Neutral-Condition Hydrogen Peroxide Electrosynthesis at Industrial-Level Current Density Over Bipyridine-Bridged...

Conductive metal-organic frameworks (c-MOFs) have been widely adopted for catalyzing two-electron oxygen reduction reaction (2e^- ORR) toward hydrogen peroxide (H₂O₂) electrosynthesis, due to their precisely designable metal-nonmetal coordinations. However, the π-π conjugated c-MOFs normally possess a fairly small interlayer spacing, leaving their internal active sites unexposed and thus severely limiting their catalytic capability. Herein, by combining the theoretical prediction based on density functional theory calculations with experimental verification, bipyridine (BPY)-bridged and Co porphine-based c-MOF (BPY-Co-TCPP, TCPP = tetra(4-carboxyphenyl)-porphine) has been designed, in which the BPY ligands remarkably expand the interlayer spacing of the Co-TCPP, thereby efficiently enabling the exposure of internal active sites for 2e^- ORR electrocatalysis. In addition, BPY ligands also create extra axial-N coordination for the CoN₄ and Co₂O₈ sites in Co-TCPP, which finely tunes the electronic properties of Co centers and further optimizes their catalytic activities. Consequently, the as-synthesized BPY-Co-TCPP achieves a stable H₂O₂ yield at an industrial-level current density of 300 mA cm^-2 in neutral media with a high Faradaic efficiency of ∼90%. Meanwhile, the as-produced H₂O₂ solution shows confirmed potential for water purification and disinfection. These findings highlight the effectiveness of precise bridging strategy in optimizing the catalytic capability of layered electrocatalysts, paving the way for highly efficient H₂O₂ electrosynthesis and other chemical transformations.