Abstract
ABSTRACT
The reverse water‐gas shift (RWGS) reaction can serve as a pivotal hub for converting CO
2
into value‐added chemicals. However, conventional Cu/CeO
2
catalysts are constrained by a limited metal‐oxide interfacial perimeter, suffering from both inadequate low‐temperature activity and poor stability. Herein, a series of CeO
2
/Cu‐x catalysts (where x is the Ce/Cu molar ratio) were synthesized via an oxalic acid‐assisted sol‐gel coprecipitation method, and tested for RWGS at 400°C and atmospheric pressure. The optimal inverse CeO
2
/Cu‐0.1 achieves an intrinsic reaction rate of 197.0 µmol·g
cat
−1
·s
−1
, which is 3.7 times higher than that of the conventional CeO
2
/Cu‐10 (53.1 µmol·g
cat
−1
·s
−1
) and is much more stable. Structural analyses revealed that the CeO
2
/Cu‐0.1 is characterized by an inverse architecture of tiny CeO
2
crystallites (4.6 nm) on larger Cu particles (12.7 nm), which is distinct from conventional architecture of Cu clusters (3.3 nm) on larger CeO
2
particles (7.1 nm) for CeO
2
/Cu‐10. The inverse architecture significantly improves the density of Cu
+
‐O
V
‐Ce
3+
sites at the interfacial perimeter of CeO
2
/Cu, which facilitates the synergistic activation of H
2
and CO
2
as well as subsequent reaction, leading to lower reaction orders and a much higher intrinsic rate. This work demonstrates the inverse oxide/metal architecture with engineered oxide‐metal interfacial sites for enhancing RWGS.