Dual Metastability in Electroless Plating: Complex Inertness Enabling the Deposition of Composition-Tunable Platinum Copper Alloy Nanostructures

Autocatalytic deposition represents a facile, versatile, and scalable wet-chemical tool for nanofabrication. However, the intricate component interplay in plating baths containing multiple metal species impedes alloy deposition. We resolved this challenge in the bimetallic copper-platinum system by exploiting the kinetic stability of platinum complexes, which allows adjusting their ligand sphere and thus reactivity independently from the present copper ions in a preceding, thermally activated ligand exchange step. By using metastable Pt^IV precursors of varying degrees of complexation, copper-platinum alloys of adjustable atomic ratio were plated from solutions of identical composition and concentration, but differing local coordination environment. Due to its excellent conformity and nanoscale homogeneity, the reaction is compatible with ambitious 3D substrate morphologies, as demonstrated in the template-assisted fabrication of nanotubes with high aspect ratio. The ability to generate additional synthetic degrees of freedom by decoupling the metal complex speciation from the solution composition is of large interest for redox-chemical synthesis techniques, such as electrodeposition or nanoparticle colloid production.     

Direct determination of selenium in sub-milligram amounts of human sperm nuclei by electrothermal atomic absorption spectrometry

In the sperm nuclei selenium is present only in form of a single selenoenzyme, the sperm nuclei glutathione peroxidase (snGPx), involved in processes to secure the structural stability of the nuclear chromatin. As changes in its expression may affect sperm function, its analysis is of interest in the diagnosis of male infertility. A method has been developed which by removal of the other selenium compounds present in other sperm components and measurement of the concentration of selenium in the purified human sperm nuclei by electrothermal atomic absorption spectrometry (ETAAS) allows the quantitative analysis of this enzyme. As the purification resulted in yields in the range of only 150 μg nuclei/ml semen and the amount of purified nuclei in the sample could only be determined by weighing, the main analytical difficulty arose from the accurate determination of the sample masses. The procedure includes preparation of purified sperm nuclei, measurement of the sample mass and direct selenium analysis in the suspensions of the compact sperm nuclei without prior digestion of the matter, using a palladium matrix modifier, a spectrometer with Zeeman background correction and a graphite atomizer with L'vov platform. The detection limit for the determination of selenium was 8.4 pg. The quality control of the results by means of instrumental neutron activation analysis (INAA) showed the reliability of the selenium determination by ETAAS. The procedure proved to be suitable to analyze selenium and thus snGPx in very small amounts of purified human sperm nuclei.     

Activity, stability and degradation of multi walled carbon nanotube (MWCNT) supported Pt fuel cell electrocatalysts

Understanding and improving durability of fuel cell catalysts are currently one of the major goals in fuel cell research. Here, we present a comparative stability study of multi walled carbon nanotube (MWCNT) and conventional carbon supported platinum nanoparticle electrocatalysts for the oxygen reduction reaction (ORR). The aim of this study was to obtain insight into the mechanisms controlling degradation, in particular the role of nanoparticle coarsening and support corrosion effects. A MWCNT-supported 20 wt.% Pt catalyst and a Vulcan XC 72R-supported 20 wt.% Pt catalyst with a BET surface area of around 150 m(2) g(-1) and with a comparable Pt mean particle size were subjected to electrode potential cycling in a "lifetime" stability regime (voltage cycles between 0.5 to 1.0 V vs. RHE) and a "start-up" stability regime (cycles between 0.5 to 1.5 V vs. RHE). Before, during and after potential cycling, the ORR activity and structural/morphological (XRD, TEM) characteristics were recorded and analyzed. Our results did not indicate any activity benefit of MWCNT support for the kinetic rate of ORR. In the "lifetime" regime, the MWCNT supported Pt catalyst showed clearly smaller electrochemically active surface area (ECSA) and mass activity losses compared to the Vulcan XC 72R supported Pt catalyst. In the "start-up" regime, Pt on MWCNT exhibited a reduced relative ECSA loss compared to Pt on Vulcan XC 72R. We directly imaged the trace of a migrating platinum particle inside a MWCNT suggesting enhanced adhesion between Pt atoms and the graphene tube walls. Our data suggests that the ECSA loss differences between the two catalysts are not controlled by particle growth. We rather conclude that over the time scale of our stability tests (10,000 potential cycles and beyond), the macroscopic ECSA loss is primarily controlled by carbon corrosion associated with Pt particle detachment and loss of electrical contact.     

Solvent-Dependent Growth and Stabilization Mechanisms of Surfactant-Free Colloidal Pt Nanoparticles

Understanding the formation of nanoparticles (NPs) is key to develop materials by sustainable routes. The Co4Cat^TM process is a new synthesis of precious metal NPs in alkaline mono-alcohols well-suited to develop active nanocatalysts. The synthesis is ‘facile’, surfactant-free and performed under mild conditions like low temperature. The reducing properties of the solvent are here shown to strongly influence the formation of Pt NPs. Based on the in situ formation of CO adsorbed on the NP surface by solvent oxidation, a model is proposed that accounts for the different growth and stabilization mechanisms as well as re-dispersion properties of the surfactant-free NPs in different solvents. Using in situ and ex situ characterizations, it is established that in methanol, a slow nucleation with a limited NP growth is achieved. In ethanol, a fast nucleation followed by continuous and pronounced particle sintering occurs.     

In Situ Observation of the Thermally Induced Growth of Platinum‐Nanoparticle Catalysts Using High‐Temperature X‐ray Diffraction

Fundamental understanding about the thermal stability of nanoparticles and deliberate control of structural and morphological changes under reactive conditions is of general importance for a wide range of reaction processes in heterogeneous and electrochemical catalysis. Herein, we present a parametric study of the thermal stability of carbon‐supported Pt nanoparticles at 80 °C and 160 °C, with an initial particle size below 3 nm, using in situ high‐temperature X‐ray diffraction (HT‐XRD). The effects on the thermal stability of carbon‐supported Pt nanoparticles are investigated with control parameters such as Brunauer–Emmet–Teller (BET) surface area, metal loading, temperature, and gas environment. We demonstrate that the growth rate exhibits a complex, nonlinear behavior and is largely controlled by the temperature, the initial particle size, and the interparticle distance. In addition, an ex situ transmission electron microscopy study was performed to verify our results obtained from the in situ HT‐XRD study.     

Size-dependent morphology of dealloyed bimetallic catalysts: linking the nano to the macro scale

Chemical dealloying of Pt binary alloy precursors has emerged as a novel and important preparation process for highly active fuel cell catalysts. Dealloying is a selective (electro)chemical leaching of a less noble metal M from a M rich Pt alloy precursor material and has been a familiar subject of macroscale corrosion technology for decades. The atomic processes occurring during the dealloying of nanoscale materials, however, are virtually unexplored and hence poorly understood. Here, we have investigated how the morphology and intraparticle composition depend on the particle size of dealloyed Pt-Co and Pt-Cu alloy nanoparticle precursor catalysts. To examine the size-morphology-composition relation, we used a combination of high-resolutionscanning transmission electron microscopy (STEM), transmission electron microscopy (TEM), electron energy loss (EEL) spectroscopy, energy-dispersive X-ray spectroscopy (EDS), and surface-sensitive cycling voltammetry. Our results indicate the existence of three distinctly different size-dependent morphology regimes in dealloyed Pt-Co and Pt-Cu particle ensembles: (i) The arrangement of Pt shell surrounding a single alloy core ("single core-shell nanoparticles") is exclusively formed by dealloying of particles below a characteristic diameter d(multiple cores) of 10-15 nm. (ii) Above d(multiple cores), nonporous bimetallic core-shell particles dominate and show structures with irregular shaped multiple Co/Cu rich cores ("multiple cores-shell nanoparticles"). (iii) Above the second characteristic diameter d(pores) of about 30 nm, the dealloyed Pt-Co and Pt-Cu particles start to show surface pits and nanoscale pores next to multiple Co/Cu rich cores. This structure prevails up to macroscopic bulklike dealloyed particles with diameter of more than 100 nm. The size-morphology-composition relationships link the nano to the macro scale and provide an insight into the existing material gap of dealloyed nanoparticles and highly porous bulklike bimetallic particles in corrosion science.     

Multiple activation of ion track etched polycarbonate for the electroless synthesis of metal nanotubes

In our study, we examined the formation of thin films of silver nanoparticles on polycarbonate and the influence of the silver loading on the electroless synthesis of metal nanotubes. Control of the silver film thickness occurred by consecutive dipping of the polymer template in tin(II) and silver(I) solutions. The deposition progress was studied using UV-Vis spectroscopy. The reaction mechanism relies on the adsorption of reactive ions on the polymer template as well as on the silver nanoparticles. The initial catalytic activity of silver-covered ion track etched polycarbonate is an important governing factor for the electroless synthesis of metal nanotubes with desired thickness and shape. Therefore, the presented method allows specific template preparation according to given synthetic demands. High aspect ratio copper, gold, and platinum nanotubes were produced by the combination of sufficiently activated templates with optimized electroless plating procedures.