Dynamic pyridinethiol ligand shuttling within iron-anchored covalent organic frameworks boosts CO 2 photoreduction

Dynamic pyridinethiol ligand shuttling within iron-anchored covalent organic frameworks boosts CO 2 photoreduction Научная публикация

Журнал

Journal of Materials Chemistry A
ISSN: 2050-7488 , E-ISSN: 2050-7496

Вых. Данные

Год: 2025, Том: 13, Номер: 2, Страницы: 1407-1419 Страниц : 13 DOI: 10.1039/d4ta07403c

Авторы

Zhang Yong-Kang ¹ , Zhao Lan ¹ , Terent'ev Alexander O. ² , He Liang-Nian ¹

Организации

1	State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, P. R. China
2	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow 119991, Russia

A covalent organic framework (COF), as a porous crystalline material, provides a versatile platform for the photocatalytic CO2 reduction reaction (PCO2RR). However, the lack of surface redox active sites and rapid photogenerated charge recombination are the major barriers limiting further enhancement of PCO2RR activity. Herein, we designed a novel photocatalytic system constructed from a dynamic D⋯M–A structure COF. Earth-abundant metal iron sites were embedded into a triazinyl COF structure containing bipyridine units (Fe-bpy-COF), and the subsequent supplementation of pyridinethiol to the system allowed efficient CO2 photoreduction without additional photosensitizers. Remarkably, the Fe-bpy-COF system achieved an impressive formate yield of 4052 μmol g−1 h−1 and CO yield of 2123 μmol g−1 h−1, being over approximately 8.2-fold higher than that of the previously reported Re-COF under visible light irradiation. On the basis of 1H NMR titration experiments and steady-state tests of the absorption spectra, the superior photocatalytic performance is accordingly attributed to the dynamic coordination interaction between the pyridinethiol ligands and Fe-bpy-COF host, thus facilitating continuous double-electron transfer from the pyridinethiol ligands to the iron center under visible light and inhibiting photogenerated charge recombination in Fe-bpy-COF. Finally, the reaction pathways of CO2 conversion catalyzed by the reductive iron active species are elucidated by combining experimental results and density functional theory studies. This provides unprecedented insights into the design of earth abundant metal-derived COF photocatalysts for efficient and selective CO2 reduction under visible light.

Zhang Y-K. , Zhao L. , Terent'ev A.O. , He L-N.
Dynamic pyridinethiol ligand shuttling within iron-anchored covalent organic frameworks boosts CO 2 photoreduction
Journal of Materials Chemistry A. 2025. V.13. N2. P.1407-1419. DOI: 10.1039/d4ta07403c WOS Scopus OpenAlex

Web of science:	WOS:001372066900001
Scopus:	2-s2.0-85211988121
OpenAlex:	W4404908965

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