RESUMEN
A stable and cost effective oxygen evolution reaction (OER) catalyst is crucial for the large-scale market penetration of proton exchange membrane (PEM) water electrolyzers. We show that the synthesis of iridium nanoparticles in either low purity ethanol or water, or in the absence of a surfactant, is detrimental to the electrocatalytic properties of the materials. Adding NaBH4 in excess improves the purity of the catalyst enhancing the OER activity up to 100 A gIr-1 at 1.51 V vs. RHE, the highest value reported so far for high purity Ir nanoparticles. The measured OER activity correlates with the capacitive current rather than with the charge corresponding to the IrIII/IrIV oxidation peak. Operando near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) on membrane electrode assemblies (MEAs) with the synthesized catalysts reveals a metallic core surrounded by a thin layer of IrIII/IV oxides/hydroxides. Oxidation of IrIII leaves behind a porous ultrathin layer of IrIV oxides/hydroxides, which dominate the surface during the OER, while IrV was not detected.
RESUMEN
Thin films of the spin-crossover (SCO) molecule Fe{[Me2Pyrz]3BH}2 (Fe-pyrz) were sublimed on Si/SiO2 and quartz substrates, and their properties investigated by X-ray absorption and photoemission spectroscopies, optical absorption, atomic force microscopy, and superconducting quantum interference device. Contrary to the previously studied Fe(phen)2(NCS)2, the films are not smooth but granular. The thin films qualitatively retain the typical SCO properties of the powder sample (SCO, thermal hysteresis, soft X-ray induced excited spin-state trapping, and light induced excited spin-state trapping) but present intriguing variations even in micrometer-thick films: the transition temperature decreases when the thickness is decreased, and the hysteresis is affected. We explain this behavior in the light of recent studies focusing on the role of surface energy in the thermodynamics of the spin transition in nano-structures. In the high-spin state at room temperature, the films have a large optical gap (â¼5 eV), decreasing at thickness below 50 nm, possibly due to film morphology.
RESUMEN
One of the prerequisites for the detailed understanding of heterogeneous catalysis is the identification of the dynamic response of the catalyst surface under variable reaction conditions. The present study of methanol oxidation on different model Ru pre-catalysts, performed approaching the realistic catalytic reaction conditions, provides direct evidence of the significant effect of reactants' chemical potentials and temperature on the catalyst surface composition and the corresponding catalytic activity and selectivity. The experiments were carried out for three regimes of oxygen potentials in the 10(-1) mbar pressure range, combining in situ analysis of the catalyst surface by synchrotron-based photoelectron core level spectroscopy with simultaneous monitoring of the products released in the gas phase by mass spectroscopy. Metallic Ru with adsorbed oxygen and transient 'surface oxide', RuO(x), with varying x have been identified as the catalytically active states under specific reaction conditions, favouring partial or full oxidation pathways. It has been shown that the composition of catalytically active steady states, exhibiting different activity and selectivity, evolves under the reaction conditions, independent of the crystallographic orientation and the initial pre-catalyst chemical state, metallic Ru or RuO(2).
RESUMEN
Interactive, strong interbonding and highly electron conductive nonstoichiometric titanium suboxide catalytic supports, Magneli phases (Ti(n)O(2n-1), on average Ti(4)O(7)), have been used in the electrocatalysis of hydrogen (HELR) and oxygen (OELR) electrode reactions with remarkable consequences and advanced achievements. The theory of hypo-hyper-d-interelectronic bonding of transition metal ions and atoms has been employed for selective ordered grafting and shown to stay in the core of the strong metal-support interaction (SMSI) in heterogeneous catalysis and electrocatalysis, and thereby the substantial cause for the improved synergistic activity of composite (electro)catalysts. The same fundament has been the thermodynamic basis for the thermal production of symmetric intermetallic Laves type phases of nanostructured electrocatalysts, in particular the ones with higher oxophilic properties of hypo-d-elements. Remarkably advanced in electrocatalytic activity, highly monatomically dispersed deposits of Pt upon Magneli phases are shown to be unique and highly promising electrocatalysts for the cathodic oxygen reduction (ORR). Nanostructured Au upon a thin nanocrystalline film of anatase titania has been confirmed by X-ray photoelectron spectroscopy (XPS) as a typical classical paradigm of the SMSI, and at the same time affording the basis for gold with strained d-orbitals, as the reversible hydrogen electrode. Magneli phases have been shown to be the best electrocatalytic supports with unique properties both for low temperature PEM fuel cells (LT PEM FCs) with pronounced CO tolerance and water electrolysis in membrane type hydrogen generators.