RESUMEN
The recent transition to H2-based energy storage demands reliable H2 sensors that allow for easy, fast, and reliable detection of leaks. Conventional H2 detectors are based on the changes of physical properties of H2 probes induced by subsurface H-atoms to a material such as electrical conductivity. Herein, we report on highly reactive gasochromic H2 detectors based on the adsorption of H2 on the material surface. We prepared supraparticles (SPs) containing different types of noble metal nanoparticles (NPs), silica NPs, and the dye resazurin by spray-drying and tested their performance for H2 detection. The material undergoes a distinct color change due to the hydrogenation of the purple resazurin to pink resorufin and, finally, colorless hydroresorufin. The stepwise transition is fast and visible to the naked eye. To further improve the performance of the sensor, we tested the reactivity of SPs with different catalytically active NPs by means of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). We show that the choice of the NP catalyst has a pronounced effect on the response of the H2 indicator. In addition, we demonstrate that the performance depends on the size of the NPs. These effects are attributed to the availability of reactive H-atoms on the NP surface. Among the materials studied, Pt-containing SPs gave the best results for H2 detection.
RESUMEN
The h-BN nanomesh on Rh(111) is used as eggbox-like template for the formation of arrays of Pt nanoclusters with a narrow size distribution. Nanoclusters with sizes from 1 up to 50 atoms are prepared simultaneously in a wedge-like structure by depositing a coverage gradient on the h-BN nanomesh, and thus can be investigated under identical conditions. We studied the preparation and properties of these Pt nanoclusters of different size in situ by high-resolution X-ray photoelectron spectroscopy and scanning tunneling microscopy. For a Pt coverage of 0.1 ML, all pores of the h-BN nanomesh are filled with nanoclusters with a remarkably uniform cluster size of ≈12 Pt atoms per pore, and high stability up to 400 K. Above 0.2 ML Pt, the clusters are less stable. The coverage dependent analysis shows that for Pt coverages below 0.1 ML, the number of nanoclusters is smaller - and the number of empty pores higher - than expected for a simple hit and stick mechanism. We assign this behavior to an initially higher mobility of the Pt atoms in a hot precursor state.
RESUMEN
The water gas shift reaction (WGSR) is catalyzed by supported ionic liquid phase (SILP) systems containing homogeneous Ru complexes dissolved in ionic liquids (ILs). These systems work at very low temperatures, that is, between 120 and 160 °C, as compared to >200 °C in the conventional process. To improve the performance of this ultra-low-temperature catalysis, we investigated the influence of various additives on the catalytic activity of these SILP systems. In particular, the application of methylene blue (MB) as an additive doubled the activity. Infrared spectroscopy measurements combined with density functional theory (DFT) calculations excluded a coordinative interaction of MB with the Ru complex. In contrast, state-of-the-art theoretical calculations elucidated the catalytic effect of the additives by non-covalent interactions. In particular, the additives can significantly lower the barrier of the rate-determining step of the reaction mechanism via formation of hydrogen bonds. The theoretical predictions, thereby, showed excellent agreement with the increase of experimental activity upon variation of the hydrogen bonding moieties in the additives investigated.
RESUMEN
Understanding how reaction conditions affect metal-support interactions in catalytic materials is one of the most challenging tasks in heterogeneous catalysis research. Metal nanoparticles and their supports often undergo changes in structure and oxidation state when exposed to reactants, hindering a straightforward understanding of the structure-activity relations using only ex situ or ultrahigh vacuum techniques. Overcoming these limitations, we explored the metal-support interaction between gold nanoparticles and ceria supports in ultrahigh vacuum and after exposure to CO. A combination of in situ methods (on powder and model Au/CeO2 samples) and theoretical calculations was applied to investigate the gold/ceria interface and its reactivity toward CO exposure. X-ray photoelectron spectroscopy measurements rationalized by first-principles calculations reveal a distinctly inhomogeneous charge distribution, with Au+ atoms in contact with the ceria substrate and neutral Au0 atoms at the surface of the Au nanoparticles. Exposure to CO partially reduces the ceria substrate, leading to electron transfer to the supported Au nanoparticles. Transferred electrons can delocalize among the neutral Au atoms of the particle or contribute to forming inert Auδ- atoms near oxygen vacancies at the ceria surface. This charge redistribution is consistent with the evolution of the vibrational frequencies of CO adsorbed on Au particles obtained using diffuse reflectance infrared Fourier transform spectroscopy.
RESUMEN
Ionic liquids (ILs) are used as ultrathin films in many applications. We studied the nanoscale arrangement within the first layer of 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C1C1Im]â¯[Tf2N]) on Au(111) between 400 and 110 K in ultrahigh vacuum by scanning tunneling and noncontact atomic force microscopy with molecular resolution. Compared to earlier studies on similar ILs, a different behavior is observed, which we attribute to the small size and symmetrical shape of the cation: (a) In both AFM and STM only the anions are imaged; (b) only long-range-ordered but no amorphous phases are observed; (c) the hexagonal room-temperature phase melts 30-50 K above the IL's bulk melting point; (d) at 110 K, striped and hexagonal superstructures with two and three ion pairs per unit cell, respectively, are found. AFM turned out to be more stable at higher temperature, while STM revealed more details at low temperature.