Charting the chemical space of modular heterocyclic nucleophiles for CO₂ capture

04 November 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Carbon capture and storage (CCS) is widely recognized as a pivotal strategy in the transition to a net-zero global economy. However, widespread implementation of CCS is hindered by challenges including the high energy demands associated with solvent regeneration after capture. π-conjugated heterocyclic nucleophiles present a promising alternative to traditional solvents, offering tunable CO₂ binding through the choice of nucleophilic center, heterocycle, and ring substitution. Employing a high-throughput, automated DFT pipeline, we generated a combinatorial virtual library of over 1,800 potential binders, elucidating structure-property relationships that govern their CO₂-binding thermodynamics. Our results highlight key design principles that enable fine-tuning of binding energetics. We find that guanidine, olefin, and carbene-based systems display a much broader range of binding energies compared to traditionally tertiary amines. These energetics can be modulated through the interplay of conformational, electrophilic, and nucleophilic properties of the attached heterocycle, with heteroatom-specific behavior. Additionally, we investigate how steric and electronic properties of substituents can be leveraged to further tune binding strength and regeneration temperature. This systematic exploration enhances our understanding of π-conjugated nucleophiles as viable components for the targeted design and development of efficient carbon capture materials.

Keywords

carbon capture
amines
heterocyclic nucleophiles
computational chemistry
high-throughput screening

Supplementary materials

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Supporting Information
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Supporting text, tables, and figures.
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Binding Energetics Data
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XLS file containing nucleophile SMILES, adduct SMILES, and calculated CO₂ binding free energies for all candidate molecules.
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XYZ Coordinates
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ZIP file containing XYZ coordinates for all nucleophile and CO₂ adduct structures used in binding free energy calculations.
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