Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO2 Conversion with Carbon‐Based Materials

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N‐doped carbon (NiPACN), an electrocatalyst for the reduction of CO2 to CO (CO2R), can also selectively catalyze thermal CO2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO2R active site studies. Finally, we construct a generalized reaction driving‐force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO2R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments. Despite similar underlying phenomena, studies that directly analogize between thermal catalysis and electrocatalysis are rare. Here, we employ a Ni, N‐doped carbon catalyst that is thermally stable and electronically conductive to show that high selectivity CO production is observed under both electrochemical CO2 reduction conditions and thermal reverse‐water gas shift environments.