Modified Ceria for “Low‐Temperature” CO2 Utilization: A Chemical Looping Route to Exploit Industrial Waste Heat

Abstract Efficient CO 2 utilization is key to limit global climate change. Carbon monoxide, which is a crucial feedstock for chemical synthesis, can be produced by splitting CO 2 . However, existing thermochemical routes are energy intensive requiring high operating temperatures. A hybrid redox process (HRP) involving CO 2 ‐to‐CO conversion using a lattice oxygen‐deprived redox catalyst at relatively low temperatures (<700 °C) is reported. The lattice oxygen of the redox catalyst, restored during CO 2 ‐splitting, is subsequently used to convert methane to syngas. Operated at temperatures significantly lower than a number of industrial waste heat sources, this cyclic redox process allows for efficient waste heat‐utilization to convert CO 2 . To enable the low temperature operation, lanthanum modified ceria (1:1 Ce:La) promoted by rhodium (0.5 wt%) is reported as an effective redox catalyst. Near‐complete CO 2 conversion with a syngas yield of up to 83% at low temperatures is achieved using Rh‐promoted LaCeO 4− x . While La improves low‐temperature bulk redox properties of ceria, Rh considerably enhances the surface catalytic properties for methane activation. Density functional theory calculations further illustrate the underlying functions of La‐substitution. The highly effective redox catalyst and HRP scheme provide a potentially attractive route for chemical production using CO 2 , industrial waste heat, and methane, with appreciably lowered CO 2 emissions.