Recasting the Catalytic Legacy of Reverse Water−Gas Shift Reaction: Rational Design Strategies for Selective CO2 Valorization

Rising atmospheric CO₂ and climate pressures have intensified interest in carbon capture and utilization (CCU). The reverse water–gas shift (RWGS) reaction offers a direct route to convert CO₂ into CO, a versatile syngas component for Fischer–Tropsch, methanol synthesis, and other downstream processes, thereby supporting a circular carbon economy. RWGS is inherently challenging: it is endothermic and favored only at high temperatures (>600 °C), which promotes catalyst sintering and high energy demand, while at lower temperatures the competing Sabatier reaction dominates, producing CH₄ over Ni. Catalyst selection further complicates implementation: noble metals (Au, Pt, Rh) offer high CO selectivity but are costly, whereas base metals (Ni, Fe, Cu) are more abundant yet prone to methanation, sintering, or phase instability. Industrial deployment also demands resilience under water-rich environments, high space velocities, and thermal cycling associated with variable renewable H₂ supply.

This Account presents our efforts to address these challenges through rational catalyst design guided by three central principles: electronic modulation via promoters to control adsorption and reaction pathways; active phase engineering to tune catalytic functionality and suppress undesired reactions, and structural and interfacial design to enhance stability and durability under realistic conditions.