文献类型：期刊文献

英文题名：Alkaline-adaptive covalent organic framework photocatalysts: synergistic molecular orbital and hydrogen-bond network engineering for H2O2 production

作者：Yu, Zhiwu[1];Zhang, Jiayi[1];Zhang, Xiaolong[1];Sun, Xuwen[1];Wu, Guihong[2];Zhang, Zhiyun[1];Yu, Fengtao[2];Hua, Jianli[1]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[2]East China Univ Technol, Jiangxi Prov Key Lab Funct Organ Polymers, Nanchang 330013, Peoples R China

年份：2026

卷号：17

期号：13

起止页码：6456

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20261420442894);WOS:【SCI-EXPANDED(收录号:WOS:001680665200001)】；

基金：For financial support of this research, the authors acknowledge the projects supported by the National Natural Science Foundation of China (22271093, 21971064, 22105034, and 22465001), Young Elite Scientists Sponsorship Program by JXAST (2024QT11), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Programme of Introducing Talents of Discipline to Universities (B16017) and the Fundamental Research Funds for the Central Universities. The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the help with characterization.

语种：英文

外文关键词：Complexation - Hydrogen bonds - Hydrogen production - Hydrophilicity - Oxidation - Photocatalysts - Photocatalytic activity - Reaction kinetics - Sodium hydroxide

摘要：Alkaline hydrogen peroxide (H2O2) is highly desirable for critical applications due to its superior stability and reactivity, but it is incompatible with conventional near-neutral production methods. While covalent organic frameworks (COFs) show promise for photocatalytic H2O2 generation, their alkaline performance is severely limited by poor charge dynamics and inadequate hydrophilicity, hindering the essential 2e- oxygen reduction reaction (ORR: O2 + 2e- + H2O -> HO2- + OH-) and 4e- water oxidation reaction (WOR: 4OH- -> O2 + 2H2O + 4e-). This work pioneers a dual-engineering strategy (molecular orbital and interfacial hydrogen-bonding network engineering) within beta-ketoenamine-linked COFs to overcome these challenges simultaneously. By contrasting phenazine-based (TP-PZ-COF) and anthracene-based (TP-AN-COF) COFs, we demonstrate that strategic integration of sp2-N heteroatoms modulates molecular orbitals and enhances n -> pi* transitions, optimizing charge separation and transport for efficient 2e- ORR and 4e- WOR. Concurrently, the planar phenazine units form robust hydrogen-bonding networks that dramatically boost hydroxide ion (OH-) affinity and interfacial enrichment, thereby accelerating the 4e- WOR kinetics. This integrated approach enabled TP-PZ-COF to achieve an exceptional alkaline H2O2 production rate of 4961 mu mol g-1 h-1 in 0.01 M NaOH, representing an 8.1-fold increase over TP-AN-COF (606 mu mol g-1 h-1). The generated H2O2 efficiently degraded industrial dye pollutants. Direct experimental and theoretical validations confirmed the cooperative mechanism between charge dynamics optimization and OH- affinity enhancement, providing a new blueprint for designing on-demand alkaline H2O2 photocatalysts.