The more the better: on the formation of single-phase high entropy alloy nanoparticles as catalysts for the oxygen reduction reaction.

High entropy alloys (HEAs) are an important new material class with significant application potential in catalysis and electrocatalysis. The entropy-driven formation of HEA materials requires high temperatures and controlled cooling rates. However, catalysts in general also require highly dispersed materials, i.e., nanoparticles. Only then a favorable utilization of the expensive raw materials can be achieved. Several recently reported HEA nanoparticle synthesis strategies, therefore, avoid the high-temperature regime to prevent particle growth. In our work, we investigate a system of five noble metal single-source precursors with superior catalytic activity for the oxygen reduction reaction. Combining in situ X-ray powder diffraction with multi-edge X-ray absorption spectroscopy, we address the fundamental question of how single-phase HEA nanoparticles can form at low temperatures. It is demonstrated that the formation of HEA nanoparticles is governed by stochastic principles and the inhibition of precursor mobility during the formation process favors the formation of a single phase. The proposed formation principle is supported by simulations of the nanoparticle formation in a randomized process, rationalizing the experimentally found differences between two-element and multi-element metal precursor mixtures.

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 Co4CatTM 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.

Particle Size Effect on Platinum Dissolution: Practical Considerations for Fuel Cells.

The high costs of polymer membrane electrolyte fuel cells (PEMFCs) remain a roadblock for a competitive market with combustion engine vehicles. The PEMFC costs can be reduced by decreasing the size of Pt nanoparticles in the catalyst layer, thereby increasing the Pt dispersion and utilization. Furthermore, high-power performance loss due to O2 transport resistance is alleviated by decreasing the particle size and increasing dispersion. However, firm conclusions on how Pt particle size impacts durability remain elusive due to synthetic difficulties in exclusively varying single parameters (e.g., particle size and loading). Therefore, here the particle size of Pt nanoparticles was varied from 2.0 to 2.8 and 3.7 nm while keeping the loading constant (30 wt %) on a Vulcan support using the two-step surfactant-free toolbox method. By studying the electrochemical dissolution in situ using online inductively coupled plasma mass spectrometry (online ICP-MS), mass-specific dissolution trends are revealed and are attributed to particle-size-dependent changes in electrochemically active surface area. Such degradation trends are critical for the start/stop of PEMFCs and currently require the implementation of potential control systems in consumer vehicles. Additionally, shifts in the onset of anodic dissolution and also oxidation to more negative potentials with decreasing particle size were observed. These results indicate a similar mechanism of anodic dissolution related to place-exchange when moving from extended polycrystalline Pt to nanoparticle scales. The negative shifts in the onset as the particle size decreases highlight a practical limitation for PEMFCs during load/idle conditions: without further material improvements, which inhibit Pt dissolution, reduction in costs and improvement in high-power performance via increased Pt utilization and dispersion will not be possible by decreasing particle sizes further.

Comparative study of cytotoxicity by platinum nanoparticles and ions in vitro systems based on fish cell lines.

Emission of platinum nanoparticles (Pt NPs) especially from vehicle exhaust catalysts and pharmaceutics cause an increase in concentrations of this metal in aquatic environments. In this study, small (4-9 nm) uncoated and polyvinylpyrrolidone (PVP) coated Pt NPs were synthetized and their dispersion in different exposure media were evaluated. Pt NP uptake in two established fish cell lines were investigated and comparative in vitro cytotoxicity of Pt NPs and ions were assessed. The coated and uncoated Pt NPs dispersions in minimum essential medium (MEM) with fetal bovine serum (FBS) displayed high colloidal stability. Transmission electron microscopy (TEM) and high-resolution scanning electron microscope equipped with an energy-dispersive X-ray spectrometer (STEM/EDX) indicated no detectable cellular uptake of Pt NPs in both cell line monolayers. But with ICP-MS analysis, trace amount of Pt content was determined in all digested monolayer cell samples. The cytotoxicity of both Pt NPs and Pt ions on both fish cell lines after 48 h exposure was investigated through three assays to monitor different endpoints of cytotoxicity. In all studied concentrations (0.325-200 mg/L) no significant cytotoxicity (p > .5) compared to controls were observed in the cells exposed to coated Pt NPs. Uncoated Pt NP and ion exposed cells indicated similar concentration dependent cytotoxicity on both cell lines.

On the facile and accurate determination of the Pt content in standard carbon supported Pt fuel cell catalysts.

We introduce a new and straight-forward methodology to accurately determine the Pt content in polymer membrane electrolyte fuel cell (PEMFC) catalysts consisting of carbon supported Pt nanoparticles (Pt/C). The method is based on an indirect Pt proof (IPP) consisting of the oxidative removal of the carbon support, the digestion of the Pt in aqua regia followed by a replacement reaction to form Cu ions (CuCl2). The Pt content is then determined via the Cu-ions with the help a complexometric indicator using a simple titration. The procedure is fast and does not require any expensive equipment. Thus, it can be implemented in any standard chemistry laboratory. The advantages and disadvantages of the IPP method are evaluated in a comparison to alternative methods for the determination of the Pt content in supported catalysts, i.e. inductively coupled plasma mass spectrometry (ICP-MS) and UV/Vis spectroscopy (UV/Vis). It is demonstrated that the IPP method delivers reliable and accurate results and is less influenced than for example ICP-MS by side effects such as excess in nitric acid or organic impurities. Furthermore, during the procedure up to 60% of the Pt material is recovered during the IPP procedure.

Evaluation of polyvinylpyrrolidone and block copolymer micelle encapsulation of serine chlorin e6 and chlorin e4 on their reactivity towards albumin and transferrin and their cell uptake.

Encapsulation of porphyrinic photosensitizers (PSs) into polymeric carriers plays an important role in enhancing their efficiency as drugs in photodynamic therapy (PDT). Porphyrin aggregation and low solubility as well as the preservation of the advantageous photophysical properties pose a challenge on the design of efficient PS-carrier systems. Block copolymer micelles (BCMs) and polyvinylpyrrolidone (PVP) are promising drug delivery vehicles for physical entrapment of PSs. BCMs exhibit enhanced dynamics as compared to the less flexible PVP network. In the current work the question is addressed how these different dynamics affect PS encapsulation, release from the carrier, reaction with serum proteins, and cellular uptake. The porphyrinic compounds serine-amide of chlorin e6 (SerCE) and chlorin e4 (CE4) were used as model PSs with different lipophilicity and aggregation properties. 1H NMR and fluorescence spectroscopy were applied to study their interactions with PVP and BCMs consisting of Kolliphor P188 (KP). Both chlorins were well encapsulated by the carriers and had improved photophysical properties. Compared to SerCE, the more lipophilic CE4 exhibited stronger hydrophobic interactions with the BCM core, stabilizing the system and preventing exchange with the surrounding medium as was shown by NMR NOESY and DOSY experiments. PVP and BCMs protected the encapsulated chlorins against interaction with human transferrin (Tf). However, SerCE and CE4 were released from BCMs in favor of binding to human serum albumin (HSA) while PVP prevented interaction with HSA. Fluorescence spectroscopic studies revealed that HSA binds to the surface of PVP forming a protein corona. PVP and BCMs reduced cellular uptake of the chlorins. However, encapsulation into BCMs resulted in more efficient cell internalization for CE4 than for SerCE. HSA significantly lowered both, free and carrier-mediated cell uptake for CE4 and SerCE. In conclusion, PVP appears as the more universal delivery system covering a broad range of host molecules with respect to polarity, whereas BCMs require a higher drug-carrier compatibility. Poorly soluble hydrophobic PSs benefit stronger from BCM-type carriers due to enhanced bioavailability through disaggregation and solubilization allowing for more efficient cell uptake. In addition, increased PS-carrier hydrophobic interactions have a stabilizing effect. For more hydrophilic PSs, the main advantage of polymeric carriers like PVP or poloxamer micelles lies in their protection during the transport through the bloodstream. HSA binding plays an important role for drug release and cell uptake in carrier-mediated delivery to the target tissue.

Controlled Synthesis of Surfactant-Free Water-Dispersible Colloidal Platinum Nanoparticles by the Co4Cat Process.

The recently reported Co4Cat process is a synthesis method bearing ecological and economic benefits to prepare precious-metal nanoparticles (NPs) with optimized catalytic properties. In the Co4Cat process, a metal precursor (e.g., H2 PtCl6 ) is dissolved in an alkaline solution of a low-boiling-point solvent (methanol) and reduced to NPs at low temperature (<80 °C) without the use of surfactants. Here, the Co4Cat process to prepare Pt NPs is described in detail. The advantages of this new synthesis method for research and development but also industrial production are highlighted in a comparison with the popular "polyol" synthesis. The reduction of H2 PtCl6 from PtIV to PtII and further to Pt0 is followed by UV/Vis and XANES/EXAFS measurements. It is demonstrated how the synthesis can be accelerated, how size control is achieved, and how the colloidal dispersions can be stabilized without the use of surfactants. Despite being surfactant-free, the Pt NPs exhibit surprisingly long-term (up to 16 months) stability in water over a wide pH range (4-12) and in aqueous buffer solutions. The Co4Cat process is thus relevant to produce NPs for heterogeneous catalysis, electro-catalysis, or bio/medical applications.

Colloids for Catalysts: A Concept for the Preparation of Superior Catalysts of Industrial Relevance.

Compared to conventional preparation methods for supported heterogeneous catalysts, the use of colloidal nanoparticles (NPs) allows for a precise control over size, size distribution, and distribution/location of the NPs on the support. However, common colloidal syntheses have restrictions that limit their applicability for industrial catalyst preparation. We present a simple, surfactant-free, and scalable preparation method for colloidal NPs to overcome these restrictions. We demonstrate how precious-metal NPs are prepared in alkaline methanol, how the particle size can be tuned, and how supported catalysts are obtained. The potential of these colloids in the preparation of improved catalysts is demonstrated by two examples from heterogeneous catalysis and electrocatalysis.

On the Preparation and Testing of Fuel Cell Catalysts Using the Thin Film Rotating Disk Electrode Method.

We present a step-by-step tutorial to prepare proton exchange membrane fuel cell (PEMFC) catalysts, consisting of Pt nanoparticles (NPs) supported on a high surface area carbon, and to test their performance in thin film rotating disk electrode (TF-RDE) measurements. The TF-RDE methodology is widely used for catalyst screening; nevertheless, the measured performance sometimes considerably differs among research groups. These uncertainties impede the advancement of new catalyst materials and, consequently, several authors discussed possible best practice methods and the importance of benchmarking. The visual tutorial highlights possible pitfalls in the TF-RDE testing of Pt/C catalysts. A synthesis and testing protocol to assess standard Pt/C catalysts is introduced that can be used together with polycrystalline Pt disks as benchmark catalysts. In particular, this study highlights how the properties of the catalyst film on the glassy carbon (GC) electrode influence the measured performance in TF-RDE testing. To obtain thin, homogeneous catalyst films, not only the catalyst preparation, but also the ink deposition and drying procedures are essential. It is demonstrated that an adjustment of the ink's pH might be necessary, and how simple control measurements can be used to check film quality. Once reproducible TF-RDE measurements are obtained, determining the Pt loading on the catalyst support (expressed as Pt wt%) and the electrochemical surface area is necessary to normalize the determined reaction rates to either surface area or Pt mass. For the surface area determination, so-called CO stripping, or the determination of the hydrogen underpotential deposition (Hupd) charge, are standard. For the determination of the Pt loading, a straightforward and cheap procedure using digestion in aqua regia with subsequent conversion of Pt(IV) to Pt(II) and UV-vis measurements is introduced.