James Murowchick

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively.

Built-in Electric Field-Assisted Surface-Amorphized Nanocrystals for High-Rate Lithium-Ion Battery

High-power batteries require fast charge/discharge rates and high capacity besides safe operation. TiO2 has been investigated as a safer alternative candidate to the current graphite or incoming silicon anodes due to higher redox potentials in effectively preventing lithium deposition. However, its charge/discharge rates are reluctant to improve due to poor ion diffusion coefficients, and its capacity fades quickly with rate as only thinner surface layers can be effectively used in faster charge/discharge processes. Here, we demonstrate that surface-amorphized TiO2 nanocrystals greatly improve lithium-ion rechargeable battery performance: 20 times rate and 340% capacity improvement over crystalline TiO2 nanocrystals. This improvement is benefited from the built-in electric field within the nanocrystals that induces much lower lithium-ion diffusion resistance and facilitates its transport in both insertion and extraction processes. This concept thus offers an innovative and general approach toward designing battery materials with better performance.

Cyclic variations of sulfur isotopes in Cambrian stratabound Ni-Mo- ( PGE-Au) ores of southern China

Abstract Cyclic variations of δ 34 S values over a range of at least 48‰ in pyrite nodules from stratabound Ni-Mo-PGE(Au) ores of southern China are attributed to biogenic reduction of seawater sulfate in an anoxic, phosphogenic, and metallogenic basin. Cyclic introduction and mixing of normal seawater into typically stagnant basin waters led to extreme variations in δ 34 S values of aqueous sulfide species present at different times. Intermittent venting of metal-laden hydrothermal fluids into such a bacteriogenic sulfide-rich environment resulted in precipitation of metal sulfides as pseudomorphous replacements of organic debris and as sulfide sediments that record large δ 34 S CDT variations from −26 to +22‰. Apatite and silica dominated the replacement of the organic debris when metals were not being introduced into the basin. The combination of abundant organic debris, localized topographic basins for accumulation of the debris, bacterial production of sulfide species, and introduction of metal-bearing hydrothermal fluids provided the environment necessary to form these unusually rich Ni-Mo ores.

Directional Heat Dissipation across the Interface in Anatase–Rutile Nanocomposites

Understanding the structures and properties of interfaces in (nano-)composites helps to reveal their important influence on reactivity and overall performance. TiO2 is a technologically important material, and anatase/rutile TiO2 composites have been shown to display enhanced photocatalytic performance over pure anatase or rutile TiO2. This has been attributed to a synergistic effect between the two phases, but the origin of this effect as well as the structure of the interface has not been established. Using Raman spectroscopy, here we provide evidence of distinct differences in the thermal properties of the anatase and rutile moieties in the composite, with anatase becoming effectively much warmer than the rutile phase under laser irradiation. With the help of first-principles calculations, we analyze the atomic structure and unique electronic properties of the composite and infer possible reasons for the directional heat dissipation across the interface.

Gold and platinum in shales with evidence against extraterrestrial sources of metals

Abstract Few black shales contain concentrations of precious metals higher than average continental crust (i.e. ∼5 ppb Au). Yet Au and Pt alloys have been reported from the Kupferschiefer in Poland. Moreover, thin sulfide beds in certain Chinese and Canadian shales contain several hundred ppb Au, Pd and Pt and average ∼4% Mo and ∼2.5% Ni in an association that is difficult to explain. Volcanic and non-volcanic exhalations, hydrothermal epigenesis involving either igneous or sedex fluids, biogenic processes and low-temperature secondary enrichment are among the possible factors involved in deriving Ni, PGE and Au for black shales and sulfide beds in black shales. Extraterrestrial sources have been invoked in some cases (e.g., the Cambrian of China). However, available data on abundances of PGE indicate relatively low values for Ir (

Hydrogenated black ZnO nanoparticles with enhanced photocatalytic performance

Following our previous findings on hydrogenated black TiO2 nanoparticles, here, we would like to present our exciting findings on hydrogenated black ZnO nanoparticles, which have displayed long-wavelength absorption and excellent photocatalytic performance. This further demonstrates that hydrogenation is a powerful tool to enhance the optical and photocatalytic performance of nanomaterials.

Effect of hydrogenation on the microwave absorption properties of BaTiO3 nanoparticles

Microwave absorbing materials (MAMs) have numerous important applications in electronic communications, signal protection, radar dodging, etc. Although it has been proposed as a promising MAM, BaTiO3 has a high reflection coefficient at the interface with air, causing a large reflection. Thus, its efficiency of microwave absorption is not satisfactory. Here, we report that hydrogenation has largely improved the microwave absorption of BaTiO3 nanoparticles. Hydrogenation is performed on BaTiO3 nanoparticles by treating pristine BaTiO3 nanoparticles at 700 °C for 4 hours in a pure H2 environment. The enhanced microwave absorption efficiency with a reflection loss value (−36.9 dB) is attributed to the increased resonance of polar rotations with the incident electromagnetic field which is amplified by the increased interfacial polarization caused by the built-in electrical field along the boundaries between different grains created within these nanoparticles.

Strong Microwave Absorption of Hydrogenated Wide Bandgap Semiconductor Nanoparticles

Electromagnetic interactions in the microelectronvolt (μeV) or microwave region have numerous important applications in both civil and military fields, such as electronic communications, signal protection, and antireflective coatings on airplanes against microwave detection. Traditionally, nonmagnetic wide-bandgap metal oxide semiconductors lack these μeV electronic transitions and applications. Here, we demonstrate that these metal oxides can be fabricated as good microwave absorbers using a 2D electron gas plasma resonance at the disorder/order interface generated by a hydrogenation process. Using ZnO and TiO2 nanoparticles as examples, we show that large absorption with reflection loss values as large as -49.0 dB (99.99999%) is obtained in the microwave region. The frequency of absorption can be tuned with the particle size and hydrogenation condition. These results may pave the way for new applications for wide bandgap semiconductors, especially in the μeV regime.

Spray Drying Tenofovir Loaded Mucoadhesive and pH-Sensitive Microspheres Intended for HIV Prevention

PURPOSE To develop spray dried mucoadhesive and pH-sensitive microspheres (MS) based on polymethacrylate salt intended for vaginal delivery of tenofovir (a model HIV microbicide) and assess their critical biological responses. METHODS The formulation variables and process parameters are screened and optimized using a 2(4-1) fractional factorial design. The MS are characterized for size, zeta potential, yield, encapsulation efficiency, Carrs index, drug loading, in vitro release, cytotoxicity, inflammatory responses and mucoadhesion. RESULTS The optimal MS formulation has an average size of 4.73μm, zeta potential of -26.3mV, 68.9% yield, encapsulation efficiency of 88.7%, Carrs index of 28.3 and drug loading of 2% (w/w). The MS formulation release 91.7% of its payload in the presence of simulated human semen. At a concentration of 1mg/ml, the MS are noncytotoxic to vaginal endocervical/epithelial cells and Lactobacillus crispatus when compared to control media. There is also no statistically significant level of inflammatory cytokine (IL1-α, IL-1β, IL-6, IL-8, and IP-10) release triggered by these MS. Their percent mucoadhesion is 2-fold higher than that of 1% HEC gel formulation. CONCLUSION These data suggest the promise of using such MS as an alternative controlled microbicide delivery template by intravaginal route for HIV prevention.

Partially amorphized MnMoO4 for highly efficient energy storage and the hydrogen evolution reaction

Engineering the crystallinity of materials has been proved to be an efficient strategy to improve the material’s properties in many applications. Herein, we demonstrate the successful transformation of electrochemically inert MnMoO4 into highly active bifunctional electrode materials for supercapacitors and as catalysts for the hydrogen evolution reaction through hydrogenation (hydrogen reduction at elevated temperatures). The hydrogenated MnMoO4 is partially amorphized with a one-fold increase in the electrochemically active surface area (ECSA). A 17-fold increase in specific capacitance is achieved, and the onset overpotential to drive the hydrogen evolution reaction markedly decreased to 105 mV from 194 mV. The highly enhanced electrochemical properties are likely due to the amorphous components and highly enhanced ECSA, which expose more active sites and enhance the charge-transfer kinetics on the surface.