Fulun You, Yepeng Yang*, Qihui Wang, Yong Chen, Zhixin Wang, Weixian Li, Yizhou Li, Li Qiu, Liang Jiang, Rao Tao*

Cite this article: https://doi.org/10.1016/j.cjsc.2026.101081

Publication date:

Keywords: Photocatalytic; Hydrogen peroxide (H₂O₂); Conjugated microporous polymer (CMP); Pyridinic nitrogen; Electronic modulation

ABSTRACT

The development of efficient organic photocatalysts for sustainable hydrogen peroxide (H2O2) production provides a viable substitute for high-energy-consumption anthraquinone process. In this study, two pyrene-based conjugated microporous polymers (CMPs), Py-DBP and Py-DBB, were synthesized via Sonogashira-Hagihara coupling to systematically investigate the role of pyridinic nitrogen in modulating photocatalytic performance. Compared with benzene-linked analogue, pyridine-functionalized Py-DBP exhibits a significantly enhanced H2O2 production rate of 1560.5 μmol·g-1·h-1, 2.5 times higher than that of Py-DBB. Scaled-up reactor demonstrates consistent and stable H2O2 yield under natural sunlight. Mechanistic studies reveal that nitrogen incorporation modulates electronic structure, induces charge redistribution, and promotes separation and migration of photogenerated charge carriers. Enriched negative charge density at carbon sites adjacent to nitrogen atoms creates a favorable electrostatic environment for molecular oxygen adsorption and activation. Density functional theory calculations confirm that Py-DBP exhibits a lower Gibbs free energy for the formation of key *OOH intermediate, thereby improving both thermodynamic efficiency and kinetic favorability in two-step single-electron oxygen reduction pathway for H2O2 generation. These findings highlight heteroatom engineering as a powerful strategy for enhancing the photocatalytic performance of CMP-based materials.