Search results for "medium"

Hydrogen bonding and proton transfer involving the trihydride complexes Cp*M(dppe)H 3 (M = Mo, W) and fluorinated alcohols: the competitive role of t…

2003

International audience; The protonation of complexes Cp*M(dppe)H3 (dppe is ethylenebis(diphenylphosphine), M = Mo (1), W (2)) by a variety of fluorinated alcohols of different acid strength (FCH2CH2OH, CF3CH2OH, (CF3)2CHOH, and (CF3)3COH) was investigated experimentally by the variable temperature spectroscopic methods (IR, NMR) and stopped-flow technique (UV-Vis). The structures of the hydrogen-bonded and proton transfer products were studied by DFT calculations. In agreement with the calculation results, the IR data suggest that the initial hydrogen bond is established with a hydride site for complex 1 and with the metal site for complex 2. However, no intermediate dihydrogen complex foun…

Bio-inspired Ni dinuclear complexes as heterogeneous catalysts for hydrogen evolution

2021

Abstract A major challenge in the sustainable production of hydrogen is lowering the electrochemical overpotential and the activation energy of the hydrogen evolution reaction. Some enzymes have two metallic Ni centers and catalyze this reaction with high activity. Taking inspiration from them, we have developed two novel dinuclear Ni(II) complexes, Ni-PATIO and Ni-PACO, with promise as molecular catalysts. Ni-PACO exhibits a square-planar geometry for both Ni(II) and two-fold rotational symmetry both in solid and solution states, whereas Ni-PATIO displays one square-planar Ni(II) center and one octahedral Ni(II) configuration, which confer it magnetic properties. We show that both complexe…

The influence of external uniaxial stretching on the electromigration and diffusion of hydrogen in iron

2009

Electromigration and diffusion of hydrogen in iron, depending on unit elongation, were investigated. The resistivity method was applied in the investigations. It was found that the obtained experimental results cannot be described by means of a single flux of hydrogen, which diffuses in the electric field. In order to explain the obtained results, we assumed the existence of the following two fluxes of hydrogen in the stretched metal: migration, according to the interstitial mechanism, and migration according to the interstitial-defective mechanism. The dependence of effective valences and diffusion coefficients for both mechanisms were determined.

EQCM and EIS studies of Znaq2++2e−⇄Zn0 electrochemical reaction in moderated acid medium

2003

The zinc electrodissolution and electrodeposition have been studied by means of electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy. Relevant information on the mechanism of these electrochemical processes is provided by the analysis of experimental data. The zinc electrodeposition takes place with an important participation of hydrogen ions while the zinc electrodissolution occurs, in these experimental conditions, by a mechanism in two steps. Besides, it is proved that the presence of molecular oxygen in the solution contributes to the formation of a passive layer on the metallic zinc deposit.

Study of the phase composition of iron-containing Langmuir-Blodgett layers before and after thermal and chemical treatment

1992

Iron-containing Langmuir–Blodgett mono- and multilayers were prepared by depositing ferric stearate onto silicon wafers. Particular care should be taken in order to avoid the presence of alkali ions, which may replace iron ions in the deposited film. By a subsequent heating in air, the fatty acid chains were thermodesorbed. This results in a rather homogeneous coating of the samples by an iron oxide, most probably in the form of crystalline and amorphous γ-FeOOH, as found by conversion electron Mossbauer, photoelectron and microprobe studies. By a subsequent heating in hydrogen gas or exposure to nascent hydrogen, a partial reduction of the iron oxide layer is possible up to the metallic st…

Aluminum Nanocrystals as a Plasmonic Photocatalyst for Hydrogen Dissociation

2016

Hydrogen dissociation is a critical step in many hydrogenation reactions central to industrial chemical production and pollutant removal. This step typically utilizes the favorable band structure of precious metal catalysts like platinum and palladium to achieve high efficiency under mild conditions. Here we demonstrate that aluminum nanocrystals (Al NCs), when illuminated, can be used as a photocatalyst for hydrogen dissociation at room temperature and atmospheric pressure, despite the high activation barrier toward hydrogen adsorption and dissociation. We show that hot electron transfer from Al NCs to the antibonding orbitals of hydrogen molecules facilitates their dissociation. Hot elect…

Deuterium hyperfine splittings in the rotational spectrum of NH2D as revealed by Lamb-dip spectroscopy

2020

Abstract In the context of radio-astronomical observations, laboratory experiments constitute a cornerstone in the interpretation of rich line surveys due to the concomitant presence of numerous emitting molecules. Here, we report the investigation of three different rotational transitions of mono-deuterated ammonia (NH2D), a species of astrophysical interest, for which the contribution of the deuterium nuclear spin to the rotational spectrum has been resolved for the first time in the millimeter- and submillimeter-wave domain. The effect of hyperfine interactions on the rotational spectrum has been unveiled by a combined theoretical and experimental approach. Quantum-chemical calculations …

2020

Abstract. Fluid flow on different scales is of interest for several Earth science disciplines like petrophysics, hydrogeology and volcanology. To parameterize fluid flow in large-scale numerical simulations (e.g. groundwater and volcanic systems), flow properties on the microscale need to be considered. For this purpose experimental and numerical investigations of flow through porous media over a wide range of porosities are necessary. In the present study we sinter glass bead media with various porosities and measure the permeability experimentally. The microstructure, namely effective porosity and effective specific surface, is investigated using image processing. We determine flow proper…

Combined numerical and experimental study of microstructure and permeability in porous granular media

2020

<div> <div> <div> <p>Fluid flow on different scales is of interest for several Earth science disciplines like petrophysics, hydrogeology and volcanology. To parameterize fluid flow in large-scale numerical simulations (e.g. groundwater and volcanic systems), flow properties on the microscale need to be considered. For this purpose experimental and numerical investigations of flow through porous media over a wide range of porosities are necessary. In the present study we sinter glass bead media with various porosities, representing shallow depth crustal sediments. The microstructure, namely effective porosity …

Budgeting soil erosion from floodplain sediments of the central Rhenish Slate Mountains (Westerwald), Germany

2011

The distribution, thickness and composition of the floodplain sediments in the valleys of the Gelbach (Lower Westerwald) and Große Nister (Upper Westerwald) depend on the occurrence of loessic periglacial cover beds in their catchments as well as on historical land use. The budget of floodplain sedimentation was derived from a study of the floodloams underlying the monastery garden of Marienstatt, a village in the Große Nister valley. From the study of two occupation levels, pottery shards and radiocarbon dating, 55% of the floodloam can be attributed to the Modern period (younger than c. AD 1450). From the radiocarbon age of a charcoal fragment extracted from the base of the floodloam at …