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.

Self-assembly of a layered two-dimensional molecularly woven fabric.

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.

Atomic Au3Cu Palisade Interlayer in Core@Shell Nanostructures for Efficient Kirkendall Effect Mediation.

Plasmonic Cu@semiconductor heteronanocrystals (HNCs) have many favorable properties, but the synthesis of solid structures is often hindered by the nanoscale Kirkendall effect. Herein, we present the use of an atomically thin Au3Cu palisade interlayer to reduce lattice mismatch and mediate the Kirkendall effect, enabling the successive topological synthesis of Cu@Au3Cu@Ag, Cu@Au3Cu@Ag2S, and further transformed solid Cu@Au3Cu@CdS core-shell HNCs via cation exchange. The atomically thin and intact Au3Cu palisade interlayer effectively modulates the diffusion kinetics of Cu atoms as demonstrated by experimental and theoretical investigations and simultaneously alleviates the lattice mismatch between Cu and Ag as well as Cu and CdS. The Cu@Au3Cu@CdS HNCs feature exceptional crystallinity and atomically organized heterointerfaces between the plasmonic metal and the semiconductor. This results in the efficient plasmon-induced injection of hot electrons from Cu@Au3Cu into the CdS shell, enabling the Cu@Au3Cu@CdS HNCs to achieve high activity and selectivity for the photocatalytic reduction of CO2 to CO.

In Situ Single Particle Reconstruction Reveals 3D Evolution of PtNi Nanocatalysts During Heating.

Tailoring nanoparticles' composition and morphology is of particular interest for improving their performance for catalysis. A challenge of this approach is that the nanoparticles' optimized initial structure often changes during use. Visualizing the three dimensional (3D) structural transformation in situ is therefore critical, but often prohibitively difficult experimentally. Although electron tomography provides opportunities for 3D imaging, restrictions in the tilt range of in situ holders together with electron dose considerations limit the possibilities for in situ electron tomography studies. Here, an in situ 3D imaging methodology is presented using single particle reconstruction (SPR) that allows 3D reconstruction of nanoparticles with controlled electron dose and without tilting the microscope stage. This in situ SPR methodology is employed to investigate the restructuring and elemental redistribution within a population of PtNi nanoparticles at elevated temperatures. The atomic structure of PtNi is further examined and a heat-induced transition is found from a disordered to an ordered phase. Changes in structure and elemental distribution are linked to a loss of catalytic activity in the oxygen reduction reaction. The in situ SPR methodology employed here can be extended to a wide range of in situ studies employing not only heating, but gaseous, aqueous, or electrochemical environments to reveal in-operando nanoparticle evolution in 3D.

Biosynthesis Parameters Control the Physicochemical and Catalytic Properties of Microbially Supported Pd Nanoparticles.

The biosynthesis of Pd nanoparticles supported on microorganisms (bio-Pd) is achieved via the enzymatic reduction of Pd(II) to Pd(0) under ambient conditions using inexpensive buffers and electron donors, like organic acids or hydrogen. Sustainable bio-Pd catalysts are effective for C-C coupling and hydrogenation reactions, but their industrial application is limited by challenges in controlling nanoparticle properties. Here, using the metal-reducing bacterium Geobacter sulfurreducens, it is demonstrated that synthesizing bio-Pd under different Pd loadings and utilizing different electron donors (acetate, formate, hydrogen, no e- donor) influences key properties such as nanoparticle size, Pd(II):Pd(0) ratio, and cellular location. Controlling nanoparticle size and location controls the activity of bio-Pd for the reduction of 4-nitrophenol, whereas high Pd loading on cells synthesizes bio-Pd with high activity, comparable to commercial Pd/C, for Suzuki-Miyaura coupling reactions. Additionally, the study demonstrates the novel synthesis of microbially-supported ≈2 nm PdO nanoparticles due to the hydrolysis of biosorbed Pd(II) in bicarbonate buffer. Bio-PdO nanoparticles show superior activity in 4-nitrophenol reduction compared to commercial Pd/C catalysts. Overall, controlling biosynthesis parameters, such as electron donor, metal loading, and solution chemistry, enables tailoring of bio-Pd physicochemical and catalytic properties.

Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal-Organic Framework.

Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.

Bioproduction of cerium-bearing magnetite and application to improve carbon-black supported platinum catalysts.

BACKGROUND: Biogeochemical processing of metals including the fabrication of novel nanomaterials from metal contaminated waste streams by microbial cells is an area of intense interest in the environmental sciences. RESULTS: Here we focus on the fate of Ce during the microbial reduction of a suite of Ce-bearing ferrihydrites with between 0.2 and 4.2 mol% Ce. Cerium K-edge X-ray absorption near edge structure (XANES) analyses showed that trivalent and tetravalent cerium co-existed, with a higher proportion of tetravalent cerium observed with increasing Ce-bearing of the ferrihydrite. The subsurface metal-reducing bacterium Geobacter sulfurreducens was used to bioreduce Ce-bearing ferrihydrite, and with 0.2 mol% and 0.5 mol% Ce, an Fe(II)-bearing mineral, magnetite (Fe(II)(III)2O4), formed alongside a small amount of goethite (FeOOH). At higher Ce-doping (1.4 mol% and 4.2 mol%) Fe(III) bioreduction was inhibited and goethite dominated the final products. During microbial Fe(III) reduction Ce was not released to solution, suggesting Ce remained associated with the Fe minerals during redox cycling, even at high Ce loadings. In addition, Fe L2,3 X-ray magnetic circular dichroism (XMCD) analyses suggested that Ce partially incorporated into the Fe(III) crystallographic sites in the magnetite. The use of Ce-bearing biomagnetite prepared in this study was tested for hydrogen fuel cell catalyst applications. Platinum/carbon black electrodes were fabricated, containing 10% biomagnetite with 0.2 mol% Ce in the catalyst. The addition of bioreduced Ce-magnetite improved the electrode durability when compared to a normal Pt/CB catalyst. CONCLUSION: Different concentrations of Ce can inhibit the bioreduction of Fe(III) minerals, resulting in the formation of different bioreduction products. Bioprocessing of Fe-minerals to form Ce-containing magnetite (potentially from waste sources) offers a sustainable route to the production of fuel cell catalysts with improved performance.

Flicker and reading speed: Effects on individuals with visual sensitivity.

Flicker and patterns of stripes in the modern environment can evoke visual illusions, discomfort migraine, and seizures. We measured reading speed while striped and less striped texts were illuminated with LED lights. In Experiment 1, the lights flickered at 60 Hz and 120 Hz compared to 60 kHz (perceived as steady light). In Experiment 2, the lights flickered at 60 Hz or 600 Hz (at which frequency the phantom array is most visible), and were compared to continuous light. Two types of text were used: one containing words with high horizontal autocorrelation (striped) and another containing words with low autocorrelation (less striped). We measured the number of illusions participants saw in the Pattern Glare (PG) Test. Overall, reading speed was slowest during the 60 Hz and 600 Hz flicker and was slower when reading the high autocorrelation text. Interestingly, the low PG group showed greater effects of flicker on reading speed than the high PG group, which tended to be slower overall. In addition, reading speed in the high PG group was reduced when the autocorrelation of the text was high. These findings suggest that uncomfortable visual environments reduce reading efficiency, the more so in individuals who are visually sensitive.

Pattern glare sensitivity distinguishes subclinical autism and schizotypy.

INTRODUCTION: Schizophrenia and autism spectrum disorder are distinct neurodevelopmental disorders sharing clinically relevant behaviours. However, early sensory responses show divergent responses. Individuals with schizophrenia typically exhibit cortical hypo-excitability whereas individuals with autism show cortical hyperexcitability. Identifying reliable neurobiological differences between the disorders can diminish misdiagnosis and optimise treatments. METHODS: The pattern glare test (PGT) is a simple measure of behavioural hyperexcitability. It measures the number of illusions seen in a static horizontal grating. We collected PGT data from non-clinical adults varying in traits of autism and schizophrenia (schizotypy). 576 undergraduate students completed an online survey consisting of the Schizotypal Personality Questionnaire - Brief Revised, the Autism Spectrum Quotient, and the PGT. RESULTS: Subclinical autism and schizotypy traits were highly positively correlated. However, only schizotypy scores were significantly predictive of reporting more pattern glare (PG) illusions. When assessing the subcomponents of the schizotypy and autism scores, positive and disorganised schizotypy traits were predictive of reporting more PG illusions. Whereas, subclinical autism factors were not predictive of PG illusions. CONCLUSIONS: High schizotypy performed the PGT in a manner consistent with behavioural hyperexcitability. The PGT distinguished subclinical autistic traits from schizotypy, suggesting potential clinical application.

Ultralow Catalytic Loading for Optimised Electrocatalytic Performance of AuPt Nanoparticles to Produce Hydrogen and Ammonia.

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications.

Direct Conversion of Methane to Ethylene and Acetylene over an Iron-Based Metal-Organic Framework.

Conversion of methane (CH4) to ethylene (C2H4) and/or acetylene (C2H2) enables routes to a wide range of products directly from natural gas. However, high reaction temperatures and pressures are often required to activate and convert CH4 controllably, and separating C2+ products from unreacted CH4 can be challenging. Here, we report the direct conversion of CH4 to C2H4 and C2H2 driven by non-thermal plasma under ambient (25 °C and 1 atm) and flow conditions over a metal-organic framework material, MFM-300(Fe). The selectivity for the formation of C2H4 and C2H2 reaches 96% with a high time yield of 334 µmol gcat-1 h-1. At a conversion of 10%, the selectivity to C2+ hydrocarbons and time yield exceed 98% and 2056 µmol gcat-1 h-1, respectively, representing a new benchmark for conversion of CH4. In situ neutron powder diffraction, inelastic neutron scattering and solid-state nuclear magnetic resonance, electron paramagnetic resonance (EPR), and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modeling studies, reveal the crucial role of Fe-O(H)-Fe sites in activating CH4 and stabilizing reaction intermediates via the formation of an Fe-O(CH3)-Fe adduct. In addition, a cascade fixed-bed system has been developed to achieve online separation of C2H4 and C2H2 from unreacted CH4 for direct use. Integrating the processes of CH4 activation, conversion, and product separation within one system opens a new avenue for natural gas utility, bridging the gap between fundamental studies and practical applications in this area.

Working memory and sensory memory in subclinical high schizotypy: An avenue for understanding schizophrenia?

The search for robust, reliable biomarkers of schizophrenia remains a high priority in psychiatry. Biomarkers are valuable because they can reveal the underlying mechanisms of symptoms and monitor treatment progress and may predict future risk of developing schizophrenia. Despite the existence of various promising biomarkers that relate to symptoms across the schizophrenia spectrum, and despite published recommendations encouraging multivariate metrics, they are rarely investigated simultaneously within the same individuals. In those with schizophrenia, the magnitude of purported biomarkers is complicated by comorbid diagnoses, medications and other treatments. Here, we argue three points. First, we reiterate the importance of assessing multiple biomarkers simultaneously. Second, we argue that investigating biomarkers in those with schizophrenia-related traits (schizotypy) in the general population can accelerate progress in understanding the mechanisms of schizophrenia. We focus on biomarkers of sensory and working memory in schizophrenia and their smaller effects in individuals with nonclinical schizotypy. Third, we note irregularities across research domains leading to the current situation in which there is a preponderance of data on auditory sensory memory and visual working memory, but markedly less in visual (iconic) memory and auditory working memory, particularly when focusing on schizotypy where data are either scarce or inconsistent. Together, this review highlights opportunities for researchers without access to clinical populations to address gaps in knowledge. We conclude by highlighting the theory that early sensory memory deficits contribute negatively to working memory and vice versa. This presents a mechanistic perspective where biomarkers may interact with one another and impact schizophrenia-related symptoms.

People with high schizotypy experience more illusions in the Pattern Glare Test: Consistent with the hyperexcitability hypothesis.

Individuals diagnosed with schizophrenia spectrum disorders (SSD) exhibit a constellation of sensory and perceptual impairments, including hyporeactivity to external input. However, individuals with SSD also report subjective experiences of sensory flooding, suggesting sensory hyperexcitability. To identify the extent to which behavioural indices of hyperexcitability are related to non-psychotic symptoms of schizophrenia, we tested a non-clinical population measured for schizophrenia-like traits (schizotypy), and a behavioural measure of sensory hyperexcitability, specifically the number of illusions seen in the Pattern Glare Test. Two samples totaling 913 individuals completed an online version of the Schizotypal Personality Questionnaire - Brief Revised (SPQ-BR) and the Pattern Glare Test. Individuals with higher schizotypy traits reported more illusions in the Pattern Glare Test. Additionally, one of the three SPQ-BR factors, the disorganized factor, significantly predicted the number of illusions reported. These data illustrate the potential for research in non-clinical samples to inform clinically relevant research.

Copper bioreduction and nanoparticle synthesis by an enrichment culture from a former copper mine.

Microorganisms can facilitate the reduction of Cu2+ , altering its speciation and mobility in environmental systems and producing Cu-based nanoparticles with useful catalytic properties. However, only a few model organisms have been studied in relation to Cu2+ bioreduction and little work has been carried out on microbes from Cu-contaminated environments. This study aimed to enrich for Cu-resistant microbes from a Cu-contaminated soil and explore their potential to facilitate Cu2+ reduction and biomineralisation from solution. We show that an enrichment grown in a Cu-amended medium, dominated by species closely related to Geothrix fermentans, Azospira restricta and Cellulomonas oligotrophica, can reduce Cu2+ with subsequent precipitation of Cu nanoparticles. Characterisation of the nanoparticles with (scanning) transmission electron microscopy, energy-dispersive x-ray spectroscopy and electron energy loss spectroscopy supports the presence of both metallic Cu(0) and S-rich Cu(I) nanoparticles. This study provides new insights into the diversity of microorganisms capable of facilitating copper reduction and highlights the potential for the formation of distinct nanoparticle phases resulting from bioreduction or biomineralisation reactions. The implications of these findings for the biogeochemical cycling of copper and the potential biotechnological synthesis of commercially useful copper nanoparticles are discussed.

Microbial Reduction of Antimony(V)-Bearing Ferrihydrite by Geobacter sulfurreducens.

The reduction of Sb(V)-bearing ferrihydrite by Geobacter sulfurreducens was studied to determine the fate of the metalloid in Fe-rich systems undergoing redox transformations. Sb(V) added at a range of concentrations adsorbed readily to ferrihydrite, and the loadings had a pronounced impact on the rate and extent of Fe(III) reduction and the products formed. Magnetite dominated at low (0.5 and 1 mol%) Sb(V) concentrations, with crystallite sizes decreasing at higher Sb loadings: 37-, 25-, and 17-nm particles for no-Sb, 0.5% Sb, and 1% Sb samples, respectively. In contrast, goethite was the dominant end product for samples with higher antimony loadings (2 and 5 mol%), with increased goethite grain size in the 5% Sb sample. Inductively coupled mass spectrometry (ICP-MS) analysis confirmed that Sb was not released to solution during the bioreduction process, and X-ray photoelectron spectroscopy (XPS) analyses showed that no Sb(III) was formed throughout the experiments, confirming that the Fe(III)-reducing bacterium Geobacter sulfurreducens cannot reduce Sb(V) enzymatically or via biogenic Fe(II). These findings suggest that Fe (bio)minerals have a potential role in limiting antimony pollution in the environment, even when undergoing redox transformations. IMPORTANCE Antimony is an emerging contaminant that shares chemical characteristics with arsenic. Metal-reducing bacteria (such as Geobacter sulfurreducens) can cause the mobilization of arsenic from Fe(III) minerals under anaerobic conditions, causing widespread contamination of aquifers worldwide. This research explores whether metal-reducing bacteria can drive the mobilization of antimony under similar conditions. In this study, we show that G. sulfurreducens cannot reduce Sb(V) directly or cause Sb release during the bioreduction of the Fe(III) mineral ferrihydrite [although the sorbed Sb(V) did alter the Fe(II) mineral end products formed]. Overall, this study highlights the tight associations between Fe and Sb in environmental systems, suggesting that the microbial reduction of Fe(III)/Sb mineral assemblages may not lead to Sb release (in stark contrast to the mobilization of As in iron-rich systems) and offers potential Fe-based remediation options for Sb-contaminated environments.

Quantum Confined High-Entropy Lanthanide Oxysulfide Colloidal Nanocrystals.

We have synthesized the first reported example of quantum confined high-entropy (HE) nanoparticles, using the lanthanide oxysulfide, Ln2SO2, system as the host phase for an equimolar mixture of Pr, Nd, Gd, Dy, and Er. A uniform HE phase was achieved via the simultaneous thermolysis of a mixture of lanthanide dithiocarbamate precursors in solution. This was confirmed by powder X-ray diffraction and high-resolution scanning transmission electron microscopy, with energy dispersive X-ray spectroscopic mapping confirming the uniform distribution of the lanthanides throughout the particles. The nanoparticle dispersion displayed a significant blue shift in the absorption and photoluminescence spectra relative to our previously reported bulk sample with the same composition, with an absorption edge at 330 nm and a λmax at 410 nm compared to the absorption edge at 500 nm and a λmax at 450 nm in the bulk, which is indicative of quantum confinement. We support this postulate with experimental and theoretical analysis of the bandgap energy as a function of strain and surface effects (ligand binding) as well as calculation of the exciton Bohr radiii of the end member compounds.

Low-Temperature Exsolution of Ni-Ru Bimetallic Nanoparticles from A-Site Deficient Double Perovskites.

Exsolution of stable metallic nanoparticles for use as efficient electrocatalysts has been of increasing interest for a range of energy technologies. Typically, exsolved nanoparticles show higher thermal and coarsening stability compared to conventionally deposited catalysts. Here, A-site deficient double perovskite oxides, La2- x NiRuO6- δ (x = 0.1 and 0.15), are designed and subjected to low-temperature reduction leading to exsolution. The reduced double perovskite materials are shown to exsolve nanoparticles of 2-6 nm diameter during the reduction in the low-temperature range of 350-450 °C. The nanoparticle sizes are found to increase after reduction at the higher temperature (450 °C), suggesting diffusion-limited particle growth. Interestingly, both nickel and ruthenium are co-exsolved during the reduction process. The formation of bimetallic nanoparticles at such low temperatures is rare. From the in situ impedance spectroscopy measurements of the double perovskite electrode layers, the onset of the exsolution process is found to be within the first few minutes of the reduction reaction. In addition, the area-specific resistance of the electrode layers is found to decrease by 90% from 291 to 29 Ω cm2 , suggesting encouraging prospects for these low-temperature rapidly exsolved Ni/Ru alloy nanoparticles in a range of catalytic applications.

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.

Telluride Nanocrystals with Adjustable Amorphous Shell Thickness and Core-Shell Structure Modulation by Aqueous Cation Exchange.

Engineering the structure of core-shell colloidal semiconductor nanoparticles (CSNPs) is attractive due to the potential to enhance photo-induced charge transfer and induce favorable optical and electronic properties. Nonetheless, the sensitivity of telluride CSNPs to high temperatures makes it challenging to precisely modulate their surface crystallinity. Herein, we have developed an efficient strategy for synthesizing telluride CSNPs with thin amorphous shells using aqueous cation exchange (ACE). By changing the synthesis temperature in the range of 40-110 °C, the crystallinity of the CdTe nanoparticles was controllable from perfect crystals with no detectable amorphous shell (c-CdTe) to a core-shell structure with a crystalline CdTe NP core covered by an amorphous shell of tunable thickness up to 7-8 nm (c@a-CdTe). A second ACE step transformed c@a-CdTe to crystalline CdTe@HgTe core-shell NPs. The c@a-CdTe nanoparticles synthesized at 60 °C and having a 4-5 nm thick amorphous shell exhibited the highest surface-enhanced Raman scattering activity with a high enhancement factor around 8.82 × 105, attributed to the coupling between the amorphous shell and the crystalline core.