One-Dimensional Covalent Organic Frameworks for the 2e- Oxygen Reduction Reaction.

Abstract

Two-dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency of atom utilization is still in need of improvement, because the catalytic centers are located in the basal layers and it is difficult for the electrolytes to access them. Herein, we demonstrate the use of 1D COFs for the 2e- oxygen reduction reaction (ORR). The use of different four-connectivity blocks resulted in the prepared 1D COFs displaying good crystallinity, high surface areas, and excellent chemical stability. The more exposed catalytic sites resulted in the 1D COFs showing large electrochemically active surface areas, 4.8-fold of that of a control 2D COF, and thus enabled catalysis of the ORR with a higher H2 O2 selectivity of 85.8 % and activity, with a TOF value of 0.051 s-1 at 0.2 V, than a 2D COF (72.9 % and 0.032 s-1 ). This work paves the way for the development of COFs with low dimensions for electrocatalysis.