Synergistic Modulating Interlayer Space and Electron-Transfer of Covalent Organic Frameworks for Oxygen Reduction Reaction.

Covalent organic frameworks (COFs) are an ideal template to construct high-efficiency catalysts for oxygen reduction reaction (ORR) due to their predictable properties. However, the closely parallel-stacking manner and lacking intramolecular electron transfer ability of COFs limit atomic utilization efficiency and intrinsic activity. Herein, COFs are constructed with large interlayer distances and enhanced electronic transfer ability by side-chain functionalization. Long chains with electron-donating features not only enlarge interlayer distance, but also narrow the bandgap. The resulting DPPS-COF displays higher electrochemical surface areas to provide more exposed active sites, despite <1/10 surface areas. DPPS-COF exhibits excellent electrocatalytic ORR activity with half-wave potential of 0.85 V, which is 30 and 60 mV positive than those of Pt/C and DPP-COF, and is the record among the reported COFs. DPPS-COF is employed as cathode electrocatalyst for zinc-air battery with a maximum power density of 185.2 mW cm -2 , which is superior to Pt/C. Theoretical calculation further reveals that longer electronic-donating chains not only facilitate the formation of intermediate OOH* from O 2 , but also promote intermediates desorption , and thus leading to higher activity.