Dual‐Functional Catalyst of Amorphous TiO₂ Embedded in Mesoporous Carbon Hollow Spheres for H₂O₂ Electrosynthesis

Abstract H₂O₂ production in coupled electrochemical systems, where H₂O₂ is generated through 2e‐pathway of water oxidation (2e‐WOR) at anode and 2e‐pathway of oxygen reduction (2e‐ORR) at cathode, offers an advanced alternative to the anthraquinone process. However, the efficiency of such coupled system is often hindered by the limited activity and selectivity of electrocatalysts. Herein, a dual‐functional catalyst composed of amorphous TiO₂ embedded in mesoporous carbon hollow spheres (TiO_x@MCHS) is reported, which exhibits exceptional electrocatalytic performance for both 2e‐WOR and 2e‐ORR. By employing TiO_x@MCHS‐loaded electrodes as both anode and cathode in a membrane‐free flow cell with 4 м K₂CO₃/KHCO₃ as electrolyte, a rate of 108.3 µmol min⁻¹ cm⁻² and a Faradaic efficiency (FE) of ≈145% for H₂O₂ production are achieved at a voltage of ≈2.5 V under a constant current of 240 mA (anode: 1 cm², cathode: 4 cm²). Experimental and computational results reveal the crucial role of low‐coordinated Ti in optimizing the adsorption of intermediates involved in the two electrode reaction pathways, thereby enhancing both activity and selectivity of these processes. This work establishes a new paradigm for the development of advanced electrocatalysts and the design of novel coupled‐electrolysis systems, enabling scalable and sustainable H₂O₂ electrosynthesis.