The capture and conversion
of CO
2
are of significant
importance in enabling the production of sustainable fuels, contributing
to alleviating greenhouse gas emissions. While there are a number
of key steps required to convert CO
2
, the initial step
of adsorption and activation by the catalyst is critical. Well-known
metal oxides such as oxidized TiO
2
or CeO
2
are
unable to promote this step. In addressing this difficult problem,
a recent experimental work shows the potential for bismuth-containing
materials to adsorb and convert CO
2
, the origin of which
is attributed to the role of the bismuth lone pair. In this paper,
we present density functional theory (DFT) simulations of enhanced
CO
2
adsorption on heterostructures composed of extended
TiO
2
rutile (110) and anatase (101) surfaces modified with
Bi
2
O
3
nanoclusters, highlighting in particular
the role of heterostructure reduction in activating CO
2
. These heterostructures show low coordinated Bi sites in the nanoclusters
and a valence band edge that is dominated by Bi–O states, typical
of the Bi
3+
lone pair. The reduction of Bi
2
O
3
–TiO
2
heterostructures can be facile and
produces reduced Bi
2+
and Ti
3+
species. The
interaction of CO
2
with this electron-rich, reduced system
can produce CO directly, reoxidizing the heterostructure, or form
an activated carboxyl species (CO
2
–
)
through electron transfer from the reduced heterostructure to CO
2
. The oxidized Bi
2
O
3
–TiO
2
heterostructures can adsorb CO
2
in carbonate-like
adsorption modes, with moderately strong adsorption energies. The
hydrogenation of the nanocluster and migration to adsorbed CO
2
is feasible with H-migration barriers less than 0.7 eV, but
this forms a stable COOH intermediate rather than breaking C–O
bonds or producing formate. These results highlight that a reducible
metal oxide heterostructure composed of a semiconducting metal oxide
modified with suitable metal oxide nanoclusters can activate CO
2
, potentially overcoming the difficulties associated with
the difficult first step in CO
2
conversion.