Nanocomposites based on Cu2O coated silver nanowire networks for high-performance oxygen evolution reaction.

The development of highly active, low-cost, and robust electrocatalysts for the oxygen evolution reaction (OER) is a crucial endeavor for the clean and economically viable production of hydrogen via electrochemical water splitting. Herein, cuprous oxide (Cu2O) thin films are deposited on silver nanowire (AgNW) networks by atmospheric-pressure spatial atomic layer deposition (AP-SALD). AgNW@Cu2O nanocomposites supported on conductive copper electrodes exhibited superior OER activity as compared to bare copper substrate and bare AgNWs. Moreover, a relationship between Cu2O thickness and OER activity was established. Notably, the most effective catalyst (AgNW@50nm-thick Cu2O) demonstrated very high OER activity with a low overpotential of 409 mV to deliver a current density of 10 mA cm-2 (η 10), a Tafel slope of 47 mV dec-1, a turnover frequency (TOF) of 4.2 s-1 at 350 mV, and good durability in alkaline media (1 M KOH). This highlights the potential of AgNWs as a powerful platform for the formation of highly efficient copper oxide catalysts towards OER. This work provides a foundation for the development of nanostructured Cu-based electrocatalysts for future clean energy conversion and storage systems.

Optimization of Oxygen Evolution Reaction with Electroless Deposited Ni-P Catalytic Nanocoating.

The low efficiency of water electrolysis mostly arises from the thermodynamic uphill oxygen evolution reaction. The efficiency can be greatly improved by rationally designing low-cost and efficient oxygen evolution anode materials. Herein, we report the synthesis of Ni-P alloys adopting a facile electroless plating method under mild conditions on nickel substrates. The relationship between the Ni-P properties and catalytic activity allowed us to define the best conditions for the electroless synthesis of highperformance Ni-P catalysts. Indeed, the electrochemical investigations indicated an increased catalytic response by reducing the thickness and Ni/P ratio in the alloy. Furthermore, the Ni-P catalysts with optimized size and composition deposited on Ni foam exposed more active sites for the oxygen evolution reaction, yielding a current density of 10 mA cm-2 at an overpotential as low as 335 mV, exhibiting charge transfer resistances of only a few ohms and a remarkable turnover frequency (TOF) value of 0.62 s-1 at 350 mV. The present study provides an advancement in the control of the electroless synthetic approach for the design and large-scale application of high-performance metal phosphide catalysts for electrochemical water splitting.

Synthesis and Photochemical Properties of Monolithic TiO2 Nanowires Diode.

In this paper, the structural and photochemical properties of a monolithic photochemical diode are discussed. The present structure is composed, from the top to the bottom, of a TiO2 nanowire layer, a TiO2 film, a Ti foil, and a porous layer made of Pt nanoparticles. The synthesis of the nanowires was simply carried out by Au-catalysed-assisted process; the effects of the annealing temperature and time were deeply investigated. Morphological and structural characterizations were performed by scanning electron microscopy and Raman spectroscopy. The analyses showed the rutile structure of the TiO2 nanowires. The photocatalytic properties were studied through the degradation of methylene blue (MB) dye under UV light irradiation. The nanowires induced an enhancement of the photo-degradation rate, compared to TiO2 in a bulk form, due to an increase in the surface area. Moreover, the presence of a nano-porous Pt layer deposited on the rear side of the samples provided a further increase in the MB degradation rate, related to the scavenging effect of Pt nanoparticles. The overall increment of the photo-activity, due to the nano-structuration of the TiO2 and to the presence of the Pt layer, resulted a factor 7, compared to the bulk reference. In addition, photovoltage measurements allowed to assess the effects of TiO2 nano-structuration and Pt nanoparticles on the electron accumulation.

Strong Modulations of Optical Reflectance in Tapered Core-Shell Nanowires.

Random assemblies of vertically aligned core-shell GaAs-AlGaAs nanowires displayed an optical response dominated by strong oscillations of the reflected light as a function of the incident angle. In particular, angle-resolved specular reflectance measurements showed the occurrence of periodic modulations in the polarization-resolved spectra of reflected light for a surprisingly wide range of incident angles. Numerical simulations allowed for identifying the geometrical features of the core-shell nanowires leading to the observed oscillatory effects in terms of core and shell thickness as well as the tapering of the nanostructure. The present results indicate that randomly displaced ensembles of nanoscale heterostructures made of III-V semiconductors can operate as optical metamirrors, with potential for sensing applications.

Heterobimetallic Sodium Rare-Earth Complexes: "Third-Generation" MOCVD Precursors for the Deposition of NaREF4 (RE = Y, Gd) Films.

We report the synthesis of novel heterobimetallic precursors of the formula [RE(hfa)4]-[Na·tetraglyme]+ [RE = Y, Gd; Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane], which can be efficiently used as a single source for the metal-organic chemical vapor deposition of NaREF4 films.

Nanoparticle Stability in Axial InAs-InP Nanowire Heterostructures with Atomically Sharp Interfaces.

The possibility to expand the range of material combinations in defect-free heterostructures is one of the main motivations for the great interest in semiconductor nanowires. However, most axial nanowire heterostructures suffer from interface compositional gradients and kink formation, as a consequence of nanoparticle-nanowire interactions during the metal-assisted growth. Understanding such interactions and how they affect the growth mode is fundamental to achieve a full control over the morphology and the properties of nanowire heterostructures for device applications. Here we demonstrate that the sole parameter affecting the growth mode (straight or kinked) of InP segments on InAs nanowire stems by the Au-assisted method is the nanoparticle composition. Indeed, straight InAs-InP nanowire heterostructures are obtained only when the In/Au ratio in the nanoparticles is low, typically smaller than 1.5. For higher In content, the InP segments tend to kink. Tailoring the In/Au ratio by the precursor fluxes at a fixed growth temperature enables us to obtain straight and radius-uniform InAs-InP nanowire heterostructures (single and double) with atomically sharp interfaces. We present a model that is capable of describing all the experimentally observed phenomena: straight growth versus kinking, the stationary nanoparticle compositions in pure InAs and InAs-InP nanowires, the crystal phase trends, and the interfacial abruptness. By taking into account different nanowire/nanoparticle interfacial configurations (forming wetting or nonwetting monolayers in vertical or tapered geometry), our generalized model provides the conditions of nanoparticle stability and abrupt heterointerfaces for a rich variety of growth scenarios. Therefore, our results provide a powerful tool for obtaining high quality InAs-InP nanowire heterostructures with well-controlled properties and can be extended to other material combinations based on the group V interchange.

The quest towards epitaxial BaMgF4 thin films: exploring MOCVD as a chemical scalable approach for the deposition of complex metal fluoride films.

Conventional and Pulsed Liquid Injection MOCVD processes (C-MOCVD and PLI-MOCVD) have been explored as synthetic routes for the growth of BaMgF4 on Si (100) and single crystalline SrTiO3 (100) substrates. For the two applied approaches, the volatile, thermally stable ß-diketonate complexes Ba(hfa)2tetraglyme and Mg(hfa)2(diglyme)2(H2O)2 have been used as single precursors (C-MOCVD) or as a solution multimetal source (PLI-MOCVD). Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial BaMgF4 films on SrTiO3 substrates. Energy dispersive X-ray (EDX) analyses have been used to confirm composition and purity of deposited films. The impact of process parameters on film properties has been addressed, highlighting the strong influence of precursor ratio, deposition temperature and oxygen partial pressure on composition, microstructure and morphology of the films. Both methods appear well suited for the growth of the BaMgF4 phase, but while PLI-MOCVD yields a more straightforward control of the precursor composition that reflects on film stoichiometry, C-MOCVD provides easier control of the degree of texturing as a function of temperature.