Electronic Structure-Reactivity Relationship on Ruthenium Step-Edge Sites from Carbonyl 13 C Chemical Shift Analysis

The Journal of Physical Chemistry Letters
Lucas FoppaChristophe Coperet

Abstract

Ru nanoparticles are highly active catalysts for the Fischer-Tropsch and the Haber-Bosch processes. They show various types of surface carbonyl sites upon CO adsorption according to NMR. Compared to terminal and bridging η1 adsorption modes on terraces or edges, little is known about side-on η2 CO species coordinated to B5 or B6 step-edges, the proposed active sites for CO and N2 cleavage. By using solid-state NMR and DFT calculations, we analyse 13C chemical shift tensors (CSTs) of side-on carbonyls on a molecular cluster model for Ru nanoparticles, Ru6(η2-μ4-CO)2(CO)13(η6-C6Me6), and show that contrary to η1 carbonyls, the CST principal components parallel to the C-O bond is extremely deshielded in the η2 species due to the population of the C-O π* anti-bonding orbital, which weakens the bond prior to dissociation. The carbonyl CST is thus an indicator of the reactivity of both Ru clusters and step-edge sites towards C-O bond cleavage.

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