In
this work, we explore the decomposition of CO2 on unsupported
and TiO2-supported Cu5 clusters via computational
modeling, using both finite cluster and periodic slab structures of
the rutile TiO2(110) surface. While the energy needed for
C=O bond breaking is already significantly reduced upon adsorption
onto the unsupported metal catalyst (it drops from 7.8 to 1.3 eV),
gas desorption before bond activation is still the inevitable outcome
due to the remaining barrier height even at 0 K. However, when the
Cu5 cluster itself is supported on TiO2, reactant
and product adsorption is strongly enhanced, the barrier for bond
breaking is further reduced, and a spontaneous decomposition of the
molecule is predicted. This finding is linked to our previous work
on charge-transfer processes in the Cu5–TiO2 system triggered by solar photons, since a combination of
both phenomena at suitable temperatures would allow for a photoinduced
activation of CO2 by sunlight.