Self‐Photocatalysis Boosted Electrochemiluminescence System of Pyrene Based Hydrogen‐Bonded Organic Framework: Oxygen‐Vacancy Mediated Adsorption and Peroxydisulfate Radical Activation

Abstract Rational design and optimization of the electrochemiluminescence (ECL) system undoubtedly underpins critical future advances in the field of sensing. Herein, an efficient ECL system is prepared by the integration of pyrene self‐assembled hydrogen‐bonded organic frameworks (PSA‐HOF) and defective hydrated tungsten oxide nanosheets (dWO₃•H₂O), displaying a self‐cycling photocatalytic activation mechanism to boost ECL performances. PSA‐HOF was exploited as the ECL luminophor to produce a light source with sufficient intensity due to the unique structure and aggregation‐induced emission‐enhanced emission. Meanwhile, dWO₃•H₂O exhibited dual functionality: 1) serving as highly efficient adsorbents for capturing peroxydisulfate (PDS), 2) acting as photoactive materials, which can be activated by the light emitted from PSA‐HOF. Notably, the presence of oxygen vacancies within dWO₃•H₂O can not only lowered adsorption energy and increase exposure of active sites, but also enhance the photocatalytic performance, thus activating PDS through a radical‐mediated mechanism, which can further stimulate the photocatalytic materials in turn to achieve self‐circulation within the system. As a proof of concept, an ECL biosensor for detecting microcystin‐RR (MC‐RR) is successfully established, which displays a wide detection range and a low detection limit. This work offers a new perspective on the development of ECL technology with high efficiency and stability.