Tracking single adatoms in liquid in a transmission electron microscope.

Single atoms or ions on surfaces affect processes from nucleation1 to electrochemical reactions2 and heterogeneous catalysis3. Transmission electron microscopy is a leading approach for visualizing single atoms on a variety of substrates4,5. It conventionally requires high vacuum conditions, but has been developed for in situ imaging in liquid and gaseous environments6,7 with a combined spatial and temporal resolution that is unmatched by any other method-notwithstanding concerns about electron-beam effects on samples. When imaging in liquid using commercial technologies, electron scattering in the windows enclosing the sample and in the liquid generally limits the achievable resolution to a few nanometres6,8,9. Graphene liquid cells, on the other hand, have enabled atomic-resolution imaging of metal nanoparticles in liquids10. Here we show that a double graphene liquid cell, consisting of a central molybdenum disulfide monolayer separated by hexagonal boron nitride spacers from the two enclosing graphene windows, makes it possible to monitor, with atomic resolution, the dynamics of platinum adatoms on the monolayer in an aqueous salt solution. By imaging more than 70,000 single adatom adsorption sites, we compare the site preference and dynamic motion of the adatoms in both a fully hydrated and a vacuum state. We find a modified adsorption site distribution and higher diffusivities for the adatoms in the liquid phase compared with those in vacuum. This approach paves the way for in situ liquid-phase imaging of chemical processes with single-atom precision.

Ion exchange in atomically thin clays and micas.

The physical properties of clays and micas can be controlled by exchanging ions in the crystal lattice. Atomically thin materials can have superior properties in a range of membrane applications, yet the ion-exchange process itself remains largely unexplored in few-layer crystals. Here we use atomic-resolution scanning transmission electron microscopy to study the dynamics of ion exchange and reveal individual ion binding sites in atomically thin and artificially restacked clays and micas. We find that the ion diffusion coefficient for the interlayer space of atomically thin samples is up to 104 times larger than in bulk crystals and approaches its value in free water. Samples where no bulk exchange is expected display fast exchange at restacked interfaces, where the exchanged ions arrange in islands with dimensions controlled by the moiré 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. This work provides atomic scale insights into ion diffusion in highly confined spaces and suggests strategies to design exfoliated clay membranes with enhanced performance.

Hydrotalcite Colloidal Stability and Interactions with Uranium(VI) at Neutral to Alkaline pH.

In the United Kingdom, decommissioning of legacy spent fuel storage facilities involves the retrieval of radioactive sludges that have formed as a result of corrosion of Magnox nuclear fuel. Retrieval of sludges may re-suspend a colloidal fraction of the sludge, thereby potentially enhancing the mobility of radionuclides including uranium. The colloidal properties of the layered double hydroxide (LDH) phase hydrotalcite, a key product of Magnox fuel corrosion, and its interactions with U(VI) are of interest. This is because colloidal hydrotalcite is a potential transport vector for U(VI) under the neutral-to-alkaline conditions characteristic of the legacy storage facilities and other nuclear decommissioning scenarios. Here, a multi-technique approach was used to investigate the colloidal stability of hydrotalcite and the U(VI) sorption mechanism(s) across pH 7-11.5 and with variable U(VI) surface loadings (0.01-1 wt %). Overall, hydrotalcite was found to form stable colloidal suspensions between pH 7 and 11.5, with some evidence for Mg2+ leaching from hydrotalcite colloids at pH ≤ 9. For systems with U present, >98% of U(VI) was removed from the solution in the presence of hydrotalcite, regardless of pH and U loading, although the sorption mode was affected by both pH and U concentrations. Under alkaline conditions, U(VI) surface precipitates formed on the colloidal hydrotalcite nanoparticle surface. Under more circumneutral conditions, Mg2+ leaching from hydrotalcite and more facile exchange of interlayer carbonate with the surrounding solution led to the formation of uranyl carbonate species (e.g., Mg(UO2(CO3)3)2-(aq)). Both X-ray absorption spectroscopy (XAS) and luminescence analysis confirmed that these negatively charged species sorbed as both outer- and inner-sphere tertiary complexes on the hydrotalcite surface. These results demonstrate that hydrotalcite can form pseudo-colloids with U(VI) under a wide range of pH conditions and have clear implications for understanding the uranium behavior in environments where hydrotalcite and other LDHs may be present.

Magnetic-Field-Induced Re-entrance of Superconductivity in Ta2PdS5 Nanostrips.

The motion of Abrikosov vortices is the dominant origin of dissipation in type II superconductors subjected to a magnetic field, which leads to a finite electrical resistance. It is generally believed that the increase in the magnetic field results in the aggravation of energy dissipation through the increase in vortex density. Here, we show a distinctive re-entrance of the dissipationless state in quasi-one-dimensional superconducting Ta2PdS5 nanostrips. Utilizing magnetotransport measurements, we unveil a prominent magnetoresistance drop with the increase in the magnetic field below the superconducting transition temperature, manifesting itself as a giant re-entrance to the superconducting phase. Time-dependent Ginzburg-Landau calculations show that this is originated from the suppression of the vortex motion by the increased energy barrier on the edges. Interestingly, both our experiments and simulations demonstrate that this giant re-entrance of superconductivity occurs only in certain geometrical regimes because of the finite size of the vortex.

Stacking Order in Graphite Films Controlled by van der Waals Technology.

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 high-temperature 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.

Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

Atomic Insights into Phase Evolution in Ternary Transition-Metal Dichalcogenides Nanostructures.

Phase engineering through chemical modification can significantly alter the properties of transition-metal dichalcogenides, and allow the design of many novel electronic, photonic, and optoelectronics devices. The atomic-scale mechanism underlying such phase engineering is still intensively investigated but elusive. Here, advanced electron microscopy, combined with density functional theory calculations, is used to understand the phase evolution (hexagonal 2H→monoclinic T'→orthorhombic Td ) in chemical vapor deposition grown Mo1-x W x Te2 nanostructures. Atomic-resolution imaging and electron diffraction indicate that Mo1-x W x Te2 nanostructures have two phases: the pure monoclinic phase in low W-concentrated (0 < x ≤ 10 at.%) samples, and the dual phase of the monoclinic and orthorhombic in high W-concentrated (10 < x < 90 at.%) samples. Such phase coexistence exists with coherent interfaces, mediated by a newly uncovered orthorhombic phase Td '. Td ', preserves the centrosymmetry of T' and provides the possible phase transition path for T'→Td with low energy state. This work enriches the atomic-scale understanding of phase evolution and coexistence in multinary compounds, and paves the way for device applications of new transition-metal dichalcogenides phases and heterostructures.

Atomic scale insights into the epitaxial growth mechanism of 2D Cr3Te4 on mica.

Two-dimensional (2D) magnetic materials are of wide research interest owing to their promising applications in spintronic devices. Among them, chromium chalcogenide compounds are some of the limited available systems that present both high stability in air and high Curie temperatures. Epitaxial growth techniques based on chemical vapour deposition (CVD) have been demonstrated to be a robust method for growing 2D non-layered chromium chalcogenides. However, the growth mechanism is not well-understood. Here, we demonstrate the epitaxial growth of Cr3Te4 nanoplates with high quality on mica. Atomic-resolution scanning transmission electron microscopy (STEM) imaging reveals that the epitaxial growth is based on nanosized chromium oxide seed particles at the interface of Cr3Te4 and mica. The chromium oxide nanoparticle exhibits a coherent interface with both mica and Cr3Te4 with a lattice mismatch within 3%, suggesting that, as a buffer layer, chromium oxide can release the interfacial strain, and induce the growth of Cr3Te4 although there is a distinct oxygen-content difference between mica and Cr3Te4. This work provides an experimental understanding behind the epitaxial growth of 2D magnetic materials at the atomic scale and facilitates the improvement of their growth procedures for devices with high crystalline quality.

Nonreciprocal superconducting NbSe2 antenna.

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.

Realizing zT of 2.3 in Ge1-x-y Sbx Iny Te via Reducing the Phase-Transition Temperature and Introducing Resonant Energy Doping.

GeTe with rhombohedral-to-cubic phase transition is a promising lead-free thermoelectric candidate. Herein, theoretical studies reveal that cubic GeTe has superior thermoelectric behavior, which is linked to (1) the two valence bands to enhance the electronic transport coefficients and (2) stronger enharmonic phonon-phonon interactions to ensure a lower intrinsic thermal conductivity. Experimentally, based on Ge1-x Sbx Te with optimized carrier concentration, a record-high figure-of-merit of 2.3 is achieved via further doping with In, which induces the distortion of the density of states near the Fermi level. Moreover, Sb and In codoping reduces the phase-transition temperature to extend the better thermoelectric behavior of cubic GeTe to low temperature. Additionally, electronic microscopy characterization demonstrates grain boundaries, a high-density of stacking faults, and nanoscale precipitates, which together with the inevitable point defects result in a dramatically decreased thermal conductivity. The fundamental investigation and experimental demonstration provide an important direction for the development of high-performance Pb-free thermoelectric materials.

Continuous flow synthesis of phosphate binding h-BN@magnetite hybrid material.

Hexagonal boron nitride (h-BN) is rendered magnetically responsive in aqueous media by binding superparamagnetic magnetite nanoparticles 8.5-18.5 nm in diameter on the surface. The composite material was generated under continuous flow in water in a dynamic thin film in a vortex fluidic device (VFD) with the source of iron generated by laser ablation of a pure iron metal target in the air above the liquid using a Nd:YAG pulsed laser operating at 1064 nm and 360 mJ. Optimum operating parameters of the VFD were a rotational speed of 7.5k rpm for the 20 mm OD (17.5 mm ID) borosilicate glass tube inclined at 45 degrees, with a h-BN concentration at 0.1 mg mL-1, delivered at 1.0 mL min-1 using a magnetically stirred syringe to keep the h-BN uniformly dispersed in water prior to injection into the base of the rapidly rotating tube. The resulting composite material, containing 5.75% weight of iron, exhibited high phosphate ion adsorption capacity, up to 171.2 mg PO4 3- per gram Fe, which was preserved on recycling the material five times.

Laser-Ablated Vortex Fluidic-Mediated Synthesis of Superparamagnetic Magnetite Nanoparticles in Water Under Flow.

Selective formation of only one iron oxide phase is a major challenge in conventional laser ablation process, as is scaling up the process. Herein, superparamagnetic single-phase magnetite nanoparticles of hexagonal and spheroidal-shape, with an average size of ca. 15 nm, are generated by laser ablation of bulk iron metal at 1064 nm in a vortex fluidic device (VFD). This is a one-step continuous flow process, in air at ambient pressure, with in situ uptake of the nanoparticles in the dynamic thin film of water in the VFD. The process minimizes the generation of waste by avoiding the need for any chemicals or surfactants and avoids time-consuming purification steps in reducing any negative impact of the processing on the environment.

Signature of quantum Griffiths singularity state in a layered quasi-one-dimensional superconductor.

Quantum Griffiths singularity was theoretically proposed to interpret the phenomenon of divergent dynamical exponent in quantum phase transitions. It has been discovered experimentally in three-dimensional (3D) magnetic metal systems and two-dimensional (2D) superconductors. But, whether this state exists in lower dimensional systems remains elusive. Here, we report the signature of quantum Griffiths singularity state in quasi-one-dimensional (1D) Ta2PdS5 nanowires. The superconducting critical field shows a strong anisotropic behavior and a violation of the Pauli limit in a parallel magnetic field configuration. Current-voltage measurements exhibit hysteresis loops and a series of multiple voltage steps in transition to the normal state, indicating a quasi-1D nature of the superconductivity. Surprisingly, the nanowire undergoes a superconductor-metal transition when the magnetic field increases. Upon approaching the zero-temperature quantum critical point, the system uncovers the signature of the quantum Griffiths singularity state arising from enhanced quenched disorders, where the dynamical critical exponent becomes diverging rather than being constant.

Superconductivity and magnetotransport of single-crystalline NbSe2 nanoplates grown by chemical vapour deposition.

NbSe2 is a typical transition metal dichalcogenide with a rich variety of electronic ground states existing in its nanostructures, including two-dimensional superconductivity and charge density wave. However, the direct growth of high-quality single-crystalline NbSe2 nanostructures is still challenging, which limits their applications in electronic devices. Here, we report the growth of high-quality NbSe2 nanoplates by a single-step chemical vapour deposition. Their temperature and magnetic-field dependent superconducting behaviors were investigated by four-terminal devices fabricated on individual nanostructures. The NbSe2 nanoplates show two-dimensional characteristics of superconducting transitions and strong anisotropy with magnetic field orientation, providing potential platforms for the exploration of new physics in nanoelectronic devices.

Surface-energy engineered Bi-doped SnTe nanoribbons with weak antilocalization effect and linear magnetoresistance.

The rational design of semiconductor nanocrystals with well-defined surfaces is a crucial step towards the realization of next-generation photodetectors, and thermoelectric and spintronic devices. SnTe nanocrystals, as an example, are particularly attractive as a type of topological crystalline insulator, where surface facets determine their surface states. However, most of the available SnTe nanocrystals are dominated by thermodynamically stable {100} facets, and it is challenging to grow uniform nanocrystals with {111} facets. In this study, guided by surface-energy calculations, we employ a chemical vapour deposition approach to fabricate Bi doped SnTe nanostructures, in which their surface facets are tuned by Bi doping. The obtained Bi doped SnTe nanoribbons with distinct {111} surfaces show a weak antilocalization effect and linear magnetoresistance under high magnetic fields, which demonstrate their great potential for future spintronic applications.

Planar Vacancies in Sn1-xBixTe Nanoribbons.

Vacancy engineering is a crucial approach to manipulate physical properties of semiconductors. Here, we demonstrate that planar vacancies are formed in Sn1-xBixTe nanoribbons by using Bi dopants via a facile chemical vapor deposition. Through combination of sub-angstrom-resolution imaging and density functional theory calculations, these planar vacancies are found to be associated with Bi segregations, which significantly lower their formation energies. The planar vacancies exhibit polymorphic structures with local variations in the lattice relaxation level, determined by their proximity to the nanoribbon surface. Such polymorphic planar vacancies, in conjunction with Bi dopants, trigger distinct localized electronic states, offering platforms for device applications of ternary chalcogenide materials.