35 Search Results

Electrochemical approaches toward clean energy production have been the focus of significant attention. Here, the nitrogen (N₂) reduction reaction (NRR) and the hydrogen (H₂) evolution reaction (HER) offer a promising method for producing NH₃ and H₂, respectively. Nevertheless, practical obstacles that must be overcome in creating optimal catalysts are the sluggish kinetics and low selectivity of NRR and HER. Herein, we report on the synthesis of a Ru-RuO₂-decorated boron nitride (BN) catalyst that shows excellent activity toward NRR. A rate of NH3 formation (V_NH3) of 16.8 μg h^-1 mg^-1 and a corresponding Faradaic efficiency (FE) of 52.9% were noted atmore » a potential of −0.5 V in 0.1 M HCl. However, the HER activity of Ru-RuO₂@BN was found to be highly suppressed in 0.1 M HCl and did not yield a reasonable overpotential value. Thus, the capability of this material toward NRR suggests its viability as a promising catalyst for clean NH₃ production.« less

High-entropy oxides (HEOs) featuring 5 or more metals in approximately equimolar ratios, such as the prototypical rock-salt-structured (CoCuMgNiZn)O, have attracted interest for their potential to display material properties superior to oxides with combinations of 4 or fewer of the component metals. In particular, (CoCuMgNiZn)O has shown promise as an anode for lithium-ion batteries with a high specific capacity retention over extended cycling. Previous studies have suggested that magnesium, despite being electrochemically inert, provides a crucial contribution to the favorable performance of this HEO by stabilizing the crystal structure through repeated charge–discharge cycles. This paper probes the extent and mechanism ofmore » the magnesium effect by using a facile microwave-assisted hydrothermal synthesis method to vary the level of Mg content. Moreover, we extensively characterized the product with techniques such as 4D-STEM and ICP-OES, which have not previously been applied in combination with this material, in order to elucidate the relationships among chemical composition, nanostructure, and performance. Here, we show that the level of Mg incorporation is positively correlated with long-term stability and negatively correlated with rate capacity, and that the latter effect yields a stronger influence upon the overall performance, with the best-performing sample possessing a Mg quantity equivalent to ∼1/5 that of an equimolar concentration. This finding demonstrates not only that the variation of individual elemental levels offers a promising and relatively unexplored avenue to optimize the electrochemical performance of HEO materials but also that it should not be assumed that equimolar compositions of constituent elements are necessarily the best.« less

Artificial N₂ fixation via the electrocatalytic nitrogen (N₂) reduction reaction (NRR) has been recently promoted as a rational route toward reducing energy consumption and CO₂ emission as compared with the traditional Haber–Bosch process. Nevertheless, optimizing NRR relies on developing highly efficient electrocatalysts. Herein, we report on the reliable and reproducible synthesis of two promising electrocatalysts in either the presence or absence of Ketjenblack (KB), namely, ZrO₂–ZrN@KB and ZrO₂–ZrN systems, synthesized through the nitriding of Zr. Both materials had never previously been considered for NRR, to the best of our knowledge. Nevertheless, both of these electrocatalysts incorporated a combination of tetragonalmore » ZrO₂, ZrON, and cubic ZrN and showed excellent activity and durability toward NH₃ formation. Moreover, the maximum NH3 production rate of 84.1 μg h^–1 mg^–1 at -0.7 V vs a reversible hydrogen electrode (RHE) was achieved with the ZrO₂–ZrN electrocatalyst with an impressive Faradaic efficiency of 21.2% at -0.6 V vs RHE, indicating a high selectivity associated with the NRR. Additionally, the catalysts demonstrated excellent stability during the electrolysis process and recycling tests. Here we postulate that the combination of exposed active sites of ZrN and ZrO₂ likely contributes to the enhanced NRR performance attributed to ZrO₂–ZrN.« less

A combination of several in-situ techniques (XRD, XAS, AP-XPS, E-TEM) was used to explore links between the structural and chemical properties of a Cu@TiO_x catalyst under CO₂ hydrogenation conditions. The active phase of the catalyst involved an inverse oxide/metal configuration, but the initial core@shell motif was disrupted during the pre-treatment in H₂. As a consequence of strong metal-support interactions, the titania shell cracked and Cu particles migrated from the core to on top of the oxide with the simultaneous formation of a Cu-Ti-O_x phase. The generated Cu particles had a diameter of 20-40 nm and were decorated by small clustersmore » of TiO_x (< 5 nm in size). Results of in-situ XAS and XRD and images of E-TEM showed a very dynamic system, where the inverse oxide/metal configuration promoted the reactivity of the system towards CO₂ and H₂. At room temperature, CO₂ oxidized the Cu nanoparticles (CO_2,gas → CO_gas + O_oxide) inducing a redistribution of the TiO_x clusters and big modifications in catalyst surface morphology. The generated oxide overlayer disappeared at elevated temperatures (> 180 °C) upon exposure to H₂, producing a transient surface that was very active for the reverse water-gas shift reaction (CO₂ + H₂ → CO + H₂O) but was not stable at 250 °C. When oxidation and reduction occurred at the same time, under a mixture of CO₂ and H₂, the surface structure evolved toward a dynamic equilibrium that strongly depended on the temperature. Neither CO₂ nor H₂ can be considered as passive reactants. In the Cu@TiO_x system, morphological changes were linked to variations in the composition of metal-oxide interfaces which were reversible with temperature or chemical environment and affected the catalytic activity of the system. Finally, the present study illustrates the dynamic nature of phenomena associated with the trapping and conversion of CO₂.« less

Zinc tungstate is a semiconductor known for its favorable photocatalytic, photoluminescence, and scintillation properties, coupled with its relatively low cost, reduced toxicity, and high stability in biological and catalytic environments. In particular, zinc tungstate evinces scintillation properties, namely the ability to emit visible light upon absorption of energetic radiation such as x rays, which has led to applications not only as radiation detectors but also for biomedical applications involving the delivery of optical light to deep tissue, such as photodynamic therapy and optogenetics. Here, we report on the synthesis of zinc tungstate nanorods generated via an optimized but facile method,more » which allows for synthetic control over the aspect ratio of the as-synthesized anisotropic motifs via rational variation of the solution pH. Additionally, we investigate the effect of aspect ratio on their resulting photoluminescent and radioluminescent properties. We further demonstrate the potential of these zinc tungstate nanorods for biomedical applications, such as photodynamic therapy for cancer treatment, by analyzing their toxicological profile within cell lines and neurons.« less

Using microscopy and spectroscopy to assess ultrathin nanowire structure.

We have successfully synthesized ultrathin nanowires of pure Pt, Pt₉₉Ni₁, Pt₉Ni₁, and Pt₇Ni₃ using a modified room-temperature soft-template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt₇Ni₃ samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm² respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre-reduction treatment; however, after annealing in H₂, we detected significantly improved CO₂ formation for both Pt₉Ni₁ and Pt₇Ni₃more » motifs. These observations highlight the importance of pre-treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x-ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt-rich shell coupled with a Ni-rich core. Here, we also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.« less

Abstract The syntheses of FeS ₂ and Fe ₃ S ₄ nanomaterials were optimized using a novel facile, surfactant-free, and microwave-assisted, one-pot synthesis method, run under ambient and reasonably mild reaction conditions. Synthetic parameters, such as metal precursor salt identity, reaction time, reaction temperature, metal:sulfur molar ratios, and solvent combinations, were all systematically investigated and optimized. A series of FeS ₂ (pyrite) samples was initially fabricated using thioacetamide (TAA) as the sulfur precursor to generate a distinctive, uniform octahedra-based morphology. Switching the sulfur precursor from TAA to L-cysteine resulted in a corresponding transformation in not only chemical composition from FeSmore » ₂ to an iron thiospinel structure, Fe ₃ S ₄ (otherwise known as greigite), but also an associated morphological evolution from octahedra to nanosheet aggregates. The study of these materials has enabled crucial insights into the formation mechanisms of these materials under a relatively non-conventional microwave-assisted setting. Furthermore, in separate experiments, multi-walled carbon nanotubes (MWNTs) and graphene were added in with underlying metal sulfide species to create conductive Fe–S/MWNT composites and Fe–S/graphene composites, respectively. The method of addition of either MWNTs or graphene was also explored, wherein an ‘ ex-situ ’ synthetic procedure was found to be the least disruptive means of attachment and immobilization onto iron sulfide co-reagents as a means of preserving the latter’s inherent composition and morphology. The redox acidity for the parent material and associated composites demonstrates the utility of our as-developed synthetic methods for creating motifs relevant for electrochemical applications, such as energy storage.« less

We have synthesized several morphologies and crystal structures of MgWO₄ using a one-pot hydrothermal method, producing not only monoclinic stars and large nanoparticles but also triclinic wool balls and sub-10 nm nanoparticles. Herein we describe the importance of reaction parameters in demonstrating morphology control of as-prepared MgWO₄. Moreover, we correlate structure and composition with the resulting photoluminescence and radioluminescence properties. Specifically, triclinic-phase samples yielded a photoluminescence emission of 421 nm, whereas monoclinic-phase materials gave rise to an emission maximum of 515 nm. The corresponding radioluminescence data were characterized by a broad emission peak, located at 500 nm for all samples.more » Annealing the wool balls and sub-10 nm particles to transform the crystal structure from a triclinic to a monoclinic phase yielded a radioluminescence (RL) emission signal that was two orders of magnitude greater than that of their unannealed counterparts. Finally, to confirm the practical utility of these materials for biomedical applications, a series of sub-10 nm particles, including as-prepared and annealed samples, were functionalized with biocompatible PEG molecules, and subsequently were found to be readily taken up by various cell lines as well as primary cultured hippocampal neurons with low levels of toxicity, thereby highlighting for the first time the potential of this particular class of metal oxides as viable and readily generated platforms for a range of biomedical applications.« less

Ultrathin Pt nanowires possess high activity for various electrocatalytic applications. However, little work has focused on understanding their growth mechanisms. Herein, we utilize a combination of time-dependent, ex situ transmission electron microscopy (TEM) and small angle x-ray scattering (SAXS) techniques to observe the growth process in addition to associated surfactant-based interactions. TEM images indicate that initially nanoparticles are formed within 30 s; these small 'seed' particles quickly elongate to form ultrathin nanowires after 2 min. These motifs remain relatively unchanged in size and shape up to 480 min of reaction. Complementary SAXS data suggests that the initial nanoparticles, which aremore » coated by a surfactant bilayer, arrange into a bcc superlattice. With increasing reaction time, the bcc lattice disappears as the nanoparticles grow into nanowires, which then self-assemble into a columnar hexagonal structure in which the individual nanowires are covered by a CTAB monolayer. The hexagonal structure eventually degrades, thereby leading to the formation of lamellar stacking phases comprised of surfactant bilayers. To the best of our knowledge, this is the first time that SAXS has been used to monitor the growth and self-assembly of Pt nanowires. In conclusion, these insights can be used to better understand and rationally control the formation of anisotropic motifs of other metallic nanostructures.« less