Structure of Active Sites of Fe-N-C Nano-Catalysts for Alkaline Exchange Membrane Fuel Cells.

Platinum group metal-free (PGM-free) catalysts based on transition metal-nitrogen-carbon nanomaterials have been studied by a combination of ex situ and in situ synchrotron X-ray spectroscopy techniques; high-resolution Transmission Electron Microscope (TEM); Mößbauer spectroscopy combined with electrochemical methods and Density Functional Theory (DFT) modeling/theoretical approaches. The main objective of this study was to correlate the HO2- generation with the chemical nature and surface availability of active sites in iron-nitrogen-carbon (Fe-N-C) catalysts derived by sacrificial support method (SSM). These nanomaterials present a carbonaceous matrix with nitrogen-doped sites and atomically dispersed and; in some cases; iron and nanoparticles embedded in the carbonaceous matrix. Fe-N-C oxygen reduction reaction electrocatalysts were synthesized by varying several synthetic parameters to obtain nanomaterials with different composition and morphology. Combining spectroscopy, microscopy and electrochemical reactivity allowed the building of structure-to-properties correlations which demonstrate the contributions of these moieties to the catalyst activity, and mechanistically assign the active sites to individual reaction steps. Associated with Fe-Nx motive and the presence of Fe metallic particles in the electrocatalysts showed the clear differences in the variation of composition; processing and treatment conditions of SSM. From the results of material characterization; catalytic activity and theoretical studies; Fe metallic particles (coated with carbon) are main contributors into the HO2- generation.

A theoretical study of the reactivity of Cu2O(111) surfaces: the case of NO dissociation.

We compare the electronic properties of Cu(111) and Cu(2)O(111) surfaces in relation to the dissociation of NO using first principles calculations within density functional theory. We note a well-defined three-fold site on both O- and Cu-terminated Cu(2)O surfaces which is verified as the active site for the adsorption and dissociation of NO. The interaction of Cu with O atoms results in the forward shifting of the local density of states and formation of unoccupied states above the Fermi level, compared to the fully occupied d band of pure Cu. These results give valuable insights in the realization of a catalyst without precious metal for the dissociation of NO.