When experimental results diverge from scientists’ predictions, the typical assumption is that the predictions were flawed. However, groundbreaking research into materials designed to capture carbon dioxide directly from the air suggests that such mismatches can be valuable clues, leading to discoveries that may redefine the design of future materials.
In a paper published on December 21 in the Journal of the American Chemical Society (JACS), a team led by Professor Laura Gagliardi from the University of Chicago Pritzker School of Molecular Engineering (UChicago PME) and Department of Chemistry, alongside Nobel laureate Professor Omar Yaghi from the University of California, Berkeley, introduced a novel method for excluding water when using covalent organic frameworks (COFs) to develop carbon capture materials.
Recognizing the scientific significance and potential real-world impact of this research, JACS selected the paper as its “Editor’s Choice.” According to first author Hilal Daglar, who conducted the research as a postdoctoral researcher in Gagliardi’s lab and is now with UL Research Institutes, “Mismatches between simulations and experiments are not failures, but opportunities. In this project, those discrepancies guided us toward residual water and subtle structural features that were not obvious at first glance.”
Exploring the Mystery of COFs
The research originated from The Center for Advanced Materials for Environmental Solutions (CAMES), co-directed by Gagliardi as part of the University of Chicago Institute for Climate & Sustainable Growth. By outlining a design strategy that introduces hydrophobic pore environments to exclude retained water, the study aims to enable scientists to develop more effective solutions for air pollution.
“We think of CAMES as a bridge between materials discovered in the lab and real-world environmental impact,” said CAMES Co-Director Doug Weinberg. “Our role isn’t just to support breakthrough science. It’s to help ensure those breakthroughs matter beyond the lab. Hilal’s work is a great example of that mission in action.”
Gagliardi has been investigating the potential of COFs and reticular chemistry for the past decade. COFs gained wider attention this year after Gagliardi’s collaborator Yaghi won the 2025 Nobel Prize in Chemistry alongside Susumu Kitagawa and Richard Robson. “These materials are known as reticular frameworks, meaning they are built from well-defined molecular building blocks connected through strong chemical bonds into extended crystalline networks,” Gagliardi explained.
Harnessing Computational Modeling
Using her expertise in theoretical modeling, Gagliardi, along with Daglar, conducted complex computer simulations predicting the structure of COF-999-NH2, a promising material for CO2 capture from air. However, a disconnect emerged between their predictions and the experimental results from Yaghi’s team.
Instead of assuming failure, the theorists and experimentalists collaborated to unravel this mystery, leading to new and unexpected insights. “In this back and forth between experiment and theory, we started to hypothesize that there were some residual water molecules in the synthesized material, which we initially did not include in our model because the experimentalists thought that the material had been completely dehydrated,” Gagliardi said.
New Insights and Future Implications
This investigation not only uncovered the cause of the predictive mismatch but also paved the way for more effective carbon capture strategies. The research established a simple design rule for future researchers: controlling pore hydrophobicity during the polymerization of COF-999 prevents water retention.
“This prevents adsorption site blockage and undesired side reactions, enabling more effective carbon capture,” Daglar stated.
Beyond this core finding, the study also revealed previously unknown insights about COFs, including that the stacking heterogeneity, buckling, and lattice contraction observed were intrinsic features of their precursor chemical.
Gagliardi emphasized the importance of computational modeling in these discoveries. “To advance these discoveries, computations and simulations are indispensable. On the computer, you can try things that maybe your chemical intuition might not suggest right away. The computer can give you some useful answers that allow you to think in a different way.”
As the scientific community continues to explore the potential of COFs in carbon capture, the insights gained from this research could significantly influence future material design and environmental strategies.
Citation: “Discovery of Stacking Heterogeneity Layer Buckling and Residual Water in COF-999-NH2 and Implications on CO2 Capture,” Daglar et al, Journal of the American Chemical Society, December 21, 2025. DOI: 10.1021/jacs.5c18608
