Project description:We report the superconducting properties between a conventional strong-coupled Pb and weak-coupled Sn superconductor. A series of SnrPb1-r nanoalloys with various compositions r were synthesized, and their superconducting properties were measured using superconducting quantum interference devices (SQUIDs) magnetometer. Our results reveal a superconducting proximity effect (SPE) between immiscible Sn and Pb granules in the range of r = 0.2~0.9, as a weak superconducting coupling can be established with the coexistence of phonon hardening and increased Ginzburg-Landau coherence length. Furthermore, our results provide new insights into improving the study of the superconducting proximity effect introduced by Sn doping.
Project description:Cr-surface segregation is a main roadblock encumbering many magneto-biomedical applications of bimetallic M-Cr nanoalloys (where M = Fe, Co and Ni). To overcome this problem, we developed Ni95Cr5:Ag nanocomposite as a model system, consisting of non-interacting Ni95Cr5 nanoalloys (5 ± 1 nm) immersed in non-magnetic Ag matrix by controlled simultaneous co-sputtering of Ni95Cr5 and Ag. We employed Curie temperature (TC) as an indicator of phase purity check of these nanocomposites, which is estimated to be around the bulk Ni95Cr5 value of 320 K. This confirms prevention of Cr-segregation and also entails effective control of surface oxidation. Compared to Cr-segregated Ni95Cr5 nanoalloy films and nanoclusters, we did not observe any unwanted magnetic effects such as presence Cr-antiferromagnetic transition, large non-saturation, exchange bias behavior (if any) or uncompensated higher TC values. These nanocomposites films also lose their unique magnetic properties only at elevated temperatures beyond application requirements (≥800 K), either by showing Ni-type behavior or by a complete conversion into Ni/Cr-oxides in vacuum and air environment, respectively.
Project description:Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi4 phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi4 catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction.
Project description:Development of cost-effective electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is key to enabling advanced electrochemical energy conversion technologies. Here, a novel nitrogen-doped metal-carbon hybrid (NiCo/CN) with a unique 3D hierarchical structure, consisting of uniformly distributed bimetallic nanoparticles encapsulated by partially graphitized N-doped carbon shells, is fabricated by a one-step pyrolysis of a nanoscale metal-organic framework as precursor, which exhibits excellent activity for both ORR and OER. The surface chemical changes on the carbon hybrid probed by X-ray photoelectron spectroscopy (XPS) reveal the presence of favorable electronic interaction at the metal-nitrogen-carbon interface. Remarkably, the NiCo/CN catalyst prepared at high temperature (800°C) manifests a comparable performance to a commercial Pt/C catalyst for the ORR, but also superior stability, path selectivity and methanol tolerance. On the other hand, the E onset (1.48 V vs. reversible hydrogen electrode) and E j = 10 mA/cm 2 of NiCo/CN-800 for OER is very close to the state-of-the-art noble catalyst RuO2 (Eonset = 1.46 and E j = 10 mA/cm 2 ) along with superior stability over 20 h of operation. The excellent catalytic property is attributable to the unique nanostructure, high porosity and the constructive synergistic effects of the elements M, N, and C.
Project description:In the present work, the chemical synthesis of AgPt nanoalloys is reported by the polyol method using polyvinylpyrrolidone (PVP) as a surfactant and a heterogeneous nucleation approach. Nanoparticles with different atomic compositions of the Ag and Pt elements (1:1 and 1:3) were synthesized by adjusting the molar ratios of the precursors. The physicochemical and microstructural characterization was initially performed using the UV-Vis technique to determine the presence of nanoparticles in suspension. Then, the morphology, size, and atomic structure were determined using XRD, SEM, and HAADF-STEM techniques, confirming the formation of a well-defined crystalline structure and homogeneous nanoalloy with an average particle size of less than 10 nm. Finally, the cyclic voltammetry technique evaluated the electrochemical activity of bimetallic AgPt nanoparticles supported on Vulcan XC-72 carbon for the ethanol oxidation reaction in an alkaline medium. Chronoamperometry and accelerated electrochemical degradation tests were performed to determine their stability and long-term durability. The synthesized AgPt (1:3)/C electrocatalyst presented significative catalytic activity and superior durability due to the introduction of Ag that weakens the chemisorption of the carbonaceous species. Thus, it could be an attractive candidate for cost-effective ethanol oxidation compared to commercial Pt/C.
Project description:Electrochemical CO2 reduction (ECR) is one of the promising CO2 recycling technologies sustaining the natural carbon cycle and offering more sustainable higher-energy chemicals. Zn- and Pb-based catalysts have improved formate selectivity, but they suffer from relatively low current activities considering the competitive CO selectivity on Zn. Here, lead-doped zinc (Zn(Pb)) electrocatalyst is optimized to efficiently reduce CO2 to formate, while CO evolution selectivity is largely controlled. Selective formate is detected with Faradaic efficiency (FEHCOOH ) of ≈95% at an outstanding partial current density of 47 mA cm-2 in a conventional H-Cell. Zn(Pb) is further investigated in an electrolyte-fed device achieving a superior conversion rate of ≈100 mA cm-2 representing a step closer to practical electrocatalysis. The in situ analysis demonstrates that the Pb incorporation plays a crucial role in CO suppression stem from the generation of the Pb-O-C-O-Zn structure rather than the CO-boosted Pb-O-C-Zn. Density functional theory (DFT) calculations reveal that the alloying effect tunes the adsorption energetics and consequently modifies the electronic structure of the system for an optimized asymmetric oxo-bridged intermediate. The alloying effect between Zn and Pb controls CO selectivity and achieves a superior activity for a selective CO2 -to-formate reduction.
Project description:The rapid development of supramolecular chemistry provides a powerful bottom-up approach to construct various well-defined nano-architectures with increasing complexity and functionality. Compared to that of small and simple nanometric objects, the self-assembly of larger and more complex nanometric objects, such as nanocages, remains a significant challenge. Herein, we used a discrete nanocage as the monomer to successfully construct a novel three-dimensional (3D) supramolecular architecture, which comprises two types of nanocage building units with different connectivity, using the solvent-assisted coordination-driven assembly approach. The mechanism of this supramolecular assembly process was investigated by electrospray ionization mass spectrometry (ESI-MS) studies, which identified for the first time the formation of a nanocage dimer intermediate during the assembly process. The assembly of discrete nanocages into a 3D supramolecular architecture led to remarkable enhancement of stability and gas adsorption properties.
Project description:The optical properties of hollow nanoparticles (Au-Ag nanoboxes and nanocages) were investigated by recording Rayleigh scattering spectra of single particles, whose morphology and composition had been analyzed by scanning electron microscopy (SEM). This was achieved by depositing the particles on optically transparent substrates with registration marks, which are compatible with SEM imaging. Fitting the experimental spectra to a Lorentzian function yields the frequencies and homogeneous line widths of the plasmon resonance for the particles. The resonances are extremely broad, with dephasing times of 2-5 fs. Analysis of the line width data using the dimensions determined by SEM shows that the broadening is due to a combination of electron-surface scattering and radiation damping. The sensitivity of the plasmon resonance to the dielectric constant of the environment was also investigated by adding a drop of water to the substrate. The nanoboxes show similar dielectric sensitivities compared to other metal nanoparticle systems. A significant increase in the line width was also observed for the nanoboxes in water compared with air. This was attributed to increased radiation damping in the environment with a higher dielectric constant. Both the red shift and the increase in line width are reversible.
Project description:Electrospun nanofiber membrane-supported thin film composite (TFC) membranes exhibit great potential in water purification. In this work, electrospun polyphenylsulfone (PPSU) nanofiber membranes were prepared and modified by heat and plasma treatments. The resulting membranes were used as support layers for biomimetic TFC-based forward osmosis membranes. Thermal treatment transformed a loose non-woven nanofiber structure into a robust interconnected 3-dimensional PPSU network displaying a 930% increase in elastic modulus, 853% increase in maximum stress, and two-fold increase in breaking strain. Superior hydrophilicity of PPSU nanofiber membranes was achieved by low-pressure plasma treatment, changing the contact angle from 137° to 0°. The fabricated exemplary TFC-based forward osmosis membrane showed an osmotic water flux J w > 14 L m-2 h-1 with a very low reserve salt flux J s (J s/J w = 0.08 g L-1) demonstrating the potential for making high quality membranes for water treatment using PPSU-based support layers for TFC membranes.
Project description:The response of nanoparticles to exposure to ambient conditions and especially oxidation is fundamental to the application of nanotechnology. Bimetallic platinum-titanium nanoparticles of selected mass, 30 kDa and 90 kDa, were produced using a magnetron sputtering gas condensation cluster source and deposited onto amorphous carbon TEM grids. The nanoparticles were analysed with a Cs-corrected Scanning Transmission Electron Microscope (STEM) in High Angle Annular Dark Field (HAADF) mode. It was observed that prior to full Ti oxidation, Pt atoms were dispersed within a Ti shell. However, after full oxidation by prolonged exposure to ambient conditions prior to STEM, the smaller size 30 kDa particles form a single Pt core and the larger size 90 kDa particles exhibit a multi-core structure. Electron beam annealing induced a single core morphology in the larger particles. First principles density functional theory (DFT) calculations were employed to calculate the lowest energy structure of the Pt-Ti nanoparticles with and without the presence of oxygen. It was demonstrated that, as the concentration of oxygen increases, the lowest energy structure changes from dispersed Pt to multiple Pt cores and finally a single Pt core, which is in good agreement with the experimental observations.