Liquid organic hydrogen carriers: surface science studies of carbazole derivatives.

ABSTRACT

We review recent results towards a molecular understanding of the adsorption and dehydrogenation of carbazole-derived liquid organic hydrogen carriers on platinum and palladium single crystals and on Al2 O3 -supported Pt and Pd nanoparticles. By combining synchrotron-based high-resolution X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy, advanced molecular beam methods and temperature-programmed desorption spectroscopy, detailed insights into the reaction mechanism are obtained. On Pt(111), dehydrogenation of perhydro-N-ethylcarbazole, H12 -NEC, starts with activation of the hydrogen atoms at the pyrrole unit, yielding H8 -NEC as the first stable reaction intermediate at ∼340 K, followed by further dehydrogenation to NEC at ∼380 K. Above 390 K, dealkylation starts, yielding carbazole as an undesired byproduct. On small supported Pt particles, the dealkylation sets in at lower temperatures, due to the higher reactivity of low-coordinated sites, while on larger particles with (111) facets a reactivity as on the flat surface is observed. Carbazole derivatives with ethyl, propyl and butyl chains show an overall very similar reactivity, both on Pt(111) and on Pt nanoparticles. When comparing the dealkylation behavior of H12 -NEC on Pt(111) and Pt nanoparticles to that on Pd(111) and Pd nanoparticles, we find a higher reactivity for the Pd systems.