Nanoparticle suspensions from carbon-rich fluid make high-grade gold deposits.

Economic gold deposits result from a 100- to 10,000-fold enrichment in gold relative to crustal background. In hydrothermal systems, this enrichment is achieved through the transport and accumulation of metals via deeply sourced fluids to a site of deposition. However, the generally low metal solubility of Au in aqueous solutions in orogenic systems requires additional processes in order to explain high-grade gold formation. Reports of Au nanoparticles in high-grade gold veins infer that their formation is linked to mineralisation. However, processes leading to nanoparticle nucleation and deposition remain poorly understood. Here we show that formation of metal nanoparticles (Au, AuAg, Cu, Ag2O) is one of the essential contributors to efficient and focused gold deposition. We report systematic and previously unrecognized metal nanoparticles preserved in amorphous silica and/or carbonic phases in five high-grade deposits. The association of metal, silica and carbonic phases helps to constrain the multiple reactive processes involved in Au, Cu and Ag metallogenesis and formation of high-grade gold mineralisation.

Gallium Plasmonic Nanoantennas Unveiling Multiple Kinetics of Hydrogen Sensing, Storage, and Spillover.

Hydrogen is the key element to accomplish a carbon-free based economy. Here, the first evidence of plasmonic gallium (Ga) nanoantennas is provided as nanoreactors supported on sapphire (α-Al2 O3 ) acting as direct plasmon-enhanced photocatalyst for hydrogen sensing, storage, and spillover. The role of plasmon-catalyzed electron transfer between hydrogen and plasmonic Ga nanoparticle in the activation of those processes is highlighted, as opposed to conventional refractive index-change-based sensing. This study reveals that, while temperature selectively operates those various processes, longitudinal (LO-LSPR) and transverse (TO-LSPR) localized surface plasmon resonances of supported Ga nanoparticles open selectivity of localized reaction pathways at specific sites corresponding to the electromagnetic hot-spots. Specifically, the TO-LSPR couples light into the surface dissociative adsorption of hydrogen and formation of hydrides, whereas the LO-LSPR activates heterogeneous reactions at the interface with the support, that is, hydrogen spillover into α-Al2 O3 and reverse-oxygen spillover from α-Al2 O3. This Ga-based plasmon-catalytic platform expands the application of supported plasmon-catalysis to hydrogen technologies, including reversible fast hydrogen sensing in a timescale of a few seconds with a limit of detection as low as 5 ppm and in a broad temperature range from room-temperature up to 600 °C while remaining stable and reusable over an extended period of time.

Ultrathin High-Quality SnTe Nanoplates for Fabricating Flexible Near-Infrared Photodetectors.

This work demonstrates a controlled van der Waals growth of two-dimensional SnTe nanoplates on mica substrates and their applications in flexible near-infrared photodetectors. The growth of nonlayered rock-salt structured SnTe crystals into two-dimensional SnTe nanoplate structures is mainly caused by the two-dimensional nature of the mica surface, which also results in the ultrathin nanoplates obtained (3.6 nm, equivalent to 6 monolayers). Furthermore, it is found that the shape of the SnTe nanoplates can be well engineered by changing their growth temperature due to the competition between the surface energy of the {100} crystallographic plane and that of the {111} plane. As a result of the favorable physical properties of topological crystalline insulators such as metallic surface (high electron mobility) and narrow bandgap, near-infrared photodetectors based on single SnTe nanoplate with the thickness of 3.6 nm present excellent device performance with a responsivity of 698 mA/W, a specific detectivity of 3.89 × 108 jones, and an external quantum efficiency of 88.5% under the illumination of a 980 nm laser at room temperature (300 K) without applying a gate voltage (Vg). Upon increasing the gate voltage from -30 to 30 V, the detector responsivity increases from 2.96 to 723 mA/W and the detector detectivity increases from 2.4 × 106 to 5.3 × 108 jones. Furthermore, upon increasing the thickness of SnTe nanoplate from 3.6 to 35 nm, the detector responsivity increases from 0.698 to 1.468 A/W. The device performance measured after bending for 300 times as well as after bending with different radii presents no obvious degradation, which exhibits the excellent flexibility of the SnTe nanoplate detectors. These results not only contribute to a deep understanding of the mechanisms of the van der Waals growth of nonlayered materials into two-dimensional structure but also demonstrate the immense potential of SnTe nanoplates to be used in flexible near-infrared detectors.

Colloidal Single-Layer Photocatalysts for Methanol-Storable Solar H2 Fuel.

Molecular surfactants are widely used to control low-dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single-layer growth for 2D materials. A scalable stacking-hinderable strategy to not only enable exclusive single-layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single-layer TMDs' photoredox activities is developed. The single-layer growth mechanism is well explained by theoretical calculation. Three types of single-layer TMDs, including MoS2 , WS2 , and ReS2 , are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen-stored liquid carrier-methanol. Such H2 fuel production from single-layer MoS2 nanosheets is COx -free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g-1 h-1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol-storable solar H2 fuel with facile chemical rebonding actualized by 2D single-layer photocatalysts.

Colloidal quasi-one-dimensional dual semiconductor core/shell nanorod couple heterostructures with blue fluorescence.

Herein we report a nanorod couple heterostructure made of dual semiconductors, in which two parallelly aligned ZnSe nanorods are connected by the growth of ZnS on both end and side facets, producing hetero-ZnS (short arms)-ZnSe (long arms)/ZnS shell nanorod couples. As evidenced by electronic structure studies, both experimental and theoretical, such core/shell nanorod couple heterostructures can act as a platform to precisely tailor the quantum confinement of charge carriers between the constituting components within a single nano-object, generating blue fluorescence after the overgrowth of an alloyed ZnCdS layer on the heterostructures. We foresee the mechanistic insights gained and electronic structures revealed in this work would shed light on the rational design of more complex heterostructures with novel functionalities.

Thermally stable coexistence of liquid and solid phases in gallium nanoparticles.

Gallium (Ga), a group III metal, is of fundamental interest due to its polymorphism and unusual phase transition behaviours. New solid phases have been observed when Ga is confined at the nanoscale. Herein, we demonstrate the stable coexistence, from 180 K to 800 K, of the unexpected solid γ-phase core and a liquid shell in substrate-supported Ga nanoparticles. We show that the support plays a fundamental role in determining Ga nanoparticle phases, with the driving forces for the nucleation of the γ-phase being the Laplace pressure in the nanoparticles and the epitaxial relationship of this phase to the substrate. We exploit the change in the amplitude of the evolving surface plasmon resonance of Ga nanoparticle ensembles during synthesis to reveal in real time the solid core formation in the liquid Ga nanoparticle. Finally, we provide a general framework for understanding how nanoscale confinement, interfacial and surface energies, and crystalline relationships to the substrate enable and stabilize the coexistence of unexpected phases.

A new metal-free carbon hybrid for enhanced photocatalysis.

Carbon nitride (C3N4) is a layered, stable, and polymeric metal-free material that has been discovered as a visible-light-response photocatalyst. Owing to C3N4 having a higher conduction band position, most previous studies have been focused on its reduction capability for solar fuel production, such as hydrogen generation from water splitting or hydrocarbon production from CO2. However, photooxidation ability of g-C3N4 is weak and has been less explored, especially for decomposition of chemically stable phenolics. Carbon spheres prepared by a hydrothermal carbonization of glucose have been widely applied as a support material or template due to their interesting physicochemical properties and the functional groups on the reactive surface. This study demonstrated that growth of carbon nanospheres onto g-C3N4 (CN-CS) can significantly increase the photooxidation ability (to about 4.79 times higher than that of pristine g-C3N4) in phenol degradation under artificial sunlight irradiations. The crystal structure, optical property, morphology, surface groups, recombination rate of electron/hole pairs, and thermal stability of CN-CS were investigated by a variety of characterization techniques. This study contributes to the further promising applications of carbon nitride in metal-free catalysis.

Demonstrating the capability of the high-performance plasmonic gallium-graphene couple.

Metal nanoparticle (NP)-graphene multifunctional platforms are of great interest for exploring strong light-graphene interactions enhanced by plasmons and for improving performance of numerous applications, such as sensing and catalysis. These platforms can also be used to carry out fundamental studies on charge transfer, and the findings can lead to new strategies for doping graphene. There have been a large number of studies on noble metal Au-graphene and Ag-graphene platforms that have shown their potential for a number of applications. These studies have also highlighted some drawbacks that must be overcome to realize high performance. Here we demonstrate the promise of plasmonic gallium (Ga) nanoparticle (NP)-graphene hybrids as a means of modulating the graphene Fermi level, creating tunable localized surface plasmon resonances and, consequently, creating high-performance surface-enhanced Raman scattering (SERS) platforms. Four prominent peculiarities of Ga, differentiating it from the commonly used noble (gold and silver) metals are (1) the ability to create tunable (from the UV to the visible) plasmonic platforms, (2) its chemical stability leading to long-lifetime plasmonic platforms, (3) its ability to n-type dope graphene, and (4) its weak chemical interaction with graphene, which preserves the integrity of the graphene lattice. As a result of these factors, a Ga NP-enhanced graphene Raman intensity effect has been observed. To further elucidate the roles of the electromagnetic enhancement (or plasmonic) mechanism in relation to electron transfer, we compare graphene-on-Ga NP and Ga NP-on-graphene SERS platforms using the cationic dye rhodamine B, a drug model biomolecule, as the analyte.

The iron distribution and magnetic properties of schistosome eggshells: implications for improved diagnostics.

BACKGROUND: Schistosoma mansoni and Schistosoma japonicum are the most frequent causative agents of human intestinal schistosomiasis. Approximately 200 million people in the world are infected with schistosomes. Diagnosis of schistosomiasis is often difficult. High percentages of low level infections are missed in routine fecal smear analysis and current diagnostic methodologies are inadequate to monitor the progress of parasite control, especially in areas with low transmission. Improved diagnostic methods are urgently needed to evaluate the success of elimination programs. Recently, a magnetic fractionation method for isolation of parasite eggs from feces was described, which uses magnetic microspheres to form parasite egg - magnetic microsphere conjugates. This approach enables screening of larger sample volumes and thus increased diagnostic sensitivity. The mechanism of formation of the conjugates remains unexplained and may either be related to specific surface characteristics of eggs and microspheres or to their magnetic properties. METHODS/PRINCIPAL FINDINGS: Here, we investigated iron localization in parasite eggs, specifically in the eggshells. We determined the magnetic properties of the eggs, studied the motion of eggs and egg-microsphere conjugates in magnetic fields and determined species specific affinity of parasite eggs to magnetic microspheres. Our study shows that iron is predominantly localized in pores in the eggshell. Parasite eggs showed distinct paramagnetic behaviour but they did not move in a magnetic field. Magnetic microspheres spontaneously bound to parasite eggs without the presence of a magnetic field. S. japonicum eggs had a significantly higher affinity to bind microspheres than S. mansoni eggs. CONCLUSIONS/SIGNIFICANCE: Our results suggest that the interaction of magnetic microspheres and parasite eggs is unlikely to be magnetic in origin. Instead, the filamentous surface of the eggshells may be important in facilitating the binding. Modification of microsphere surface properties may therefore be a way to optimize magnetic fractionation of parasite eggs.

Optical properties of silicon semiconductor-supported gold nanoparticles obtained by sputtering.

Gold nanoclusters are deposited directly on silicon by sputtering of a target of metallic gold using an argon plasma to provide a semiconductor-based plasmonic platform. The effects of annealing and substrate temperatures during the nanoparticles deposition and of the silicon surface energy on the shape of the nanoparticles and resulting surface plasmon resonance are investigated. The Au nanoparticles are characterized optically, structurally and morphologically using spectroscopic ellipsometry, transmission electron microscopy and atomic force microscopy to establish a correlation among the Au/Si interface reactivity, the Au nanoparticles shape and plasmonic resonance properties. It is found that post-growth annealing up to 600 degrees C of nanoparticles deposited at 60 degrees C causes aggregation of nanoparticles. Increasing the temperature of the substrate during the sputtering of gold on Si yields pancake-like nanoparticles with a large Si/Au interface reactivity forming a gold-silicides interface layer. The O2 plasma treatment of the Si surface forming a thin intentional SiO2 interface layer prevents the Au/Si interdiffusion yielding polyedrical nanoparticles whose plasmon resonance can be shifted down to 1.5 eV.

Influence of nanowire density on the shape and optical properties of ternary InGaAs nanowires.

We have synthesized ternary InGaAs nanowires on (111)B GaAs surfaces by metal-organic chemical vapor deposition. Au colloidal nanoparticles were employed to catalyze nanowire growth. We observed the strong influence of nanowire density on nanowire height, tapering, and base shape specific to the nanowires with high In composition. This dependency was attributed to the large difference of diffusion length on (111)B surfaces between In and Ga reaction species, with In being the more mobile species. Energy dispersive X-ray spectroscopy analysis together with high-resolution electron microscopy study of individual InGaAs nanowires shows large In/Ga compositional variation along the nanowire supporting the present diffusion model. Photoluminescence spectra exhibit a red shift with decreasing nanowire density due to the higher degree of In incorporation in more sparsely distributed InGaAs nanowires.

Charge-related problems associated with X-ray microanalysis in the variable pressure scanning electron microscope at low pressures.

In variable pressure scanning electron microscopy (VPSEM) the current data suggests that considerable caution is required in the interpretation of X-ray data from nonconductive samples, depending on the operating conditions. This article reviews some of the documented approaches and presents data that illustrate the nature and magnitude of the effects of charge above, on, and in the sample on the detected X-ray emissions from the sample and from elsewhere within the VPSEM specimen chamber. The collection of reliable and reproducible X-ray data has been found to require relatively high specimen chamber gas pressures, at the upper end of or beyond the available pressures for most VPSEMs. It is also shown that sample characteristics, including composition, strongly influence local charge effects, which can significantly affect the primary electron landing energy and consequently the resultant emitted X-ray signal under low pressure environments.