Tuning the p-band center of carbon via push-pull coupling in adjacent BN pairs enables near-unity H2O2 selectivity over a wide potential window

B N pairs create push-pull coupling to upshift p-band center for optimal *OOH adsorption. • B,N co-doped carbon achieves 99% H 2 O 2 selectivity over wide window in 2e − ORR. • The catalyst yields 788 mmol g cat −1  h −1 H 2 O 2 in H-cell and stable 250 mA cm −2 operation for 14 h. • B N synergy breaks π-conjugation uniformity to enable near-unity 2e − ORR. Selective electrocatalytic two-electron oxygen reduction (2e − ORR) offers a green alternative to the energy-intensive anthraquinone process for hydrogen peroxide (H 2 O 2 ) production. However, the inert π-conjugation of carbon catalysts homogenizes the electronic environment of active sites, making it intrinsically difficult to achieve the optimal *OOH adsorption energy essential for high 2e − selectivity. In this study, we developed B,N co-doped carbon catalysts through a cost-effective pyrolysis method, achieving 99% H 2 O 2 selectivity across a remarkably wide potential window (0.20–0.70 V vs. RHE), an H-cell production rate of 788 mmol g cat −1  h −1 , and sustained operation in a flow cell at 250 mA cm −2 for 14 h with a Faradaic efficiency above 80%. It was demonstrated that engineering adjacent B N pairs within a carbon matrix established a localized push-pull electronic coupling that precisely upshifts the p-band center of active carbon atoms into the theoretically predicted “golden zone” for *OOH adsorption via combined experimental and theoretical analysis. These findings highlight the critical role of heteroatom doping in tailoring electronic structures and provide a scalable strategy for efficient, environmentally friendly H 2 O 2 production using carbon-based catalysts. This work develops B,N co-doped carbon catalysts that achieve 99% H 2 O 2 selectivity and 8 mol g cat −1  h −1 yield via 2e − ORR, leveraging synergistic doping and pyrrolic nitrogen optimization for scalable production. Download: Download high-res image (113KB) Download: Download full-size image