at the single-atom level.

Three-Dimensional Nitrogen-Doped Carbonaceous Networks Anchored with Cobalt as Separator Modification Layers for Low-Polarization and Long-Lifespan Aluminum-Sulfur Batteries.

Aluminum-sulfur (Al-S) batteries have attracted extensive interest due to their high theoretical energy density, inherent safety, and low cost. However, severe polarization and poor cycling performance significantly limit the development of Al-S batteries. Herein, three-dimensional (3D) nitrogen-doped carbonaceous networks anchored with cobalt (Co@CMel-ZIF) is proposed as a separator modification layer to mitigate these issues, prepared via carbonizations of a mixture of ZIF-7, melamine, and CoCl2. It exhibits a 3D network structure with a moderate surface area and high average pore diameter, which is demonstrated to be effective in adsorbing the aluminum polysulfides and hindering the mobility of polysulfides across the separator for enhanced cyclic stability of Al-S batteries. Meanwhile, Co@CMel-ZIF are characterized by abundant catalytic pyridinic-N and Co-Nx active sites that effectively eliminate the barrier of sulfides' conversion and thereby facilitate the polarization reduction. As a result, Al-S cells based on the separator modified with Co@CMel-ZIF exhibit a low voltage polarization of 0.47 V under the current density of 50 mA g-1 at 20 °C and a high discharge specific capacity of 503 mAh g-1 after 150 cycles. In contrast, the cell employing a bare separator exhibits a polarization of 1.01 V and a discharge capacity of 300 mAh g-1 after 70 cycles under the same conditions. This work demonstrates that modifying the separators is a promising strategy to mitigate the high polarization and poor cyclability of Al-S batteries.

Enhancing Photocatalysis: Understanding the Mechanistic Diversity in Photocatalysts Modified with Single-Atom Catalytic Sites.

Surface modification of heterogeneous photocatalysts with single-atom catalysts (SACs) is an attractive approach for achieving enhanced photocatalytic performance. However, there is limited knowledge of the mechanism of photocatalytic enhancement in SAC-modified photocatalysts, which makes the rational design of high-performance SAC-based photocatalysts challenging. Herein, a series of photocatalysts for the aerobic degradation of pollutants based on anatase TiO2 modified with various low-cost, non-noble SACs (vanadate, Cu, and Fe ions) is reported. The most active SAC-modified photocatalysts outperform TiO2 modified with the corresponding metal oxide nanoparticles and state-of-the-art benchmark photocatalysts such as platinized TiO2 and commercial P25 powders. A combination of in situ electron paramagnetic resonance spectroscopy and theoretical calculations reveal that the best-performing photocatalysts modified with Cu(II) and vanadate SACs exhibit significant differences in the mechanism of activity enhancement, particularly with respect to the rate of oxygen reduction. The superior performance of vanadate SAC-modified TiO2 is found to be related to the shallow character of the SAC-induced intragap states, which allows for both the effective extraction of photogenerated electrons and fast catalytic turnover in the reduction of dioxygen, which translates directly into diminished recombination. These results provide essential guidelines for developing efficient SAC-based photocatalysts.

Subnanometer-Wide Indium Selenide Nanoribbons.

Indium selenides (InxSey) have been shown to retain several desirable properties, such as ferroelectricity, tunable photoluminescence through temperature-controlled phase changes, and high electron mobility when confined to two dimensions (2D). In this work we synthesize single-layer, ultrathin, subnanometer-wide InxSey by templated growth inside single-walled carbon nanotubes (SWCNTs). Despite the complex polymorphism of InxSey we show that the phase of the encapsulated material can be identified through comparison of experimental aberration-corrected transmission electron microscopy (AC-TEM) images and AC-TEM simulations of known structures of InxSey. We show that, by altering synthesis conditions, one of two different stoichiometries of sub-nm InxSey, namely InSe or ß-In2Se3, can be prepared. Additionally, in situ AC-TEM heating experiments reveal that encapsulated ß-In2Se3 undergoes a phase change to γ-In2Se3 above 400 °C. Further analysis of the encapsulated species is performed using X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX), and Raman spectroscopy, corroborating the identities of the encapsulated species. These materials could provide a platform for ultrathin, subnanometer-wide phase-change nanoribbons with applications as nanoelectronic components.

POM@ZIF Derived Mixed Metal Oxide Catalysts for Sustained Electrocatalytic Oxygen Evolution.

The design of efficient and stable oxygen evolution reaction (OER) catalysts based on noble-metal-free materials is crucial for energy conversion and storage. In this work, it was demonstrated how polyoxometalate (POM)-doped ZIF-67 can be converted into a stable oxygen evolution electrocatalyst by chemical etching, cation exchange, and thermal annealing steps. Characterization by X-ray photoelectron spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy and Raman spectroscopy indicate that POM-doped ZIF-67 derived carbon-supported metal oxides were synthesized. The resulting composite shows structural and compositional advantages which lead to low overpotential (306 mV at j=10 mA ⋅ cm-2 ) and long-term stability under harsh OER conditions (1.0 M aqueous KOH).

Computationally Efficient Handling of Partially Coherent Electron Sources in (S)TEM Image Simulations via Matrix Diagonalization.

We introduce a novel method to improve the computational efficiency for (S)TEM image simulation by employing matrix diagonalization of the mixed envelope function (MEF). The MEF is derived by taking the finite size and the energy spread of the effective electron source into account, and is a component of the transmission cross-coefficient that accounts for the correlation between partially coherent waves. Since the MEF is a four-dimensional array and its application in image calculations is time-consuming, we reduce the computation time by using its eigenvectors. By incorporating the aperture function into the matrix diagonalization, only a small number of eigenvectors are required to approximate the original matrix with high accuracy. The diagonalization enables for each eigenvector the calculation of the corresponding image by employing the coherent model. The individual images are weighted by the corresponding eigenvalues and then summed up, resulting in the total partially coherent image.

Chemical Vapor Deposition of High-Optical-Quality Large-Area Monolayer Janus Transition Metal Dichalcogenides.

One-pot chemical vapor deposition (CVD) growth of large-area Janus SeMoS monolayers is reported, with the asymmetric top (Se) and bottom (S) chalcogen atomic planes with respect to the central transition metal (Mo) atoms. The formation of these 2D semiconductor monolayers takes place upon the thermodynamic-equilibrium-driven exchange of the bottom Se atoms of the initially grown MoSe2 single crystals on gold foils with S atoms. The growth process is characterized by complementary experimental techniques including Raman and X-ray photoelectron spectroscopy, transmission electron microscopy, and the growth mechanisms are rationalized by first principle calculations. The remarkably high optical quality of the synthesized Janus monolayers is demonstrated by optical and magneto-optical measurements which reveal the strong exciton-phonon coupling and enable an exciton g-factor of -3.3.

Enhanced Electrochemical Capacity of Spherical Co-Free Li1.2 Mn0.6 Ni0.2 O2 Particles after a Water and Acid Treatment and its Influence on the Initial Gas Evolution Behavior.

Li-rich layered oxides (LRLO) with specific energies beyond 900 Wh kg-1 are one promising class of high-energy cathode materials. Their high Mn-content allows reducing both costs and the environmental footprint. In this work, Co-free Li1.2 Mn0.6 Ni0.2 O2 was investigated. A simple water and acid treatment step followed by a thermal treatment was applied to the LRLO to reduce surface impurities and to establish an artificial cathode electrolyte interface. Samples treated at 300 °C show an improved cycling behavior with specific first cycle capacities of up to 272 mAh g-1 , whereas powders treated at 900 °C were electrochemically deactivated due to major structural changes of the active compounds. Surface sensitive analytical methods were used to characterize the structural and chemical changes compared to the bulk material. Online DEMS measurements were conducted to get a deeper understanding of the effect of the treatment strategy on O2 and CO2 evolution during electrochemical cycling.

Integrated Differential Phase Contrast (IDPC)-STEM Utilizing a Multi-Sector Detector for Imaging Thick Samples.

The integrated differential phase contrast (IDPC) method is useful for generating the potential map of a thin sample. We evaluate theoretically the potential of IDPC imaging for thick samples by varying the focus at different sample thicknesses. Our calculations show that high defocus values result in enhanced anisotropy of the contrast transfer function (CTF) and uninterpretable images, if a quadrant detector is applied. We further show that applying a multi-sector detector can result in an almost isotropic CTF. By sector number-dependent calculations for both Cc/C3-corrected and C3-corrected scanning transmission electron microscopy (STEM), we show that the increase of detector sectors not only removes the anisotropy of the CTF, but also improves image contrast and resolution. For a proof-of-principle IDPC-STEM (uncorrected) experiment, we realize the functionality of a 12-sector detector from a physical quadrant detector and demonstrate the improvement in contrast and resolution on the example of InGaN/GaN quantum well structure.

Anatase-Wrapped Rutile Nanorods as an Effective Electron Collector in Hybrid Photoanodes for Visible Light-Driven Oxygen Evolution.

Arrays of single crystal TiO2 rutile nanorods (RNRs) appear highly promising as electron-collecting substrates in hybrid photoanodes as the RNRs offer direct charge carriers transport pathways, contrary to the conventional electrodes prepared from TiO2 powders that suffer from the numerous charge traps at the grain boundaries. However, the specific surface area of the nanorods is highly limited by their smooth morphology, which might be detrimental in view of utilizing the RNR as a substrate for immobilizing other functional materials. In this study, we developed a novel anatase-wrapped RNR (ARNR) material fabricated by a facile seed layer-free hydrothermal method. The ARNR comprises polycrystalline anatase nanoparticles formed on the surface of RNR, resulting in a large surface area that provides more deposition sites compared to the bare nanorods. Herein, we functionalize ARNR and RNR electrodes with polymeric carbon nitride (CNx) coupled with a CoO(OH)x cocatalyst for dioxygen evolution. The anatase wrapping of the rutile nanorod scaffold is found to be crucial for effective deposition of CNx and for improved photoanode operation in visible light-driven (λ > 420 nm) oxygen evolution, yielding a significant enhancement of photocurrent (by the factor of ∼3.7 at 1.23 V vs. RHE) and faradaic efficiency of oxygen evolution (by the factor of ∼2) as compared to photoanodes without anatase interlayer. This study thus highlights the importance of careful interfacial engineering in constructing photoelectrocatalytic systems for solar energy conversion and paves the way for the use of ARNR-based electron collectors in further hybrid and composite photochemical architectures for solar fuel production.

Single-molecule imaging and kinetic analysis of intermolecular polyoxometalate reactions.

We induce and study reactions of polyoxometalate (POM) molecules, [PW12O40]3- (Keggin) and [P2W18O62]6- (Wells-Dawson), at the single-molecule level. Several identical carbon nanotubes aligned side by side within a bundle provided a platform for spatiotemporally resolved imaging of ca. 100 molecules encapsulated within the nanotubes by transmission electron microscopy (TEM). Due to the entrapment of POM molecules their proximity to one another is effectively controlled, limiting molecular motion in two dimensions but leaving the third dimension available for intermolecular reactions between pairs of neighbouring molecules. By coupling the information gained from high resolution structural and kinetics experiments via the variation of key imaging parameters in the TEM, we shed light on the reaction mechanism. The dissociation of W-O bonds, a key initial step of POM reactions, is revealed to be reversible by the kinetic analysis, followed by an irreversible bonding of POM molecules to their nearest neighbours, leading to a continuous tungsten oxide nanowire, which subsequently transforms into amorphous tungsten-rich clusters due to progressive loss of oxygen atoms. The overall intermolecular reaction can therefore be described as a step-wise reductive polycondensation of POM molecules, via an intermediate state of an oxide nanowire. Kinetic analysis enabled by controlled variation of the electron flux in TEM revealed the reaction to be highly flux-dependent, which leads to reaction rates too fast to follow under the standard TEM imaging conditions. Although this presents a challenge for traditional structural characterisation of POM molecules, we harness this effect by controlling the conditions around the molecules and tuning the imaging parameters in TEM, which combined with theoretical modelling and image simulation, can shed light on the atomistic mechanisms of the reactions of POMs. This approach, based on the direct space and real time chemical reaction analysis by TEM, adds a new method to the arsenal of single-molecule kinetics techniques.

Electrocatalytic Oxygen Evolution by Hierarchically Structured Cobalt-Iron Composites.

The development of scalable routes to highly active and efficient oxygen evolution reaction (OER) electrocatalysts based on earth-abundant materials is crucial for post-fossil fuel energy schemes. Here, we demonstrate how commercial copper foam electrodes can be functionalized for water oxidation using a facile electrodeposition process. The resulting composite electrode features hierarchically structured cobalt-iron-based catalyst particles, which offer channel-like structures for the transport of electrolyte and release of oxygen gas bubbles. We report high electrocatalytic OER performance as demonstrated by high current densities at low overpotentials (293 mV at j = 50 mA cm-2) and long-term stability under technologically relevant alkaline conditions (>24 h in 1.0 M aqueous KOH).

Lattice contrast in the core-loss EFTEM signal of graphene.

The realization of chromatic aberration correction enables energy-filtered transmission electron microscopy (EFTEM) at atomic resolution even for large energy windows. Previous works have demonstrated lattice contrast from ionization-edge signals such as the L2,3 edges of silicon or titanium. However, the direct interpretation as chemical information was found to be hampered by contributions from elastic contrast with dynamic scattering, especially for thick samples. Here we demonstrate that even for thin samples with light atoms, the interpretation of the ionization-edge signal is complicated by inversions from bright-atom to dark-atom contrast. Our EFTEM experiments for graphene show lattice contrast in the carbon K-edge signal, and we find bright-atom and dark-atom contrast for different defoci.

Direct Imaging of Atomic Permeation Through a Vacancy Defect in the Carbon Lattice.

Porous graphene has shown promise as a new generation of selective membrane for sieving atoms, ions and molecules. However, the atomistic mechanisms of permeation through defects in the graphenic lattice are still unclear and remain unobserved in action, at the atomic level. Here, the direct observation of palladium atoms from a nanoparticle passing through a defect in a single-walled carbon nanotube one-by-one has been achieved with atomic resolution in real time, revealing key stages of the atomic permeation. Bonding between the moving atom and dangling bonds around the orifice, immediately before and after passing through the subnano-pore, plays an important role in the process. Curvature of the graphenic lattice crucially defines the direction of permeation from concave to convex side due to a difference in metal-carbon bonding at the curved surfaces as confirmed by density functional theory calculations, demonstrating the potential of porous carbon nanotubes for atom sieving.

Atomic mechanism of metal crystal nucleus formation in a single-walled carbon nanotube.

Knowing how crystals nucleate at the atomic scale is crucial for understanding, and in turn controlling, the structure and properties of a wide variety of materials. However, because of the scale and highly dynamic nature of nuclei, the formation and early growth of nuclei are very difficult to observe. Here, we have employed single-walled carbon nanotubes as test tubes, and an 'atomic injector' coupled with aberration-corrected transmission electron microscopy, to enable in situ imaging of the initial steps of nucleation at the atomic scale. With three different metals we observed three main processes prior to heterogeneous nucleation: formation of crystal nuclei directly from an atomic seed (Fe), from a pre-existing amorphous nanocluster (Au) or by coalescence of two separate amorphous sub-nanometre clusters (Re). We demonstrate the roles of the amorphous precursors and the existence of an energy barrier before nuclei formation. In all three cases, crystal nucleus formation occurred through a two-step nucleation mechanism.

Bond Dissociation and Reactivity of HF and H2O in a Nano Test Tube.

Molecular motion and bond dissociation are two of the most fundamental phenomena underpinning the properties of molecular materials. We entrapped HF and H2O molecules within the fullerene C60 cage, encapsulated within a single-walled carbon nanotube (X@C60)@SWNT, where X = HF or H2O. (X@C60)@SWNT represents a class of molecular nanomaterial composed of a guest within a molecular host within a nanoscale host, enabling investigations of the interactions of isolated single di- or triatomic molecules with the electron beam. The use of the electron beam simultaneously as a stimulus of chemical reactions in molecules and as a sub-angstrom resolution imaging probe allows investigations of the molecular dynamics and reactivity in real time and at the atomic scale, which are probed directly by chromatic and spherical aberration-corrected high-resolution transmission electron microscopy imaging, or indirectly by vibrational electron energy loss spectroscopy in situ during scanning transmission electron microscopy experiments. Experimental measurements indicate that the electron beam triggers homolytic dissociation of the H-F or H-O bonds, respectively, causing the expulsion of the hydrogen atoms from the fullerene cage, leaving fluorine or oxygen behind. Because of a difference in the mechanisms of penetration through the carbon lattice available for F or O atoms, atomic fluorine inside the fullerene cage appears to be more stable than the atomic oxygen under the same conditions. The use of (X@C60)@SWNT, where each molecule X is "packaged" separately from each other, in combination with the electron microscopy methods and density functional theory modeling in this work, enable bond dynamics and reactivity of individual atoms to be probed directly at the single-molecule level.

Imaging an unsupported metal-metal bond in dirhenium molecules at the atomic scale.

Metallic bonds remain one of the most important and least understood of the chemical bonds. In this study, we generated Re2 molecules in which the Re-Re core is unsupported by ligands. Real-time imaging of the atomic-scale dynamics of Re2 adsorbed on a graphitic lattice allows direct measurement of Re-Re bond lengths for individual molecules that changes in discrete steps correlating with bond order from one to four. Direct imaging of the Re-Re bond breaking process reveals a new bonding state with the bond order less than one and a high-amplitude vibrational stretch, preceding the bond dissociation. The methodology, based on aberration-corrected transmission electron microscopy imaging, is shown to be a powerful analytical tool for the investigation of dynamics of metallic bonding at the atomic level.