The
growing concern over the escalating levels of anthropogenic
CO2 emissions necessitates effective strategies for its
conversion to valuable chemicals and fuels. In this research, we embark
on a comprehensive investigation of the nature of zirconia on a copper
inverse catalyst under the conditions of CO2 hydrogenation
to methanol. We employ density functional theory calculations in combination
with the Grand Canonical Basin Hopping method, enabling an exploration
of the free energy surface including a variable amount of adsorbates
within the relevant reaction conditions. Our focus centers on a model
three-atom Zr cluster on a Cu(111) surface decorated with various
OH, O, and formate ligands, noted Zr3O
x
(OH)
y
(HCOO)
z
/Cu(111), revealing major changes in the active site induced
by various reaction parameters such as the gas pressure, temperature,
conversion levels, and CO2/H2 feed ratios. Through
our analysis, we have unveiled insights into the dynamic behavior
of the catalyst. Specifically, under reaction conditions, we observe
a large number of composition and structures with similar free energy
for the catalyst, with respect to changing the type, number, and binding
sites of adsorbates, suggesting that the active site should be regarded
as a statistical ensemble of diverse structures that interconvert.