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[M-COF] Linkage Engineering by Harnessing Supramolecular Interactions to Fabricate 2D Hydrazone-Linked COFs Platforms
Summary:
Professor Yanli Zhao's team from Nanyang Technological University developed a series of 2D hydrazone-linked covalent organic frameworks (COFs) with enhanced stability and porosity through metal coordination, achieving significant improvements in catalytic performance for the Suzuki−Miyaura cross-coupling reaction.
Background:
1. To address the challenge of limited stability and functionality of COFs under various conditions, previous researchers explored covalent modifications and noncovalent interactions, achieving some success. However, these methods often resulted in decreased porosity or limited functional versatility.
2. The authors in this work proposed a supramolecular strategy-based linkage engineering approach, utilizing metal coordination to enhance the crystallinity, stability, and functionality of COFs, and obtained promising results.
Research Content:
1. Synthesis:
The authors synthesized two isoreticular COFs, COF−DB and COF−DT, using an acid-catalyzed solvothermal polycondensation reaction of hydrazides with aldehydes.
2. Characterizations:
1) BET surface areas of COF−DB and COF−DT were 632 and 747 m² g⁻¹, respectively, with a pore size of around 31 Å. 2) SEM/TEM tests showed coral-like and fiber-like morphologies for COF−DB and COF−DT, respectively, with particle sizes above 1 μm. 3) Other tests such as FT-IR, XPS, and TGA confirmed the successful formation of hydrazone linkages and the high thermal stability of the COFs.
3. Application:
The material was tested in the Suzuki−Miyaura cross-coupling reaction, and Pd/COF−DB exhibited excellent catalytic activity and stability, outperforming its amorphous counterparts and Pd/COF−DT.
4. Mechanism:
The analysis of the experimental results indicated that the unique coordination mode in Pd/COF−DB restricted bond rotation, leading to extended π-conjugation, improved crystallinity, and enhanced stability. The synergistic supramolecular interactions facilitated better catalytic performance.
Outlook:
This research provides a novel strategy for designing 2D COFs with enhanced stability and functionality through supramolecular interactions, opening up new avenues for the development of COFs for advanced catalytic applications.
Linkage Engineering by Harnessing Supramolecular Interactions to Fabricate 2D Hydrazone-Linked Covalent Organic Framework Platforms toward Advanced Catalysis
Authors: Cheng Qian, Weiqiang Zhou, Jingsi Qiao, Dongdong Wang, Xing Li, Wei Liang Teo, Xiangyan Shi, Hongwei Wu, Jun Di, Hou Wang, Guofeng Liu, Long Gu, Jiawei Liu, Lili Feng, Yuchuan Liu, Su Ying Quek, Kian Ping Loh, Yanli Zhao
DOI: 10.1021/jacs.0c08436
Link: https://pubs.acs.org/doi/10.1021/jacs.0c08436
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