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Carboxylate-Driven Metal Pre‑Fixation COF@MOF Synthesis: Enabling Tailored Structural, Dimensional, and Defect Engineering.

Created on 18 Jun 2026

Authors

Ying Zhao, Dongmei Chen, Huilin Zheng, Min Chen, Dingtang Li, Shuyu Xie

Published in

Advanced science (Weinheim, Baden-Wurttemberg, Germany). Pages e76204. Jun 18, 2026. Epub Jun 18, 2026.

Abstract

Hierarchical composites composed of covalent-organic frameworks (COFs) and metal-organic frameworks (MOFs) (COF@MOF), exhibiting superior tunability in terms of pore structure and electronic distribution, have gained increasing attention in various fields. However, the development of a universal strategy for controllable assembly of COF@MOF composites, enabling precise tuning of composition and structure, remains a significant challenge. Here, a flexible and adjustable COF@MOF synthesis strategy (metal pre‑fixation, MPF) is proposed, which facilitates the extensive growth of MOFs with varying morphologies and particle sizes on the surface of PY-COF-COOH. By employing a hypothesis-deduction approach alongside experimental and density functional theory (DFT) calculations, systematically elucidated that the MPF strategy enables controllable modulation of morphology, size, and coordination structure through ion distribution-guided synthesis (IDGS), a proposed working hypothesis of crystal-facet shielding (CFS), and aperture synergistic regulation (ASR) effects. Furthermore, the MPF-derived PY-COF-COOH@MOFs exhibit significantly enhanced CH4/C2H6/C3H8 separation performance and sustained H2O2 activation efficiency. These results demonstrate significant potential in designing high-performance COF@MOF composites and offer a comprehensive application guide for MPF-based design.

PMID:
42312389
Bibliographic data and abstract were imported from PubMed on 18 Jun 2026.

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