Metal-organic frameworks (MOFs) are promising electrochemiluminescent (ECL) nanoemitters. Great endeavors have been made to optimize the inherent luminescent properties, yet most MOFs suffer from poor coreactant activation ability, resulting in limited ECL. Therefore, it is urgent to integrate and design efficient catalytic centers within MOFs. Herein, we decorate atomically dispersed Ru onto the Zr-nodes of NU-1000, constructing Ru-OH-Zr centers to synergistically activate coreactants. The proposed NU-Ru enables 7.8 times enhancement in ECL efficiency. Theoretical investigations reveal that Ru atoms with strong electronegativity not only accelerate the charge transfer but also provide superior Lewis acid sites for promoting peroxysulfate binding and activation. Assisted by Bro̷nsted acid groups, the Ru-OH-Zr centers efficiently split the O-O bonds to enrich radicals through a proton-coupled electron transfer process. Furthermore, a direct mode sensor was established for sensitive organophosphorus pesticide analysis based on the interaction between the P═O bond and Lewis acid sites.
Keywords: Charge transfer; Electrochemiluminescence; Metal−organic frameworks; Sensing; Synergistic catalysis.