Preparation of Pt-skin PtRhNi Nanoframes Decorated with Small SnO2 Nanoparticles as an Efficient Catalyst for Ethanol Oxidation Reaction.

Pt-based nanoframes are one of the most promising catalysts for ethanol oxidation reaction in direct ethanol fuel cells. It is important to understand the mechanisms responsible for creating these hollow nanoframe-based catalysts. Herein, for the first time, Pt-skin PtRhNi rhombic dodecahedral nanoframes were decorated with small SnO2 nanoparticles and were used as an efficient catalyst for the ethanol oxidation reaction. Moreover, by combining the ex situ scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy observations at various stages of synthesis, along with density functional theory calculations, it was possible to track the synthesis route of solid rhombic dodecahedral PtRhNi nanoparticles, which are the precursors of PtRhNi nanoframes. After the chemical etching of the Ni core from solid PtRhNi nanoparticles, the obtained nanoframes were decorated with SnO2 nanoparticles. The resulting SnO2@PtRhNi heteroaggregates were deposited on high-surface-area carbon and electrochemically tested, showing a 6-fold higher mass activity and 10-fold higher specific activity toward ethanol oxidation reaction than commercially available Pt catalysts.

Conversion of bimetallic PtNi3 nanopolyhedra to ternary PtNiSn nanoframes by galvanic replacement reaction.

Hollow multimetallic PtNiSn nanoparticles (NPs) were formed from solid Ni-core/Pt-frame NPs by the galvanic replacement reaction (GRR) of Ni by Sn. The GRR was performed by adding SnCl4·5H2O dissolved in ethylene glycol into the PtNi3 NPs containing suspension. The reaction yielded nanoframes with a hollow interior, having Pt-rich edges covered with a thin, incomplete Sn layer. They were investigated using transmission electron microscopy (TEM), energy dispersion X-ray spectroscopy (EDS) and X-ray diffraction (XRD). EDS analysis showed that the GRR rate could be modified by changing the solvent and the concentration of tin ions. Indeed, compared to water, ethylene glycol was found to facilitate the reduction of tin chloride and to affect nickel dissolution. TEM analysis revealed that the galvanic replacement of nickel and tin involves two different mechanisms. The first one consists of nickel oxidation followed by reduction of tin ions. In the second mechanism, oxidation of nickel and reduction of tin ions occur simultaneously.

Design and assembly of ternary Pt/Re/SnO2 NPs by controlling the zeta potential of individual Pt, Re, and SnO2 NPs.

In this study Pt, Re, and SnO2 nanoparticles (NPs) were combined in a controlled manner into binary and ternary combinations for a possible application for ethanol oxidation. For this purpose, zeta potentials as a function of the pH of the individual NPs solutions were measured. In order to successfully combine the NPs into Pt/SnO2 and Re/SnO2 NPs, the solutions were mixed together at a pH guaranteeing opposite zeta potentials of the metal and oxide NPs. The individually synthesized NPs and their binary/ternary combinations were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) analysis. FTIR and XPS spectroscopy showed that the individually synthesized Pt and Re NPs are metallic and the Sn component was oxidized to SnO2. STEM showed that all NPs are well crystallized and the sizes of the Pt, Re, and SnO2 NPs were 2.2, 1.0, and 3.4 nm, respectively. Moreover, EDS analysis confirmed the successful formation of binary Pt/SnO2 and Re/SnO2 NP, as well as ternary Pt/Re/SnO2 NP combinations. This study shows that by controlling the zeta potential of individual metal and oxide NPs, it is possible to assemble them into binary and ternary combinations. Graphical abstractᅟ.

Single-step synthesis of Er3+ and Yb3+ ions doped molybdate/Gd2O3 core-shell nanoparticles for biomedical imaging.

Nanostructures as color-tunable luminescent markers have become major, promising tools for bioimaging and biosensing. In this paper separated molybdate/Gd2O3 doped rare earth ions (erbium, Er3+ and ytterbium, Yb3+) core-shell nanoparticles (NPs), were fabricated by a one-step homogeneous precipitation process. Emission properties were studied by cathodo- and photoluminescence. Scanning electron and transmission electron microscopes were used to visualize and determine the size and shape of the NPs. Spherical NPs were obtained. Their core-shell structures were confirmed by x-ray diffraction and energy-dispersive x-ray spectroscopy measurements. We postulated that the molybdate rich core is formed due to high segregation coefficient of the Mo ion during the precipitation. The calcination process resulted in crystallization of δ/ξ (core/shell) NP doped Er and Yb ions, where δ-gadolinium molybdates and ξ-molybdates or gadolinium oxide. We confirmed two different upconversion mechanisms. In the presence of molybdenum ions, in the core of the NPs, Yb3+-[Formula: see text] (∣2F7/2, 3T2〉) dimers were formed. As a result of a two 980 nm photon absorption by the dimer, we observed enhanced green luminescence in the upconversion process. However, for the shell formed by the Gd2O3:Er, Yb NPs (without the Mo ions), the typical energy transfer upconversion takes place, which results in red luminescence. We demonstrated that the NPs were transported into cytosol of the HeLa and astrocytes cells by endocytosis. The core-shell NPs are sensitive sensors for the environment prevailing inside (shorter luminescence decay) and outside (longer luminescence decay) of the tested cells. The toxicity of the NPs was examined using MTT assay.