Multivariate Metalloporphyrin-Based Covalent Organic Frameworks for Cataluminescence Signal Amplification

Abstract Utilizing covalent organic frameworks (COFs) without postpyrolysis for cataluminescence (CTL) remains a challenge due to deficient thermocatalytic activity and uncontrollable bimetallic ratios. Herein, we presented a multivariate (MTV) metalloporphyrin-based COF (Cu0.5/Ni0.5-COF) embedded with nonpyrolysis and atomically dispersed bimetallic sites as a high-performance CTL platform. Interestingly, the Cu0.5/Ni0.5-COF catalyst exhibited an extraordinary signal amplification of diethyl ether-based CTL as a result of the maximum exposure of the bimetallic active centers and the enrichment of Lewis acid sites. The developed CTL sensor delivered a state-of-the-art sensing profile, including an ultrafast response time of 0.8 s, a wide linear range (0.1–15.0 mM), and a remarkable detection limit of 0.02 mM. The excellent performances of the as-prepared Cu0.5/Ni0.5-COF catalyst were ascribed to the profound synergistic interaction between the bimetallic porphyrin centers and the analyte for high-efficiency light emissions. This work opens a new avenue for engineering pristine COF-based CTL platforms.