Abstract
Photocatalytic hydrogen peroxide (H(2)O(2)) production through the oxygen reduction reaction (ORR) pathway has emerged as a promising sustainable alternative. However, a significant challenge in this field lies in the development of highly efficient photocatalysts capable of achieving high-concentration H(2)O(2) production. Here the rational design of two O(2) reduction cores into one polymer framework is showcased for synergistically facilitating H(2)O(2) production via the "self-marketing & cooperation" strategy. Photoactive units of pyrrolo[3,2-b] pyrrole and porphyrin are successfully settled in covalent organic polymers (COPs) through polycyclizations of the relevant aldehydes, anilines, and butane-2,3-dione. Two orderly separated active sites not only involve each of them in the oxygen reduction reaction but also mutually promote the production of H(2)O(2), which is demonstrated by electron spin resonance experiments, in situ diffuse reflectance infrared Fourier transform spectroscopy, and a series of control experiments. Remarkably, PP-COP-4 delivers an outstanding H(2)O(2) concentration of 16.2 mM in a continuous-flow system, demonstrating its strong potential for scalable, solar-driven production of commercial-grade H(2)O(2).