Electron Reservoir Effect of Adjacent Fe Nanoclusters Boosts Atomic Fe Active Sites on Porous Carbon for the Both Electrocatalytic Oxygen Reduction and CO2 Reduction Reaction

Abstract Electrochemical oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO 2 RR) are greatly significant in renewable energy‐related devices and carbon‐neutral closed cycle, while the development of robust and highly efficient electrocatalysts has remained challenges. Herein, a hybrid electrocatalyst, featuring axial N‐coordinated Fe single atom sites on hierarchically N, P‐codoped porous carbon support and Fe nanoclusters as electron reservoir (Fe NCs /Fe SAs ‐NPC), is fabricated via in situ thermal transformation of the precursor of a supramolecular polymer initiated by intermolecular hydrogen bonds co‐assembly. The Fe NCs /Fe SAs ‐NPC catalyst manifests superior oxygen reduction activity with a half‐wave potential of 0.91 V in alkaline solution, as well as high CO 2 to CO Faraday efficiency (FE) of surpassing 90% in a wide potential window from −0.40 to −0.85 V, along with excellent electrochemical durability. Theoretical calculations indicate that the electron reservoir effect of Fe nanoclusters can trigger the electron redistribution of the atomic Fe moieties, facilitating the activation of O 2 and CO 2 molecules, lowering the energy barriers for rate‐determining step, and thus contributing to the accelerated ORR and CO 2 RR kinetics. This work offers an effective design of electron coupling catalysts that have advanced single atoms coexisting with nanoclusters for efficient ORR and CO 2 RR.