Abstract
<jats:p> Bifunctional catalysts capable of coupling in situ H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> electrogeneration with its direct utilization in selective oxidation reactions represent an attractive strategy for developing sustainable oxidation processes. In this work, Ti-containing zeolites with different framework topologies (TS-1, Ti-MWW, and Ti-Beta) were integrated with a polydopamine-derived carbon shell containing Co or Fe active sites to construct core–shell composites for the combined oxygen reduction reaction (ORR) and phenol hydroxylation. Structural and spectroscopic characterization confirmed that the zeolite frameworks remained intact after coating and thermal treatment, preserving their crystallinity and microporous structure while introducing an external metal-containing carbonaceous shell. Electrochemical measurements revealed a clear metal-dependent behaviour: Co-based composites exhibited higher Faradaic efficiencies and H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> production, whereas Fe-based materials generated lower peroxide levels, indicating higher peroxide consumption during the oxidation process. Phenol hydroxylation was strongly influenced by the interplay between the zeolite topology and the active metal, leading to distinct distributions of the valuable oxidation products (catechol, hydroquinone, and benzoquinone). In particular, the MWW-based composites showed exclusive selectivity toward benzoquinone, while TS-1 and Ti-Beta generated mixed product distributions that 2 depended on the incorporated metal. These results demonstrate that the catalytic performance is governed not only by H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> generation but also by framework-dependent peroxide activation and mass transport, providing valuable insights for the design of integrated electrocatalytic oxidation systems. </jats:p>