Tailoring the Electrocatalytic Properties of Porphyrin Covalent Organic Frameworks for Highly Selective Oxygen Sensing In Vivo

In vivo selective sensing of oxygen (O2) dynamics in the central nervous system could provide insights into energy metabolism and neural activities. Although the electrocatalytic four-electron oxygen reduction reaction (ORR) paves an effective way to the electrochemical sensing of O2 in vivo, the concurrent hydrogen peroxide reduction reaction (HPRR) within the potential windows for four-electron ORR unfortunately poses a great challenge to the conventional mechanism employed for selective electrochemical O2 sensing. In this work, we find that regulation of the linkers within the skeleton of porphyrin-based covalent organic frameworks (COFs) could improve the selectivity of the O2 sensor against hydrogen peroxide (H2O2). The electrochemical results reveal that the Co porphyrin active sites facilitate the direct four-electron pathway for ORR and that the Co porphyrin-based COF, enriched with pyrene units, shows enhanced four-electron ORR kinetics and better tolerance to HPRR. The theoretical calculation suggests that introducing pyrene units essentially weakens the adsorption of H2O2, leading to suppression of the HPRR. The microsensor fabricated with the Co porphyrin-based COF as the electrocatalyst features a high selectivity for real-time monitoring of O2 in a living rat brain.