Bionic Preparation of CeO₂-Encapsulated Nitrogen Self-Doped Biochars for Highly Efficient Oxygen Reduction

This study reports the superior performance of novel carbonaceous materials, CeO₂-encapsulated nitrogen-doped biochars [BC-Ce-X (X = 1 and 2)], for oxygen reduction reaction (ORR). The biomass precursor of this value-added biochar material was biomimetically prepared via a hydroponic operation in the Ce-enriched solution. The characterization results showed that CeO₂ with large amounts of oxygen vacancies was stably embedded in the N self-doped biochars during the pyrolytic processes. The measured specific surface areas of cerium-free biochar (BC sample), BC-Ce-1, and BC-Ce-2 were 79, 566, and 518 m²/g, respectively. The BC-Ce-X (X = 1 and 2) showed excellent ORR performances with onset potentials of ∼0.90-0.91 V, which outperformed the commercial 10 wt % Pt/C and BC. Compared with Pt/C, the BC-Ce-2 had better methanol tolerance and stability. Also, BC-Ce-2 displayed excellent electrochemical activity for Zn/air batteries. Controlled experiments and density functional theoretical calculations illustrated the synergistic effect between the pyri-N/C centers and CeO₂ with oxygen vacancies in ORR. The Lewis base sites, created by pyri-N and oxygen vacancies, greatly facilitated the chemisorption of O₂ molecules.