Understanding solvent effects on adsorption and protonation in porous catalysts.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 32103007.
- Also identified by DOI 10.1038/s41467-020-14860-6 and PMC identifier 7044222.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4 - dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.