2026-10-11T04:56:10Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34050177 2026-10-01T18:08:26Z category_1 category_4 category_146 category_915 category_21 category_873 category_135 portal_63 item_type_6 month_year_10_2026

Molecular Space-Charge Layering in Ionic Covalent Organic Frameworks for Unidirectional Charge Transfer toward Efficient H₂O₂ Photosynthesis Chao Yang (174810) Jiamin Liu (6406448) Gaoyi Xie (11239851) Linxiao Hou (6321677) Huiyin Li (25158159) Jiahui Yan (10664944) Bin Wang (30851) Li’an Hou (4846567) Biophysics Biochemistry Space Science Physical Sciences not elsewhere classified Biotechnology Chemical Sciences not elsewhere classified Computational Biology successfully engineered within rectifying valve along formidable exciton recombination driven hydrogen peroxide covalent organic frameworks promising sustainable paradigm 2 </ sup gating charge transfer significantly promoted electron 2 </ sub robust molecular space linked ionic cof sp </ molecular space powerful paradigm linked conjugation >< sup intramolecular charge charge layers charge layering charge layer work unveils withdrawing centers supramolecular systems severely restricted sacrificial agents pristine skeleton photosynthesis solar photosynthesis rate markedly outperforming incorporating n hole dissociation highly crystalline fundamental role designing high 3 without Solar-driven hydrogen peroxide (H₂O₂) production over covalent organic frameworks (COFs) represents a promising sustainable paradigm, yet its efficiency is severely restricted by formidable exciton recombination. Herein, we employed a solvent-free melt polymerization method to synthesize a highly crystalline <i>sp</i>² carbon-linked ionic COF, designated as TMB-COF-Br. Incorporating N⁺-functionalized pyridine units constructed as electron-withdrawing centers, a robust molecular space-charge layer was successfully engineered within the pristine skeleton. The tailored electrostatic environment functioned as an intramolecular charge-rectifying valve along the <i>sp</i>² carbon-linked conjugation, which significantly promoted electron/hole dissociation and enabled directional charge transport, thereby markedly boosting photocatalytic H₂O₂ production. Furthermore, the localized electropositive microenvironment effectively stabilized the crucial *OOH intermediate via electrostatic interactions. Consequently, TMB-COF-Br achieved a remarkable H₂O₂ photosynthesis rate of 5770 μmol·g^–1·h^–1 at pH = 3 without any sacrificial agents, markedly outperforming the nonionized COF. This work unveils the fundamental role of molecular space-charge layers in gating charge transfer in supramolecular systems, providing a powerful paradigm for designing high-efficiency photocatalysts. 2026-10-01T00:00:00Z Text Journal contribution 10.1021/acsnano.6c11167.s001 https://figshare.com/articles/journal_contribution/Molecular_Space-Charge_Layering_in_Ionic_Covalent_Organic_Frameworks_for_Unidirectional_Charge_Transfer_toward_Efficient_H_sub_2_sub_O_sub_2_sub_Photosynthesis/34050177 CC BY-NC 4.0