Homogeneity and elemental distribution in self-assembled bimetallic Pd-Pt aerogels prepared by a spontaneous one-step gelation process.

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd-Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd-Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd-Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd-Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd-Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd-Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd-Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

Teaching old precursors new tricks: Fast room temperature synthesis of surfactant-free colloidal platinum nanoparticles.

A fast, simple, instrument-free room temperature synthesis of stable electroactive surfactant-free colloidal Pt nanoparticles in alkaline methanol and methanol-water mixtures is presented. Pair distribution function (PDF) analysis suggests that methoxy substitution of chloride ligands from H2PtCl6 occurs in methanol. X-ray absorption spectroscopy (XAS) studies and UV-vis measurements show that solutions of H2PtCl6 in methanol age and are reduced to Pt(II) species over time. These species are ideal precursors to significantly reduce the induction period typically observed in colloidal Pt nanoparticle syntheses as well as the temperature needed to form nanoparticles. The room temperature synthesis presented here allows designing simple in situ studies of the nanoparticle formation. In situ infra-red spectroscopy gives insight into the formation and stabilization mechanism of surfactant-free nanoparticles by CO surface groups. Finally, the surfactant-free nanoparticles ca. 2-3 nm in diameter obtained are shown to be readily active electrocatalysts e.g. for methanol oxidation. The synthesis approach presented bears several advantages to design new studies and new syntheses of surfactant-free colloidal nanomaterials.

The role of polyvinylpyrrolidone (PVP) as a capping and structure-directing agent in the formation of Pt nanocubes.

In this work, we have investigated the specific role of PVP and Ag+ ions in the formation of platinum nanocubes (NCs) in polyol synthesis. Various characterization techniques such as transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed to unravel the effects of PVP and Ag+ ion concentrations on the monodispersity and particle size of the obtained Pt NCs. Very interestingly, we have already fabricated Pt NCs with similar monodispersity and particle size using only 0.4 M PVP (absence of Ag+ ions). Furthermore, the dispersity of the Pt NCs strongly depends on the initial PVP concentration. This observation underscores the important role of PVP during the NC formation processes by controlling the relative growth rates along the <100> direction with respect to those of the <111>. Time-resolved experiments show that the formation and growth of Pt NCs are much faster in the absence of Ag+ ions than with Ag+ ions, which can be explained by the enhanced growth rate along the <100> direction or/and the suppression of the growth rate along the <111>. Electronic interactions between the chemisorbed pyrrolidone ring of the PVP and Pt surface are revealed from the XPS and FTIR data, showing a negative shift of the binding energy of N 1s and a red shift of the Pt-CO vibration band. From our experimental results, we propose extended formation and growth mechanisms based on PVP as the main structure-directing agent. Our model indicates that the aliphatic chains of PVP forming a multi-layer shell influence the mass transport of precursor ions to the initial Pt seed to control the growth rate of Pt NCs with exposed {100} planes. Altogether, we provide a simple, efficient and resource-friendly synthetic guideline for the preparation of nano-sized Pt NCs with high monodispersity and high purity.