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Silica nanosheets (SN) derived from natural vermiculite (Verm) were successfully incorporated into polyethersulfone–polyvinylpyrrolidone (PES–PVP) polymer to fabricate high–temperature proton exchange membranes (HT–PEMs). The content of SN filler was varied (0.1–0.75 wt%) to study its influence on proton conductivity, power density and durability. Benefiting from the hydroxyl groups of SN that enable the formation of additional proton–transferring pathways, the inorganic–organic membrane displayed enhanced proton conductivity of 48.2 mS/cm and power density of 495 mW/cm2 at 150 °C without humidification when the content of SN is 0.25 wt%. Furthermore, exfoliated SN (E–SN) and sulfonated SN (S–SN), which were fabricated by a liquid–phase exfoliation method and silane condensation, respectively, were embedded in PES–PVP polymer matrix by a simple blending method. Due to the significant contribution from sulfonic groups in S–SN, the membrane with 0.25 wt% S–SN reached the highest proton conductivity of 51.5 mS/cm and peak power density of 546 mW/cm2 at 150 °C, 48% higher than the pristine PES–PVP membranes. Compared to unaltered PES–PVP membrane, SN added hybrid composite membrane demonstrated excellent durability for the fuel cell at 150 °C. Using a facile method to prepare 2D SN from natural clay minerals, the strategy of exfoliation and functionalization of SN can be potentially used in the production of HT–PEMs.

Fabrics—materials consisting of layers of woven fibres—are some of the most important materials in everyday life1. Previous nanoscale weaves2–16 include isotropic crystalline covalent organic frameworks12–14 that feature rigid helical strands interlaced in all three dimensions, rather than the two-dimensional17,18 layers of flexible woven strands that give conventional textiles their characteristic flexibility, thinness, anisotropic strength and porosity. A supramolecular two-dimensional kagome weave15 and a single-layer, surface-supported, interwoven two-dimensional polymer16 have also been reported. The direct, bottom-up assembly of molecular building blocks into linear organic polymer chains woven in two dimensions has been proposed on a number of occasions19–23, but has not previously been achieved. Here we demonstrate that by using an anion and metal ion template, woven molecular ‘tiles’ can be tessellated into a material consisting of alternating aliphatic and aromatic segmented polymer strands, interwoven within discrete layers. Connections between slowly precipitating pre-woven grids, followed by the removal of the ion template, result in a wholly organic molecular material that forms as stacks and clusters of thin sheets—each sheet up to hundreds of micrometres long and wide but only about four nanometres thick—in which warp and weft single-chain polymer strands remain associated through periodic mechanical entanglements within each sheet. Atomic force microscopy and scanning electron microscopy show clusters and, occasionally, isolated individual sheets that, following demetallation, have slid apart from others with which they were stacked during the tessellation and polymerization process. The layered two-dimensional molecularly woven material has long-range order, is birefringent, is twice as stiff as the constituent linear polymer, and delaminates and tears along well-defined lines in the manner of a macroscopic textile. When incorporated into a polymer-supported membrane, it acts as a net, slowing the passage of large ions while letting smaller ions through. An anion and metal ion template is used to form woven polymer patches that are joined together by polymerization into a fully woven, two-dimensional, molecular patchwork.

Single-particle reconstruction can be used to perform three-dimensional (3D) imaging of homogeneous populations of nano-sized objects, in particular viruses and proteins. Here, it is demonstrated that it can also be used to obtain 3D reconstructions of heterogeneous populations of inorganic nanoparticles. An automated acquisition scheme in a scanning transmission electron microscope is used to collect images of thousands of nanoparticles. Particle images are subsequently semi-automatically clustered in terms of their properties and separate 3D reconstructions are performed from selected particle image clusters. The result is a 3D dataset that is representative of the full population. The study demonstrates a methodology that allows 3D imaging and analysis of inorganic nanoparticles in a fully automated manner that is truly representative of large particle populations.

The rise of two-dimensional (2D) crystalline superconductors has opened a new frontier of investigating unconventional quantum phenomena in low dimensions. However, despite the enormous advances achieved towards understanding the underlying physics, practical device applications like sensors and detectors using 2D superconductors are still lacking. Here, we demonstrate nonreciprocal antenna devices based on atomically thin NbSe2. Reversible nonreciprocal charge transport is unveiled in 2D NbSe2 through multi-reversal antisymmetric second harmonic magnetoresistance isotherms. Based on this nonreciprocity, our NbSe2 antenna devices exhibit a reversible nonreciprocal sensitivity to externally alternating current (AC) electromagnetic waves, which is attributed to the vortex flow in asymmetric pinning potentials driven by the AC driving force. More importantly, a successful control of the nonreciprocal sensitivity of the antenna devices has been achieved by applying electromagnetic waves with different frequencies and amplitudes. The device’s response increases with increasing electromagnetic wave amplitude and exhibits prominent broadband sensing from 5 to 900 MHz., Here, the authors observe reversible nonreciprocal charge transport in two-dimensional NbSe2, and demonstrate antenna devices exhibiting strong sensitivity to driving AC electromagnetic waves in the superconducting regime.

Metal sulfide and metal oxide alloys of the form Mo1-x W x S2 and Mo1-x W x O3 (0 ≤ x ≤ 1) are synthesized with varying nominal stoichiometries (x = 0, 0.25, 0.50, 0.75, and 1.0) by thermolysis of the molecular precursors MoL4 and WS(S2)L2 (where L = S2CNEt2) in tandem and in various ratios. Either transition-metal dichalcogenides or transition-metal oxides can be produced from the same pair of precursors by the choice of reaction conditions; metal sulfide alloys of the form Mo1-x W x S2 are produced in an argon atmosphere, while the corresponding metal oxide alloys Mo1-x W x O3 are produced in air, both under atmospheric pressure at 450 °C and for only 1 h. Changes in Raman spectra and in powder X-ray diffraction patterns are observed across the series of alloys, which confirm that alloying is successful in the bulk materials. For the oxide materials, we show that the relatively complicated diffraction patterns are a result of differences in the tilt angle of MO6 octahedra within three closely related unit cell types. Alloying of Mo and W in the products is characterized at the microscale and nanoscale by scanning electron microscopy-energy-dispersive X-ray spectroscopy (EDX) and scanning transmission electron microscopy-EDX spectroscopy, respectively.

Liquid- phase exfoliation (LPE) is the principal method of producing two-dimensional (2D) materials such as graphene in large quantities with a good balance between quality and cost and is now widely adopted by both the academic and industrial sectors. The fragmentation and exfoliation mechanisms involved have usually been simply attributed to the force induced by ultrasound and the interaction with the solvent molecules. Nonetheless, little is known about how they actually occur, i.e., how thick and large graphite crystals can be exfoliated into thin and small graphene flakes. Here, we demonstrate that during ultrasonic LPE the transition from graphite flakes to graphene takes place in three distinct stages. First, sonication leads to the rupture of large flakes and the formation of kink band striations on the flake surfaces, primarily along zigzag directions. Second, cracks form along these striations, and together with intercalation of solvent, lead to the unzipping and peeling off of thin graphite strips that in the final stage are exfoliated into graphene. The findings will be of great value in the quest to optimize the lateral dimensions, thickness, and yield of graphene and other 2D materials in large-scale LPE for various applications.

Van der Waals heterostructures form a massive interdisciplinary research field, fueled by the rich material science opportunities presented by layer assembly of artificial solids with controlled composition, order and relative rotation of adjacent atomic planes. Here we use atomic resolution transmission electron microscopy and multiscale modeling to show that the lattice of MoS$_2$ and WS$_2$ bilayers twisted to a small angle, $\theta

In this work, we applied low-field, NMR spin–lattice measurements to evaluate for the first time the effect of carbonization temperature (range 600–1000 ℃) on the preparation of Alumina-Carbon Molecular Sieve Membranes (Al-CMSMs), providing new insights into intra-pore fluid interactions. The results show that the average Al-CMSM pore size generally increases with carbonization temperature whilst the hydrophilicity of the pore surface, and the amount of strongly adsorbed H2O, decreases with an increasing carbonization temperature. As such, lower carbonization temperatures produce more hydrophilic membranes, with further evidence provided by FTIR measurements demonstrating the presence of polar functional groups on the surface, with water interacting more strongly with the membrane surface, as evidenced by NMR. It was found that the Al-CMSM carbonization temperature significantly affected permeance and H2O/CH4 permselectivity by altering the membrane pore size distribution and pore hydrophilicity. H2O permeance values are seen to be up to 100 times larger than respective CH4 permeance values. The greater permeance of H2O is attributed to the larger kinetic diameter of CH4 relative to H2O and the adsorption of water in the hydrophilic pores enhancing the adsorption-diffusion transport mechanism. Optimal water permeation temperatures are thus higher for the more hydrophilic membranes, obtained at lower carbonization temperatures, as more energy is required to remove strongly adsorbed water blocking the pores. At higher carbonization temperatures, the Knudsen diffusion mechanism of permeance dominates over the adsorption-diffusion mechanism thereby reducing permeance as diffusion slows due to collisions between gas molecules and the pore walls. CH4 permeation always occurs via Knudsen diffusion with CH4 permeance increasing with permeation temperature due to the increased rate of CH4 diffusion.

Clays and micas are receiving attention as materials that, in their atomically thin form, could allow for novel proton conductive, ion selective, osmotic power generation, or solvent filtration membranes. The interest arises from the possibility of controlling their properties by exchanging ions in the crystal lattice. However, the ion exchange process itself remains largely unexplored in atomically thin materials. Here we use atomic-resolution scanning transmission electron microscopy to study the dynamics of the process and reveal the binding sites of individual ions in atomically thin and artificially restacked clays and micas. Imaging ion exchange after different exposure time and for different crystal thicknesses, we find that the ion diffusion constant, D, for the interlayer space of atomically thin samples is up to 10^4 times larger than in bulk crystals and approaches its value in free water. Surprisingly, samples where no bulk exchange is expected display fast exchange if the mica layers are twisted and restacked; but in this case, the exchanged ions arrange in islands controlled by the moir\'e superlattice dimensions. We attribute the fast ion diffusion to enhanced interlayer expandability resulting from weaker interlayer binding forces in both atomically thin and restacked materials. Finally, we demonstrate images of individual surface cations for these materials, which had remained elusive in previous studies. This work provides atomic scale insights into ion diffusion in highly confined spaces and suggests strategies to design novel exfoliated clays membranes., Comment: 11 pages, 4 figures, plus 35 pages supplementary information

Transmission electron microscope (TEM) specimen preparation by focused ion beam (FIB) milling requires delicate polishing of a thin window of material during the final stages of the procedure. Over or underpolishing is common and requires extra microscope resources to correct. Despite some methods for lamella thickness measurement being available, the majority of users judge the final polishing step subjectively from scanning electron microscope (SEM) images acquired between milling steps. Here we demonstrate successful thickness determination of thin silicon lamellae using calibrated secondary electron detectors in a FIB-SEM dual-beam chamber. Unlike previous thickness measurement methods it does not require long acquisition times, the use of in-chamber scanning transmission electron microscope (STEM) or energy dispersive x-ray spectroscopy detectors. The calibration aligns a SEM image to an electron energy loss spectroscopy (EELS) map of lamella thickness acquired in a TEM. This calibration reveals the greyscale-thickness dependence of two secondary electron SEM detectors: the through-lens detector (TLD) and the in-chamber electron detector (ICE). It was found that lamella thickness estimation for TLD images is accurate for areas thinner than 0.4 t/λ, whilst ICE images are most accurate for areas thicker than 0.5 t/λ up to 1.1 t/λ. The procedure presented here allows objective lamella thickness determination during the final stages of FIB specimen preparation using conventional imaging modes for common secondary electron detectors. LAY DESCRIPTION: Successful analysis of a material in a transmission electron microscope requires very thin windows of the material to be fabricated. Despite the quality of this analysis relying heavily on the thickness of the window, measuring thickness during window fabrication is not common practice. The authors show that it is possible to measure the thickness of the window directly in a focused-ion-beam chamber with a scanning electron microscope without altering the fabrication procedure, and using electron detectors common to most microscopes.

In graphite crystals, layers of graphene reside in three equivalent, but distinct, stacking positions typically referred to as A, B, and C projections. The order in which the layers are stacked defines the electronic structure of the crystal, providing an exciting degree of freedom which can be exploited for designing graphitic materials with unusual properties including predicted higherature superconductivity and ferromagnetism. However, the lack of control of the stacking sequence limits most research to the stable ABA form of graphite. Here, we demonstrate a strategy to control the stacking order using van der Waals technology. To this end, we first visualize the distribution of stacking domains in graphite films and then perform directional encapsulation of ABC-rich graphite crystallites with hexagonal boron nitride (hBN). We found that hBN encapsulation, which is introduced parallel to the graphite zigzag edges, preserves ABC stacking, while encapsulation along the armchair edges transforms the stacking to ABA. The technique presented here should facilitate new research on the important properties of ABC graphite.

Reducing the size of a material, from a bulk solid to a nanomaterial, may lead to drastic changes of various properties including reactivity and optical properties. Chemical reactivity is often inc...

PubMed: 31426634, Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

In this work, we apply an amine-assisted silica pillaring method to create the first example of a porous Mo2TiC2 MXene with nanoengineered interlayer distances. The pillared Mo2TiC2 has a surface area of 202 m2 g-1, which is among the highest reported for any MXene, and has a variable gallery height between 0.7 and 3 nm. The expanded interlayer distance leads to significantly enhanced cycling performance for Li-ion storage, with superior capacities, rate capabilities and cycling stabilities in comparison to the non-pillared version. The pillared Mo2TiC2 achieved capacities over 1.7 times greater than multilayered MXene at 20 mA g-1 (≈ 320 mAh g-1) and 2.5 times higher at 1 A g-1 (≈ 150 mAh g-1). The fast-charging properties of pillared Mo2TiC2 are further demonstrated by outstanding stability even at 1 A g-1 (under 8 min charge time), retaining 80% of the initial capacity after 500 cycles. Furthermore, we use a combination of spectroscopic techniques (i.e. XPS, NMR and Raman) to show unambiguously that the charge storage mechanism of this MXene occurs by a conversion reaction through the formation of Li2O. This reaction increases by 2-fold the capacity beyond intercalation, and therefore, its understanding is crucial for further development of this family of materials. In addition, we also investigate for the first time the sodium storage properties of the pillared and non-pillared Mo2TiC2.

We report a rapid solution-phase strategy to synthesize alloyed PtNi nanoparticles which demonstrate outstanding functionality for the oxygen reduction reaction (ORR). This one-pot co-reduction colloidal synthesis results in a monodisperse population of single-crystal nanoparticles of rhombic dodecahedral morphology, with Pt enriched edges and compositions close to Pt1Ni2. We use nanoscale 3D compositional analysis to reveal for the first time that oleylamine (OAm)-aging of the rhombic dodecahedral Pt1Ni2 particles results in Ni leaching from surface facets, producing aged particles with concave faceting, an exceptionally high surface area and a composition of Pt2Ni1. We show that the modified atomic nanostructures catalytically outperform the original PtNi rhombic dodecahedral particles by more than 2-fold and also yield improved cycling durability. Their functionality for the ORR far exceeds commercially available Pt/C nanoparticle electrocatalysts, both in terms of mass-specific activities (up to a 25-fold increase) and intrinsic area-specific activities (up to a 27-fold increase)., Comment: 14 pages, 4 figures, supplementary information

Nonspecific molecular adsorption like airborne contamination occurs on most surfaces including those of 2D materials and alters their properties. While the surface contamination is studied using a plethora of techniques, the effect of contamination on a confined system such as nanochannels, nanopores leading to their clogging is still lacking. We report a systematic investigation of hydrocarbon adsorption in the angstrom slit channels of varied heights. Hexane is chosen to mimic the hydrocarbon contamination and the clogging of the angstrom-channels is evaluated via a Helium gas flow measurement. The level of the hexane adsorption, in other words, the degree of clogging depends on the size difference between the channels and hexane. A dynamic transition of the clogging and revival process is shown in sub-2 nm thin channels. Long-term storage and stability of our angstrom-channels is demonstrated here up to three years, alleviating the contamination and unclogging the channels using thermal treatment. This study highlights the importance of the nanochannels stability and demonstrates self-cleansing nature of sub-2 nm thin channels enabling a robust platform for molecular transport and separation studies. We provide a method to assess the cleanliness of the nanoporous membranes, which is vital for the practical applications of nanofluidics in various fields such as molecular sensing, separation and power generation.

Liquid-phase transmission electron microscopy is used to study a wide range of chemical processes, where its unique combination of spatial and temporal resolution provides countless insights into nanoscale reaction dynamics. However, achieving sub-nanometer resolution has proved difficult due to limitations in the current liquid cell designs. Here, a novel experimental platform for in situ mixing using a specially developed 2D heterostructure-based liquid cell is presented. The technique facilitates in situ atomic resolution imaging and elemental analysis, with mixing achieved within the immediate viewing area via controllable nanofracture of an atomically thin separation membrane. This novel technique is used to investigate the time evolution of calcium carbonate synthesis, from the earliest stages of nanodroplet precursors to crystalline calcite in a single experiment. The observations provide the first direct visual confirmation of the recently developed liquid-liquid phase separation theory, while the technological advancements open an avenue for many other studies of early stage solution-phase reactions of great interest for both the exploration of fundamental science and developing applications.

Polycrystalline thin films of molybdenum-doped rhenium disulphide (Mo-doped ReS2) alloys were synthesised by aerosol-assisted chemical vapour deposition (AACVD) using precursor solutions containing (1) [Re(S2CC6H5)(S3CC6H5)2], and (2) [Mo(S2CNEt2)4]. Synthesised thin films were characterised using powder X-Ray diffraction (p-XRD), Raman spectroscopy, scanning electron microscope (SEM), transmission electron microscope (TEM), inductively coupled plasma-optical emission spectrometry (ICP-OES) and energy dispersive X-Ray (EDX). The p-XRD shows that interlayer spacing increases with increasing Mo content in the ReS2 matrix, and (001) plane becomes broad and weak as the molybdenum increases in the doped films. The destruction of the vibrational modes of ReS2 on increasing the Mo content and a clear shift in the Eg vibrational and Ag-like modes were also observed by Raman analysis. The presence of Mo in the ReS2 matrix was detected by ICP-OES. It was observed that the Mo content in the final material was 7.61 at% compared to the initial feed of 15 at%. The SEM images of the doped alloy films revealed nano crystal morphology, and the morphology changed when there was an increase in the Mo portion into the ReS2 crystal structure.

Quaternary MAX phases, (Ta1−xTix)3AlC2 (x = 0.4, 0.62, 0.75, 0.91 or 0.95), have been synthesised via pressureless sintering of TaC, TiC, Ti and Al powders. Via chemical etching of the Al layers, (Ta0.38Ti0.62)3C2Tz – a new MXene, has also been synthesised. All materials contain an M-layer solid solution of Ta and Ti, with a variable Ta concentration, paving the way for the synthesis of a range of alloyed (Ta,Ti)3C2Tz MXenes with tuneable compositions for a wide range of potential applications.

State of the art electrocatalysts for the hydrogen evolution reaction (HER) are based on metal nanoparticles (NPs). It has been shown that the localized surface plasmon resonance (LSPR) excitation in plasmonic NPs can be harvested to accelerate a variety of molecular transformations. This enables the utilization of visible light as an energy input to enhance HER performances. However, most metals that are active toward the HER do not support LSPR excitation in the visible or near-IR ranges. We describe herein the synthesis of gold-rhodium core-shell nanoflowers (Au@Rh NFs) that are composed of a core made up of spherical Au NPs and shells containing Rh branches. The Au@Rh NFs were employed as a model system to probe how the LSPR excitation from Au NPs can lead to an enhancement in the HER performance for Rh. Our data demonstrate that the LSPR excitation at 533 nm (and 405 nm) leads to an improvement in the HER performance of Rh, which depends on the morphological features of the Au Rh NFs, offering opportunities for optimization of the catalytic performance. Control experiments indicate that this improvement originates from the stronger interaction of Au@Rh NFs with H2O molecules at the surface, leading to an icelike configuration, which facilitated the HER under LSPR excitation.

Nitrogen doping of the carbon is an important method to improve the performance and durability of catalysts for proton exchange membrane fuel cells by platinum-nitrogen and carbon-nitrogen bonds. This study shows that p-phenyl groups and graphitic N acting bridges linking platinum and the graphene/carbon black (the ratio graphene/carbon black=2/3) hybrid support materials achieved the average size of platinum nanoparticles with (4.88 +/- 1.79) nm. It improved the performance of the lower-temperature hydrogen fuel cell up to 0.934 W cm-2 at 0.60 V, which is 1.55 times greater than that of commercial Pt/C. Doping also enhanced the interaction between Pt and the support materials, and the resistance to corrosion, thus improving the durability of the low-temperature hydrogen fuel cell with a much lower decay of 10 mV at 0.80 A cm-2 after 30k cycles of an in-situ accelerated stress test of catalyst degradation than that of 92 mV in Pt/C, which achieves the target of Department of Energy (, 22 pages, 8 figures and supplementary information

Recently, the dual beam Xe+ plasma focused ion beam (Xe+pFIB) instrument has attracted increasing interest for site‐specific transmission electron microscopy (TEM) sample preparation for a local region of interest as it shows several potential benefits compared to conventional Ga+FIB milling. Nevertheless, challenges and questions remain especially in terms of FIB‐induced artefacts, which hinder reliable S/TEM microstructural and compositional analysis. Here we examine the efficacy of using Xe+ pFIB as compared with conventional Ga+ FIB for TEM sample preparation of Al alloys. Three potential source of specimen preparation artefacts were examined, namely: (1) implantation‐induced defects such as amophisation, dislocations, or ‘bubble’ formation in the near‐surface region resulting from ion bombardment of the sample by the incident beam; (2) compositional artefacts due to implantation of the source ions and (3) material redeposition due to the milling process. It is shown that Xe+pFIB milling is able to produce improved STEM/TEM samples compared to those produced by Ga+ milling, and is therefore the preferred specimen preparation route. Strategies for minimising the artefacts induced by Xe+pFIB and Ga+FIB are also proposed. Lay Description FIB (focused ion beam) instruments have become one of the most important systems in the preparation of site‐specific TEM specimens, which are typically 50‐100 nm in thickness. TEM specimen preparation of Al alloys is particularly challenging, as convention Ga‐ion FIB produces artefacts in these materials that make microstructural analysis difficult or impossible. Recently, the use of noble gas ion sources, such as Xe, has markedly improved milling speeds and is being used for the preparation of various materials. Hence, it is necessary to investigate the structural defects formed during FIB milling and assess the ion‐induced chemical contamination in these TEM samples. Here we explore the feasibility and efficiency of using Xe+PFIB as a TEM sample preparation route for Al alloys in comparison with the conventional Ga+FIB.

Capillary condensation of water is ubiquitous in nature and technology. It routinely occurs in granular and porous media, can strongly alter such properties as adhesion, lubrication, friction and corrosion, and is important in many processes used by microelectronics, pharmaceutical, food and other industries1–4. The century-old Kelvin equation5 is frequently used to describe condensation phenomena and has been shown to hold well for liquid menisci with diameters as small as several nanometres1–4,6–14. For even smaller capillaries that are involved in condensation under ambient humidity and so of particular practical interest, the Kelvin equation is expected to break down because the required confinement becomes comparable to the size of water molecules1–22. Here we use van der Waals assembly of two-dimensional crystals to create atomic-scale capillaries and study condensation within them. Our smallest capillaries are less than four angstroms in height and can accommodate just a monolayer of water. Surprisingly, even at this scale, we find that the macroscopic Kelvin equation using the characteristics of bulk water describes the condensation transition accurately in strongly hydrophilic (mica) capillaries and remains qualitatively valid for weakly hydrophilic (graphite) ones. We show that this agreement is fortuitous and can be attributed to elastic deformation of capillary walls23–25, which suppresses the giant oscillatory behaviour expected from the commensurability between the atomic-scale capillaries and water molecules20,21. Our work provides a basis for an improved understanding of capillary effects at the smallest scale possible, which is important in many realistic situations. In the tiniest of capillaries, barely larger than a water molecule, condensation is surprisingly predictable from the macroscopic Kelvin condensation equation, a coincidence partially owing to elastic deformation of the capillary walls.

When ceria is used as a support for many redox catalysis involved in green catalysis, it is well-known that the overlying noble metal can gain access to a significant quantity of oxygen atoms with high mobility and fast reduction and oxidation properties under mild conditions. However, it is as yet unclear what the underlying principle and the nature of the ceria surface involved are. By using two tailored morphologies of ceria nanocrystals, namely cubes and rods, it is demonstrated from Scanning Transmission Electron Microscopy with Electron Energy Loss Spectroscopy (STEM-EELS) mapping and Pulse Isotopic Exchange (PIE) that ceria nanocubes terminated with a polar surface (100) can give access to more than the top most layer of surface oxygen atoms. Also, they give higher oxygen mobility than ceria nanorods with a non-polar facet of (110). A new insight for the possible additional role of polar ceria surface plays in the oxygen mobility is obtained from Density Functional Theory (DFT) calculations which suggest that the (100) surface sites that has more than half-filled O on same plane can drive oxygen atoms to oxidise adsorbate(s) on Pd due to the strong electrostatic repulsion.

Suspended specimens of 2D crystals and their heterostructures are required for a range of studies including transmission electron microscopy (TEM), optical transmission experiments and nanomechanical testing. However, investigating the properties of laterally small 2D crystal specimens, including twisted bilayers and air sensitive materials, has been held back by the difficulty of fabricating the necessary clean suspended samples. Here we present a scalable solution which allows clean free-standing specimens to be realized with 100% yield by dry-stamping atomically thin 2D stacks onto a specially developed adhesion-enhanced support grid. Using this new capability, we demonstrate atomic resolution imaging of defect structures in atomically thin CrBr3, a novel magnetic material which degrades in ambient conditions., 17 pages (+ references), 3 Figures, 1 Table

Epitaxial films may be released from growth substrates and transferred to structurally and chemically incompatible substrates, but epitaxial films of transition metal perovskite oxides have not been transferred to electroactive substrates for voltage control of their myriad functional properties. Here we demonstrate good strain transmission at the incoherent interface between a strain-released film of epitaxially grown ferromagnetic La0.7Sr0.3MnO3 and an electroactive substrate of ferroelectric 0.68Pb(Mg1/3Nb2/3)O3-0.32PbTiO3 in a different crystallographic orientation. Our strain-mediated magnetoelectric coupling compares well with respect to epitaxial heterostructures, where the epitaxy responsible for strong coupling can degrade film magnetization via strain and dislocations. Moreover, the electrical switching of magnetic anisotropy is repeatable and non-volatile. High-resolution magnetic vector maps reveal that micromagnetic behaviour is governed by electrically controlled strain and cracks in the film. Our demonstration should inspire others to control the physical/chemical properties in strain-released epitaxial oxide films by using electroactive substrates to impart strain via non-epitaxial interfaces., Key properties of transition metal perovskite oxides are degraded after epitaxial growth on ferroelectric substrates due to lattice-mismatch strain. Here, the authors use epitaxial lift-off and transfer to overcome this problem and demonstrate electric field control of a bulk-like magnetization.

Vertical stacking of atomically thin layered materials opens new possibilities for the fabrication of heterostructures with favorable optoelectronic properties. The combination of graphene, hexagonal boron nitride and semiconducting transition metal dichalcogenides allows fabrication of electroluminescence (EL) devices, compatible with a wide range of substrates. Here, we demonstrate a full integration of an electroluminescent van der Waals heterostructure in a monolithic optical microcavity made of two high reflectivity dielectric distributed Bragg reflectors (DBRs). Owing to the presence of graphene and hexagonal boron nitride protecting the WSe$_2$ during the top mirror deposition, we fully preserve the optoelectronic behaviour of the device. Two bright cavity modes appear in the EL spectrum featuring Q-factors of 250 and 580 respectively: the first is attributed directly to the monolayer area, while the second is ascribed to the portion of emission guided outside the WSe$_2$ island. By embedding the EL device inside the microcavity structure, a significant modification of the directionality of the emitted light is achieved, with the peak intensity increasing by nearly two orders of magnitude at the angle of the maximum emission compared with the same EL device without the top DBR. Furthermore, the coupling of the WSe$_2$ EL to the cavity mode with a dispersion allows a tuning of the peak emission wavelength exceeding 35 nm (80 meV) by varying the angle at which the EL is observed from the microcavity. This work provides a route for the development of compact vertical-cavity surface-emitting devices based on van der Waals heterostructures.

Accurately determining the morphology and hence the true surface areas of catalytic nanoparticles remains challenging. For many chemically synthesised nanoparticle suspensions conventional BET surface area measurements are often not feasible due to the large quantities of material required. For platinum, a paradigmatic catalyst, this issue is further complicated by the propensity of this metal to form porous aggregate structures comprised of smaller (ca. 2-5 nm) crystallites as opposed to continuous solid structures. This dendritic/porous particulate morphology leads to a large but poorly defined 'active' surface which is difficult to measure accurately. Here we compare, single nanoparticle electrochemistry with three dimensional (3D) electron tomography and quantitative 2D high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) analysis to yield insights into the porosity and chemically accessible surface area of a 30 nm diameter commercial Pt nanoparticle catalyst. Good quantitative agreement is found between 2D and 3D STEM-based measurements of the particle morphology, density and size distribution. Both 3D STEM tomography and single nanoparticle electrochemical measurements allow quantification of the surface area but the electrocatalytic surface area is found to be 2.8× larger than is measured in STEM; indicating the importance of the atomic scale roughness and structure (

MXenes are a recently discovered class of two-dimensional materials that have shown great potential as electrodes in electrochemical energy storage devices. Despite their promise in this area, MXenes can still suffer limitations in the form of restricted ion accessibility between the closely spaced multistacked MXene layers, causing low capacities and poor cycle life. Pillaring, a strategy where a secondary species is inserted between layers, has been used to increase interlayer spacings in clays with great success, but has had limited application in MXenes. We report a new amine-assisted pillaring methodology that successfully intercalates silica-based pillars between Ti3C2 layers. Using this technique, the interlayer spacing can be controlled with the choice of amine and calcination temperature, up to a maximum of 3.2 nm, the largest interlayer spacing reported for an MXene. Another effect of the pillaring is a dramatic increase in surface area, achieving BET surface areas of 235 m2 g-1, a sixty-fold increase over the unpillared material and the highest reported for MXenes using an intercalation-based method. The intercalation mechanism was revealed by different characterisation techniques, allowing the surface chemistry to be optimised for the pillaring process. The porous MXene was tested for Na-ion battery applications, and showed superior capacity, rate capability and remarkable stability compared with non-pillared materials, retaining 98.5% capacity between the 50th and 100th cycles. These results demonstrate the applicability and promise of pillaring techniques applied to MXenes, providing a new approach to optimising their properties for a range of applications. Porous MXenes are very promising materials for a range of applications including energy storage, conversion, catalysis and gas separations.

Convergent beam electron diffraction is routinely applied for studying deformation and local strain in thick crystals by matching the crystal structure to the observed intensity distributions. Recently, it has been demonstrated that CBED can be applied for imaging two-dimensional (2D) crystals where a direct reconstruction is possible and three-dimensional crystal deformations at a nanometre resolution can be retrieved. Here, we demonstrate that second-order effects allow for further information to be obtained regarding stacking arrangements between the crystals. Such effects are especially pronounced in samples consisting of multiple layers of 2D crystals. We show, using simulations and experiments, that twisted multilayer samples exhibit extra modulations of interference fringes in CBED patterns, i. e., a CBED moir\'e. A simple and robust method for the evaluation of the composition and the number of layers from a single-shot CBED pattern is demonstrated.

Activity of catalysts increase linearly with increasing ratio of Pd/Pt bimetallic to oxide species as observed in XRD. Bimetallic catalysts consisting of Pd and Pt on TiO 2 -zeolite (mordenite, beta, ZSM-5) supports were prepared and tested for the combustion of methane. The activity of the catalysts was found to be dependent on the zeolite topology and SiO 2 : Al 2 O 3 ratio and was linearly dependent on the proportion of Pd and Pt present in a bimetallic phase observed in XRD diffractograms of the catalysts. This linear dependence was valid for a range of zeolites used. STEM-EDS and electron tomography showed the Pd and Pt to be largely co-located and XAS and XPS indicated that the metals are mostly present in the form of oxide nanoparticles with a minor contribution from the metals at high SiO 2 : Al 2 O 3 ratios. Catalyst characterization showed there to be little difference overall in the metal loading and physical characteristics of the samples and NH 3 -TPD suggested that the activation of methane over acid sites is not important. Adding water to the feed, slightly reduced the conversion but did not affect the deactivation profile of the catalysts tested.

Carbon dioxide (CO2) hydrogenation to value-added molecules is an attractive way to reduce CO2 emission via upgrading. Herein, non-thermal plasma (NTP) activated CO2 hydrogenation over Ru/MgAl layered double hydroxide (LDH) catalysts was performed. The catalysis under the NTP conditions enabled significantly higher CO2 conversions (∼85 %) and CH4 yield (∼84 %) at relatively low temperatures compared with the conventional thermally activated catalysis. Regarding the catalyst preparation, it was found that the reduction temperature can affect the chemical state of the metal and metal-support interaction significantly, and thus altering the activity of the catalysts in NTP-driven catalytic CO2 hydrogenation. A kinetic study revealed that the NTP-catalysis has a lower activation energy (at ∼21 kJ mol−1) than that of the thermal catalysis (ca. 82 kJ mol−1), due to the alternative pathways enabled by NTP, which was confirmed by the comparative in situ diffuse reflectance infrared Fourier (DRIFTS) coupled with mass spectrometry (MS) characterisation of the catalytic systems.

Hexagonal boron nitride (hBN) is a prototypical high-quality two-dimensional insulator and an ideal material to study tunneling phenomena, as it can be easily integrated in vertical van der Waals devices. For spintronic devices, its potential has been demonstrated both for efficient spin injection in lateral spin valves and as a barrier in magnetic tunnel junctions (MTJs). Here we reveal the effect of point defects inevitably present in mechanically exfoliated hBN on the tunnel magnetoresistance of Co-hBN-NiFe MTJs. We observe a clear enhancement of both the conductance and magnetoresistance of the junction at well-defined bias voltages, indicating resonant tunneling through magnetic (spin-polarized) defect states. The spin polarization of the defect states is attributed to exchange coupling of a paramagnetic impurity in the few-atomic-layer thick hBN to the ferromagnetic electrodes. This is confirmed by excellent agreement with theoretical modelling. Our findings should be taken into account in analyzing tunneling processes in hBN-based magnetic devices. More generally, our study shows the potential of using atomically thin hBN barriers with defects to engineer the magnetoresistance of MTJs and to achieve spin filtering, opening the door towards exploiting the spin degree of freedom in current studies of point defects as quantum emitters.

Atoms start behaving as waves rather than classical particles if confined in spaces commensurate with their de Broglie wavelength. At room temperature this length is only about one angstrom even for the lightest atom, hydrogen. This restricts quantum-confinement phenomena for atomic species to the realm of very low temperatures(1-5). Here, we show that van der Waals gaps between atomic planes of layered crystals provide angstrom-size channels that make quantum confinement of protons apparent even at room temperature. Our transport measurements show that thermal protons experience a notably higher barrier than deuterons when entering van der Waals gaps in hexagonal boron nitride and molybdenum disulfide. This is attributed to the difference in the de Broglie wavelengths of the isotopes. Once inside the crystals, transport of both isotopes can be described by classical diffusion, albeit with unexpectedly fast rates comparable to that of protons in water. The demonstrated angstrom-size channels can be exploited for further studies of atomistic quantum confinement and, if the technology can be scaled up, for sieving hydrogen isotopes.

Four-dimensional scanning transmission electron microscopy is demonstrated to be a powerful technique for interrogating local strain of twisted graphene bilayers, revealing a two-regime lattice reconstruction process below the ‘magic’ angle.

This work studies the impact of adding 0.5 wt.% Si on the formation of Al3(Sc,Zr) L12 precipitates in a lean Al-Sc-Zr alloy. Precipitation kinetics are significantly accelerated when ageing at 300 and 375 °C in the presence of Si. At 375 °C, peak hardness occurs in a few minutes and is maintained up to 200 h at 375 °C . High resolution TEM reveals the presence of very fine core-shell L12 dispersoids ~5 nm in size that remain stable for up to 200 h at 375 °C. Using high-resolution energy dispersive X-ray spectroscopy (EDX) and atom probe tomography (APT), the presence of Si and Fe is detected in the core of the dispersoids, where their content decreases as a function of ageing time. Similar Si and Fe compositions were observed inside the dispersoids for both alloys regardless of bulk Si content. Both Si and Fe are found to have preference for the Al site in the L12 structure, which is supported by density functional theory (DFT) calculations. DFT also explains the decrease of Si and Fe over time, showing that there is no thermodynamic driving force for either Si or Fe to be present in the L12. Instead Si and Fe are found to play a crucial role at the early stages of clustering, but are expelled from the particles when they stabilise into L12 structures.

We have investigated the structure of atomic defects within monolayer NbSe2 encapsulated in graphene by combining atomic resolution transmission electron microscope imaging, density functional theory (DFT) calculations, and strain mapping using geometric phase analysis. We demonstrate the presence of stable Nb and Se monovacancies in monolayer material and reveal that Se monovacancies are the most frequently observed defects, consistent with DFT calculations of their formation energy. We reveal that adventitious impurities of C, N, and O can substitute into the NbSe2 lattice stabilizing Se divacancies. We further observe evidence of Pt substitution into both Se and Nb vacancy sites. This knowledge of the character and relative frequency of different atomic defects provides the potential to better understand and control the unusual electronic and magnetic properties of this exciting two-dimensional material.

Control over the electronic spectrum at low energy is at the heart of the functioning of modern advanced electronics: high electron mobility transistors, semiconductor and Capasso terahertz lasers, and many others. Most of those devices rely on the meticulous engineering of the size quantization of electrons in quantum wells. This avenue, however, hasn't been explored in the case of 2D materials. Here we transfer this concept onto the van der Waals heterostructures which utilize few-layers films of InSe as quantum wells. The precise control over the energy of the subbands and their uniformity guarantees extremely high quality of the electronic transport in such systems. Using novel tunnelling and light emitting devices, for the first time we reveal the full subbands structure by studying resonance features in the tunnelling current, photoabsorption and light emission. In the future, these systems will allow development of elementary blocks for atomically thin infrared and THz light sources based on intersubband optical transitions in few-layer films of van der Waals materials., Comment: 12 pages, 3 figures

Carbon nanomaterials, including 2D graphene-based materials, have shown promising applicability to drug delivery, tissue engineering, diagnostics, and various other biomedical areas. However, to exploit the benefits of these materials in some of the areas mentioned, it is necessary to understand their possible toxicological implications and long-term fate in vivo. We previously demonstrated that following intravenous administration, 2D graphene oxide (GO) nanosheets were largely excreted via the kidneys; however, a small but significant portion of the material was sequestered in the spleen. Herein, we interrogate the potential consequences of this accumulation and the fate of the spleen-residing GO over a period of nine months. We show that our thoroughly characterized GO materials are not associated with any detectable pathological consequences in the spleen. Using confocal Raman mapping of tissue sections, we determine the sub-organ biodistribution of GO at various time points after administration. The cells largely responsible for taking up the material are confirmed using immunohistochemistry coupled with Raman spectroscopy, and transmission electron microscopy (TEM). This combination of techniques identified cells of the splenic marginal zone as the main site of GO bioaccumulation. In addition, through analyses using both bright-field TEM coupled with electron diffraction and Raman spectroscopy, we reveal direct evidence of in vivo intracellular biodegradation of GO sheets with ultrastructural precision. This work offers critical information about biological processing and degradation of thin GO sheets by normal mammalian tissue, indicating that further development and exploitation of GO in biomedicine would be possible., This work was partially supported by the EPSRC NOWNANO DTC program and grants EP/K016946/1 and EP/M010619/1. This work has received funding from the European Union’s Horizon 2020 Research and Innovation Programme under Grant Agreement numbers GrapheneCore1 (696656) and GrapheneCore2 (785219). D.J. and K.K. would like to acknowledge the support by the UKRI, EPSRC from the Programme Grant 2D-Health (EP/P00119X/1). The DTRA, USA (grant HDTRA1-12-1-0013), is also acknowledged for partial support.

There is a critical research need for efficient luminescent colloidal nanocrystals, free from cadmium and lead whose toxicity subjects them to usage restrictions, with applications from display devices to biology. Approaches to directly replace cadmium-based materials have mainly focused on indium phosphide-based nanocrystals, however these too are subject to concerns over toxicity. Few other alternatives have been found that can compete with the emission range and efficiency of Cd and Pb-based nanocrystals. Group III-nitride nanocrystals, and their alloys, offer the exciting potential to tune bandgap energies from the ultraviolet to the near infrared yet a robust route towards efficient luminescent nitride nanocrystals is lacking. Here, the synthesis of photoluminescent indium zinc nitride quantum dots exhibiting tunable emission through the visible to near infrared spectra region, with quantum yields of up to 30% is reported. Capping the nanocrystals with both a GaN and ZnS shell significantly increased air stability and emission quantum yields. A proof-of-principle indium zinc nitride nanocrystal light emitting diode is also demonstrated. This work overcomes the significant challenges that have prevented the full exploration of nitride-based semiconductor nanocrystal development, providing a new system for further exploration as a heavy-metal free alternative to current state-of-the-art materials.

We develop herein plasmonic-catalytic Au-IrO2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO2, by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au-IrO2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO2 and to the activation of Ir-O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

To fully exploit van der Waals materials and their vertically stacked heterostructures, new mass-scalable production routes which are low cost but preserve the high electronic and optical quality of the single crystals are required. Here, we demonstrate an approach to realise a variety of functional heterostructures based on van der Waals nanocrystal films produced through the mechanical abrasion of bulk powders. We find significant performance enhancements in abraded heterostructures compared to those fabricated through inkjet printing of nanocrystal dispersions. To highlight the simplicity, applicability and scalability of the device fabrication, we demonstrate a multitude of different functional heterostructures such as resistors, capacitors and photovoltaics. We also demonstrate the creation of energy harvesting devices, such as large area catalytically active coatings for the hydrogen evolution reaction and enhanced triboelectric nanogenerator performance in multilayer films. The ease of device production makes this a promising technological route for up-scalable films and heterostructures., Low-cost, mass-scalable production routes which preserve the quality of the single crystals are required to up-scale van der Waals materials. Here, the authors demonstrate an approach to realise a variety of functional heterostructures based on van der Waals nanocrystal films produced through the mechanical abrasion of bulk powders.

The room temperature polar vapor sensing behavior of a graphene-TiS3 heterojunction material and TiS3 nanoribbons is described. The nanoribbons were synthesized via chemical vapor transport (CVT) and their structure was investigated by scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, Raman and Fourier transform infrared spectroscopies. The gas sensing performance was assessed by following the changes in their resistivities. Sensing devices were fabricated with gold contacts and with lithographically patterned graphene (Gr) electrodes in a heterojunction Gr-TiS3-Gr. The gold contacted TiS3 device has a rather linear I-V behavior while the Gr-TiS3-Gr heterojunction forms a contact with a higher Schottky barrier (250 meV). The I-V responses of the sensors were recorded at room temperature at a relative humidity of 55% and for different ethanol vapor concentrations (varying from 2 to 20 ppm). The plots indicate an increase in the resistance of Gr-TiS3-Gr due to adsorption of water and ethanol with a relatively high sensing response (~495% at 2 ppm). The results reveal that stable responses to 2 ppm concentrations of ethanol are achieved at room temperature. The response and recovery times are around 8 s and 72 s, respectively. Weaker responses are obtained for methanol and acetone.

State-of-the-art electrocatalysts for electrolyzer and fuel cell applications currently rely on platinum group metals, which are costly and subject to supply risks. In recent years, a vast collection of research has explored the possibility of reducing the Pt content in such catalysts by alloying with earth-abundant and cheap metals, enabling co-optimization of cost and activity. Here, using nanoparticle beam deposition, we explore the electrocatalytic performance of PtCu alloy clusters in the hydrogen evolution reaction (HER). Elemental compositions of the produced bimetallic clusters were shown by X-ray photoelectron spectroscopy (XPS) to range from 2 at. % to 38 at. % Pt, while high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) combined with energy dispersive X-ray (EDX) spectroscopy indicated that the predominant cluster morphologies could be characterized as either a fully mixed alloy or as a mixed core with a Cu-rich shell. In contrast with previous studies, a monotonic decrease in HER activity with increasing Cu content was observed over the composition range studied, with the current density measured at -0.3 V (vs reversible hydrogen electrode) scaling approximately linearly with Pt at. %. This trend opens up the possibility that PtCu could be used as a reference system for comparing the composition-dependent activity of other bimetallic catalysts.

Electrochemical exfoliation is one of the most promising methods for scalable production of graphene. However, limited understanding of its Raman spectrum as well as lack of measurement standards for graphene strongly limit its industrial applications. In this work we show a systematic study of the Raman spectrum of electrochemically exfoliated graphene, produced using different electrolytes and different types of solvents in varying amounts. We demonstrate that no information on the thickness can be extracted from the shape of the 2D peak as this type of graphene is defective. Furthermore, the number of defects and the uniformity of the samples strongly depend on the experimental conditions, including post-processing. Under specific conditions, formation of short conductive trans-polyacetylene chains has been observed. Our Raman analysis provides guidance for the community on how to get information on defects coming from electrolyte, temperature and other experimental conditions, by making Raman spectroscopy a powerful metrology tool., This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Nano Letters, American Chemical Society after peer review. To access the final edited and published work, included the SI, see DOI: 10.1021/acs.nanolett.0c00332

Zinc nitride (Zn3N2) colloidal quantum dots are composed of non-toxic, low-cost and earth-abundant elements. The effects of quantum confinement on the optical properties and charge dynamics of these dots are studied using steady state optical characterization and ultrafast fluence-dependent transient ab-sorption. The absorption and emission energies are observed to be size tunable, with the optical band gap increasing from 1.5 eV to 3.2 eV as the dot diameter decreased from 8.9 nm to 2.7 nm. Size dependent absorption cross sections (σ = 1.22 ± 0.02 × 10-15 cm2 to 2.04 ± 0.03 × 10-15 cm2), single exciton lifetimes (0.36 ± 0.02 ns to 0.65 ± 0.03 ns), as well as Auger recombination lifetimes of biexcitons (3.2 ± 0.4 ps to 5.0 ± 0.1 ps) and trions (20.8 ± 1.8 ps to 46.3 ± 1.3 ps) are also measured. The degeneracy of the con-duction band minimum (푔 = 2) is determined from the analysis of the transient absorption spectra at different excitation fluences. The performance of Zn3N2 colloidal quantum dots thus broadly matches that of established visible light emitting quantum dots based on toxic or rare elements, making them a viable alternative for QD-LED displays.

Additive manufacturing (AM) technologies appear as a paradigm for scalable manufacture of electrochemical energy storage (EES) devices, where complex 3D architectures are typically required but are hard to achieve using conventional techniques. The combination of these technologies and innovative material formulations that maximize surface area accessibility and ion transport within electrodes while minimizing space are of growing interest. Herein, aqueous inks composed of atomically thin (1-3 nm) 2D Ti3 C2 Tx with large lateral size of about 8 µm possessing ideal viscoelastic properties are formulated for extrusion-based 3D printing of freestanding, high specific surface area architectures to determine the viability of manufacturing energy storage devices. The 3D-printed device achieves a high areal capacitance of 2.1 F cm-2 at 1.7 mA cm-2 and a gravimetric capacitance of 242.5 F g-1 at 0.2 A g-1 with a retention of above 90% capacitance for 10 000 cycles. It also exhibits a high energy density of 0.0244 mWh cm-2 and a power density of 0.64 mW cm-2 at 4.3 mA cm-2 . It is anticipated that the sustainable printing and design approach developed in this work can be applied to fabricate high-performance bespoke multiscale and multidimensional architectures of functional and structural materials for integrated devices in various applications.

Two dimensional III–VI metal monochalcogenide materials, such as GaSe and InSe, are attracting considerable attention due to their promising electronic and optoelectronic properties. Here, an investigation of point and extended atomic defects formed in mono-, bi-, and few-layer GaSe and InSe crystals is presented. Using state-of-the-art scanning transmission electron microscopy, it is observed that these materials can form both metal and selenium vacancies under the action of the electron beam. Selenium vacancies are observed to be healable: recovering the perfect lattice structure in the presence of selenium or enabling incorporation of dopant atoms in the presence of impurities. Under prolonged imaging, multiple point defects are observed to coalesce to form extended defect structures, with GaSe generally developing trigonal defects and InSe primarily forming line defects. These insights into atomic behavior could be harnessed to synthesize and tune the properties of 2D post-transition-metal monochalcogenide materials for optoelectronic applications.

We have explored the synthesis of Au@HgxCd1-xTe core@shell nanorods by sequential aqueous cation exchange (ACE) for near-infrared photodetector application. A number of related Au@telluride core/shell nanorod structures were put forwarded, taking advantage of multi-step transformations through a binary and then a ternary phase for the telluride shells. The latter have a high degree of crystallinity thanks to the step-wise ACE method. The use of only trace amounts of Cd2+ coordinated with tri-n-butylphosphine, assisted the phase transformation from an amorphous Ag2Te shell to a highly crystalline Ag3AuTe2 shell in the first stage; this was followed by a further cation exchange (CE) step with far higher Cd2+ levels to fabricate a highly crystalline CdTe shell, and with an additional CE with Hg2+ to convert it to a HgxCd1-xTe shell. The composition of the shell components and the well-controlled thickness of the shells enabled tunable surface plasmon resonance properties of the Au@telluride nanorods in the NIR region. Utilizing the enhanced NIR absorption, a hybrid photodetector structure of Au@HgxCd1-xTe nanorods on graphene was fabricated, showing visible to NIR (vis-NIR) broadband detection with high photoresponsivity (~106 A/W).