Abstract
Metal-free carbon-based materials are considered as promising oxygen reduction reaction (ORR) electrocatalysts for clean energy conversion, and their highly dense and exposed carbon active sites are crucial for efficient ORR. In this work, two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks (Q3CTP-COFs) and their nanosheets were successfully synthesized and applied as ORR electrocatalysts. The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites, and the unique bilayer stacking of [6 + 3] imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR. In particular, bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets (NSs) due to the weak interlayer π-π interactions. Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity (half-wave potential of 0.72 V vs. RHE in alkaline electrolyte), which is one of the best COF-based ORR electrocatalysts reported so far. Furthermore, Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries (delivered power density of 156 mW cm(-2) at 300 mA cm(-2)). This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.