Refining Metal-Free Carbon Nanoreactors through Electronic and Geometric Comodification for Boosted H<sub>2</sub>O<sub>2</sub> Electrosynthesis toward Efficient Water Decontamination
Yifei Wang, Beibei Li, Guangheng Chen, Yuhan Wu, Meng Tian, Yongzhen Peng, Shi Xue Dou, Laiquan Li, Jingyu Sun
Abstract
Hydrogen peroxide (H 2 O 2 ) electrosynthesis using metal-free carbon materials via the 2e – oxygen reduction pathway has sparked considerable research interest. However, the scalable preparation of carbon electrocatalysts to achieve satisfactory H 2 O 2 yield in acidic media remains a grand challenge. Here, we present the design of a carbon nanoreactor series that integrates precise O/N codoping alongside well-regulated geometric structures targeting high-efficiency electrosynthesis of H 2 O 2 . Theoretical computations reveal that strategic N/O codoping facilitates partial electron transfer from C sites to O sites, realizing electronic rearrangement that optimizes C-site adsorption of *OOH. Concurrently, the O–O bond in *OOH is strengthened by charge transfer from antibonding to π-orbitals, stabilizing the O–O bond and preventing its dissociation. The carbon nanoreactor with a hollow bowl geometry also facilitates the mass transport of O 2 and H 2 O 2, achieving an H 2 O 2 selectivity of 96% in acidic media. Furthermore, a flow cell integrated with the refined nanoreactor catalyst achieves an impressive H 2 O 2 production rate of 2942.4 mg L –1 h –1, coupled with stable operation of nearly 80 h, surpassing the state-of-the-art metal-free analogs. The feasibility of the electro-synthesized H 2 O 2 is further demonstrated to be highly efficient in wastewater remediation.