Deconvoluting the Convoluted: Structural Ramifications of Postsynthetic Linkage Modification in COF-366-Co Catalysts
4 affiliations
- 1Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart, Germany.
- 2Department of Chemistry, Ludwig-Maximilians-Universität (LMU), Butenandtstr. 5-13, 81377 Munich, Germany.
- 3Collaborative Research Center 1333, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
- 4South China University of Technology, State Key Laboratory of Luminescent Materials and Devices, 510640 Guangzhou, China.
Abstract
Postsynthetic modification (PSM) is a powerful strategy for modifying properties such as pore environment, stability and catalytic activity in covalent organic frameworks (COFs). While the chemical outcomes of PSMs are well documented, their impact on the underlying crystal lattice is rarely quantified. Yet, when translating modified COF systems toward catalytic applications, such structural changes can impact performance. In this work we interrogate precisely that blind spot for the benchmark electrocatalyst COF-366-Co. We apply three chemical PSM routes to the imine backbone: (i) quinoline cyclization (q-COF-366-Co), (ii) amine reduction (r-COF-366-Co), and (iii) nitrone oxidation (o-COF-366-Co) and investigate chemical as well as structural modifications induced by the functionalization. The catalysts are further investigated toward the electrochemical carbon dioxide reduction reaction in an attempt to decouple the multitude of convoluted aspects that affect catalytic activity, stability and selectivity such as particle size, disorder, strain, catalytic environment, and framework stability. Among the series, q-COF-366-Co showed a higher stability toward CO selectivity over time compared to the pristine COF-366-Co at -0.88 V vs reversible hydrogen electrode (RHE). Investigating q-COF-366-Co further showed, however, that higher functionalization concentrations led to simultaneous increase in disorder and a lower selectivity toward CO during catalysis. This indicates that a balance must be found between functionalization and preservation of crystalline lattice, offering insights into the design importance of maintaining structural coherence when comparing COF-based materials toward applications.
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BibTeX
@article{gele2026deconvoluting,
title = {{Deconvoluting the Convoluted: Structural Ramifications of Postsynthetic Linkage Modification in COF-366-Co Catalysts}},
author = {Samuel Van Gele and Amelie Heilmaier and Fabian Heck and Kathrin Küster and Armin Schulz and Artem Shevchenko and Liang Yao and Bettina V Lotsch},
journal = {Chemistry of materials : a publication of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/acs.chemmater.6c01374},
url = {https://europepmc.org/article/PMC/PMC13718983},
note = {CC BY},
}
RIS
TY - JOUR
TI - Deconvoluting the Convoluted: Structural Ramifications of Postsynthetic Linkage Modification in COF-366-Co Catalysts
AU - Samuel Van Gele
AU - Amelie Heilmaier
AU - Fabian Heck
AU - Kathrin Küster
AU - Armin Schulz
AU - Artem Shevchenko
AU - Liang Yao
AU - Bettina V Lotsch
PY - 2026
DA - 2026/10/07
JO - Chemistry of materials : a publication of the American Chemical Society
DO - 10.1021/acs.chemmater.6c01374
UR - https://europepmc.org/article/PMC/PMC13718983
AB - Postsynthetic modification (PSM) is a powerful strategy for modifying properties such as pore environment, stability and catalytic activity in covalent organic frameworks (COFs). While the chemical outcomes of PSMs are well documented, their impact on the underlying crystal lattice is rarely quantified. Yet, when translating modified COF systems toward catalytic applications, such structural changes can impact performance. In this work we interrogate precisely that blind spot for the benchmark electrocatalyst COF-366-Co. We apply three chemical PSM routes to the imine backbone: (i) quinoline cyclization (q-COF-366-Co), (ii) amine reduction (r-COF-366-Co), and (iii) nitrone oxidation (o-COF-366-Co) and investigate chemical as well as structural modifications induced by the functionalization. The catalysts are further investigated toward the electrochemical carbon dioxide reduction reaction in an attempt to decouple the multitude of convoluted aspects that affect catalytic activity, stability and selectivity such as particle size, disorder, strain, catalytic environment, and framework stability. Among the series, q-COF-366-Co showed a higher stability toward CO selectivity over time compared to the pristine COF-366-Co at -0.88 V vs reversible hydrogen electrode (RHE). Investigating q-COF-366-Co further showed, however, that higher functionalization concentrations led to simultaneous increase in disorder and a lower selectivity toward CO during catalysis. This indicates that a balance must be found between functionalization and preservation of crystalline lattice, offering insights into the design importance of maintaining structural coherence when comparing COF-based materials toward applications.
SN - 0897-4756
SN - 1520-5002
ER -