Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates.

The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal-air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO2 -) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur-functionalized vanadium-based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM-based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR-based devices.

Electrochemically Versatile Graphite Nanoplatelets Prepared by a Straightforward, Highly Efficient, and Scalable Route.

Nanostructured carbon materials with tailor-made structures (e.g., morphology, topological defect, dopant, and surface area) are of significant interest for a variety of applications. However, the preparation method selected for obtaining these tailor-made structures determines the area of application, precluding their use in other technological areas of interest. Currently, there is a lack of simple and low-cost methodologies versatile enough for obtaining freestanding carbon nanostructures that can be used in either energy storage or chemical detection. Here, a novel methodology for the development of a versatile electrochemically active platform based on freestanding graphite nanoplatelets (GNP) has been developed by exploiting the interiors of hollow carbon nanofibers (CNF) comprising nanographene stacks using dry ball-milling. Even though ball-milling could be considered as a universal method for any carbonaceous material, often, it is not as simple (one step, no purification, and no solvents), efficient (just GNP without tubular structures), and quick (just 20 min) as the sustainable method developed in this work, free of surfactants and stabilizer agents. We demonstrate that the freestanding GNP developed in this work (with an average thickness of 3.2 nm), due to the selective edge functionalization with the minimal disruption of the basal plane, can act either as a supercapacitor or as a chemical sensor, showing both a dramatic improvement in the charge storage ability of more than 30 times and an enhanced detection of electrochemically active molecules such as ascorbic acid with a 236 mV potential shift with respect to CNF in both cases. As shown here, GNP stand as an excellent versatile alternative compared to the standard commercially available carbon-based materials. Overall, our approach paves the way for the discovery of new nanocarbon-based electrochemical active platforms with a wide electrochemical applicability.

Magnetic Hyperthermia Enhancement in Iron-based Materials Driven by Carbon Support Interactions.

Magnetic hyperthermia (MH) shows great potential in clinical applications because of its very localized action and minimal side effects. Because of their high saturation magnetization values, reduced forms of iron are promising candidates for MH. However, they must be protected in order to overcome their toxicity and instability (i. e., oxidation) under biological conditions. In this work, a novel methodology for the protection of iron nanoparticles through confinement within graphitic carbon layers after thermal treatment of preformed nanoparticles supported on carbon is reported. We demonstrate that the size and composition of the nascent confined iron nanoparticles, as well as the thickness of their protective carbon layer can be controlled by selecting the nature of the carbon support. Our findings reveal that a higher nanoparticle-carbon interaction, mediated by the presence of oxygen-containing groups, induces the formation of small and well-protected α-Fe-based nanoparticles that exhibit promising results towards MH based on their enhanced specific absorption rate values.

A New Type of Supramolecular Fluid Based on H2 O-Alkylammonium/Phosphonium Solutions.

Here we show that by adjusting the concentration of tetrabutyl ammonium and phosphonium salts in water (≈1.5-2.0 m), hydrophobic solvation triggers the formation of a unique, highly incompressible supramolecular liquid, with a dynamic structure similar to clathrates, involving essentially all H2 O molecules of the solvent. Despite the increasing local order, the thermal diffusivity, and compressibility of these supramolecular liquids is strongly decreased with respect to bulk water due to slower relaxation dynamics. The results presented in this paper open an avenue to design a new family of supramolecular fluids, stable under atmospheric conditions, which can find important technological applications in energy storage and conversion.