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Updated: Sep 24, 2026

Microfluidic-based Synthesis of Covalent Organic Frameworks (COFs): A Tool for Continuous Production of COF Fibers and Direct Printing on a Surface
Published on: July 10, 2017
Engineering van der Waals Heterojunctions Within a 2D Hydrogen-Bonded Organic Framework for Boosting CO2
Qiu-Jin Wu1,2, An-An Zhang1,2, Jia-Tong Huang2
1Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, P.R. China.
Abstract:
Unlike conventional strategies that regulate charge transport in framework electrocatalysts by modifying covalent skeletons or compositions, we demonstrate efficient directional electron transfer by constructing interlayer van der Waals donor-acceptor (D-A) heterojunctions within a hydrogen-bonded organic frameworks (HOFs). The porphyrin-based HOF, PFC-45-Co, is assembled from electron-donating 5,10,15,20-tetra(4-carboxyphenyl)porphyrin (Co-TPyP) and electron-accepting cobalt 5,10,15,20-tetra(4-carboxyphenyl)porphyrin (Co-TCPP) through strong O─H···N hydrogen bonds, while periodic alternating interlayer π-π stacking generates vertical D-A heterojunctions. Mechanistic studies show that close π-π contacts enable through-space charge transport, and the D-A energy offset drives electron transfer from Co-TPyP to Co-TCPP, producing electron-enriched Co-TCPP sites that promote CO2 activation and suppress hydrogen evolution. As a result, PFC-45-Co outperforms the single-component HOF PFC-72-Co in both neutral and acidic media. In neutral electrolyte, PFC-45-Co delivers a CO Faradaic efficiency (FECO) of 98.4% at -0.9 V versus reversible hydrogen electrode (vs. RHE) and a CO partial current density (jCO) of 31.3 mA cm-2 at -1.2 V versus RHE. In acidic media, it maintains FECO values of 92%-99% and achieves jCO of 111.1 mA cm-2 at -1.6 V versus RHE. This work establishes interlayer van der Waals D-A heterojunctions as an effective motif for regulating charge transfer in HOF electrocatalysts.
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