Ultrafast Intercalation Enabled by Strong Solvent-Host Interactions: Understanding Solvent Effect at the Atomic...

Area of Science:

• Materials Chemistry
• Solution Chemistry
• Physical Chemistry

Background:

• Solvents are crucial for solution-phase reactions, influencing chemical reactivity.
• Solvent effects are known in intercalation reactions, but their thermodynamic and kinetic impacts are not well understood.
• Intercalation chemistry lacks detailed insights into solvent-dependent reaction mechanisms.

Purpose of the Study:

• To investigate the solvent-dependent kinetics of ferrocene intercalation into vanadyl phosphate (VOPO4·2H2O).
• To explore the influence of primary alcohols on intercalation and exfoliation rates.
• To elucidate the atomic-level mechanisms governing solvent effects in intercalation using computational methods.

Main Methods:

• Experimental study of ferrocene intercalation kinetics using layered vanadyl phosphate as a host.
• Systematic variation of primary alcohol solvents (methanol to 1-hexanol).
• Density Functional Theory (DFT) calculations to analyze solvent interactions and layer dynamics.

Main Results:

• Intercalation rates varied significantly across different primary alcohols, peaking with 1-propanol (80x faster than methanol).
• Similar solvent-dependent kinetics were observed for the exfoliation of vanadyl phosphate without ferrocene.
• DFT calculations revealed that pre-intercalated solvent molecules mediate intralayer interactions, interlayer expansion, and layer sliding.

Conclusions:

• Solvent choice is a critical factor controlling the kinetics of ferrocene intercalation and vanadyl phosphate exfoliation.
• 1-Propanol demonstrates optimal solvent properties for enhancing intercalation and exfoliation rates.
• The study provides a fundamental understanding of solvent-mediated mechanisms in layered material intercalation at the atomic scale.