Electrocatalytic hydrogen peroxide (H₂O₂) production via the two-electron oxygen reduction reaction is a promising alternative to the energy-intensive and high-pollution anthraquinone oxidation process. However, developing advanced electrocatalysts with high H₂O₂ yield, selectivity, and durability is still challenging, because of the limited quantity and easy passivation of active sites on typical metal-containing catalysts, especially for the state-of-the-art single-atom ones. To address this, we report a graphene/mesoporous carbon composite for high-rate and high-efficiency 2e⁻ oxygen reduction catalysis. The coordination of pyrrolic-N sites -modulates the adsorption configuration of the *OOH species to provide a kinetically favorable pathway for H₂O₂ production. Consequently, the H₂O₂ yield approaches 30 mol g⁻¹ h⁻¹ with a Faradaic efficiency of 80% and excellent durability, yielding a high H₂O₂ concentration of 7.2 g L⁻¹. This strategy of manipulating the adsorption configuration of reactants with multiple non-metal active sites provides a strategy to design efficient and durable metal-free electrocatalyst for 2e⁻ oxygen reduction.

Layered vanadium oxides are promising cathode materials for zinc‐ion batteries (ZIBs) owing to their high capacity, but the sluggish electron/ion migration kinetics and structural collapse/dissolution severely limit their Zn²⁺‐storage performance. Herein, poly(3,4‐ethylenedioxythiophene) coated and Mn²⁺‐intercalated vanadium oxides with rich oxygen vacancies (MnVOH@PEDOT) are prepared as the cathodes for ZIBs. The PEDOT coating, synergistic with oxygen vacancies, tailors the electron conductivity, and the Mn²⁺‐intercalation enlarges the interlayer spacing for rapid Zn²⁺‐ions diffusion. In addition, the pre‐intercalated Mn²⁺‐ions act as “pillars” to stabilize the structure, and the PEDOT coating prevents the direct contact of vanadium oxides with electrolyte to inhibit its dissolution during cycling. Thus, the MnVOH@PEDOT cathode exhibits superior discharge capacity, favorable rate capability (336.0 mAh g⁻¹ at 8 A g⁻¹), and satisfying cyclic durability (84.8% capacity retention over 2000 cycles). This work offers a facile and synergistic design strategy for achieving favorable cathodes for ZIBs. image

Tailoring the electronic structure of electrocatalysts for oxygen reduction reaction (ORR) has been widely adopted to optimize their performance. However, the steric effect originating from the layered or crystal structure of a catalyst is often neglected. Herein, we demonstrate the importance of such steric effect in a one-dimensional π-d conjugated metal-organic framework with Ni-(NH)₄ nodes (Ni-BTA) for optimizing its electrocatalytic performance, where the activity and selectivity towards two-electron ORR for H₂O₂ production are largely enhanced. Theoretical simulation and in-situ characterization demonstrate the formation of inter-layer H-bonds between *OOH intermediates and -N-H groups in the adjacent top layers of the Ni-sites, enhancing the *OOH binding energy to an optimum value. Thus, the as-prepared Ni-BTA catalyst exhibits an outstanding electrocatalytic 2e⁻-ORR performances under neutral and alkaline conditions (e.g., >85% H₂O₂ selectivity from −0.1-0.4 V vs. RHE and >13.5 mol g⁻¹ h⁻¹ H₂O₂ yield in neutral electrolytes), also showing great potential on water treatment and disinfection. Here, we highlight the alternative avenues for utilizing the non-coordinated structure to regulate the catalytic performance, thus providing opportunities for the design of catalysts and beyond.