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Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

The rock material pentlandite with the composition Fe4.5Ni4.5S8 was synthesized via high temperature synthesis from the elements. The structure and ...

Ruhr-University Bochum

Steady state and time-resolved fluorescence measurements compare the photophysical properties of Coumarin 152 (C152) and Coumarin 461 (C461) in bulk methanol solution and adsorbed to silica/vapor and silica/methanol interfaces. C152 and C461 share the same structure except for a -CF(3) (C152) or -CH(3) (C461) group at the molecule's 4-position. This modest structural difference leads to markedly different emission behavior in bulk solution and different organization when adsorbed to silica surfaces. Steady state emission spectra of C152 and C461 adsorbed to silica surfaces from bulk methanol solutions show that the two solutes have similar surface activities (ΔG(ads) of -29.0 kJ/mol and -30.8 kJ/mol for C152 and C461, respectively) and that the interface itself has a polarity similar to that of short chain alcohols. Both solutes appear to form multilayers at higher bulk concentrations given observed linear growth in fluorescence emission intensities. At higher C152 surface concentrations a second emissive state appears at longer wavelengths, whereas the emission of C461 remains dominated by a single feature. Time dependent emission of C152 and C461 adsorbed to the silica/methanol interface shows that the silica surface inhibits C152's fast, nonradiative pathway inferred from bulk solution measurements but the fluorescence lifetime of adsorbed C461 remains unchanged from bulk solution limits. These findings are discussed in terms of the interface's ability to restrict C152 isomerization into a nonradiative, twisted intramolecular charge-transfer (TICT) state, despite the fact that this conformation represents an energetic minimum in polar solvation environments.

Surface induced changes in coumarin solvation and photochemistry at polar solid/liquid interfaces.

The need for sustainable catalysts for an efficient hydrogen evolution reaction is of significant interest for modern society. Inspired by comparable structural properties of [FeNi]-hydrogenase, here we present the natural ore pentlandite (Fe4.5Ni4.5S8) as a direct 'rock' electrode material for hydrogen evolution under acidic conditions with an overpotential of 280 mV at 10 mA cm(-2). Furthermore, it reaches a value as low as 190 mV after 96 h of electrolysis due to surface sulfur depletion, which may change the electronic structure of the catalytically active nickel-iron centres. The 'rock' material shows an unexpected catalytic activity with comparable overpotential and Tafel slope to some well-developed metallic or nanostructured catalysts. Notably, the 'rock' material offers high current densities (≤650 mA cm(-2)) without any loss in activity for approximately 170 h. The superior hydrogen evolution performance of pentlandites as 'rock' electrode labels this ore as a promising electrocatalyst for future hydrogen-based economy.

Stefan Piontek

Faculty of Chemistry and Biochemistry,
Inorganic Chemistry I,
Faculty of Chemistry and Biochemistry, Inorganic Chemistry I

Ruhr-University Bochum

Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

Stefan Piontek

Faculty of Chemistry and Biochemistry,Inorganic Chemistry I,Faculty of Chemistry and Biochemistry, Inorganic Chemistry I

Ruhr-University Bochum

Simple Methods for the Preparation of Non-noble Metal Bulk-electrodes for Electrocatalytic Applications

Faculty of Chemistry and Biochemistry,
Inorganic Chemistry I,
Faculty of Chemistry and Biochemistry, Inorganic Chemistry I