Prediction of a highly activated state of CO adsorbed on an Al/Fe(100) bimetallic surface

Using periodic slab density functional theory, we investigate CO adsorption, diffusion, and dissociation energetics on a monolayer of Al covering Fe(100) [Al/Fe(100)]. We predict a weakly chemisorbed state of CO to exist on Al/Fe(100), with CO adsorbing on the 4-fold hollow site in a very tilted fashion. This state is predicted to have an extremely low CO stretching frequency of only 883 cm(-1), indicating a dramatically weakened CO bond relative to gaseous CO, even though the molecule is predicted to bind to Al/Fe(100) quite weakly. We predict that dissociation of CO starting from this weakly adsorbed state has a barrier of only approximately 0.35 eV, which is approximately 0.70 eV lower than that on Fe(100). To understand how the underlying substrate changes the electronic properties of the supported Al monolayer, we compare CO adsorption on Al/Fe(100) to its adsorption on analogous pure Al(100) surfaces. This highly activated yet weakly bound state of CO on Al/Fe(100) suggests that Al/Fe(100) could be an effective low-temperature bimetallic catalyst in reducing environments.