Encapsulation of Highly Dispersed Au NPs by Strong Metal–Support Interactions in Porous Titania Nanoplates for Efficient Electrosynthesis of H2O2

Tuning the electrocatalytic selectivity and long‐term stability for industrially significant, yet reactively unfavorable products, remains a challenge in oxygen reduction. Herein, the Au/TiO2 catalysts with strong metal–support interactions (SMSI) are designed and synthesized through an in situ auto‐reduction of Au‐modified Ti‐MOF. Highly dispersed ultra‐low loading of Au NPs strongly capsulated in porous TiO2 substrate, together with conductive carbon derivated from MOFs, enables Au/TiO2 electrocatalysts to achieve excellent H2O2 electrosynthesis through the two‐electron oxygen reduction reaction (2e ORR). Au(1.0)/TiO2 (0.52 wt% Au loading) exhibited a high selectivity of 90%, a remarkable Faradaic efficiency of 98%, and 72.2 mg L−1 h−1 H2O2 production. Highly dispersed Au NPs promote active site exposure, while the conductive carbon and the porous superstructure enhance mass diffusion. Notably, the SMSI between Au NPs and TiO2 substrate leads to superb stability (over 168 h) of the electrocatalysts, as it ensures continuous electronic interactions. Experimental characterizations and density functional theory (DFT) simulations further revealed that the SMSI effect medicates the activation of the *OOH intermediate formation and the d‐band center, which are conductive to 2e ORR. Moreover, this strategy provides a potential way toward high‐performance electrocatalysts in flow system devices for continuously purifying sewage and chemical bleaching in extreme environments. A strong metal–support interaction (SMSI) effect is realized in the Au/TiO2 electrocatalysts via an in situ auto‐reduction of Au‐modified Ti‐MOF. The synergy SMSI effect within a porous superstructure successfully optimizes adsorption energies toward the *OOH intermediates, while also protecting active sites, facilitating mass transfer, promoting electrotransfer, and enhancing chemical stability, thus leading to superior electrocatalytic activity and selectivity for H2O2 evolution.