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Title: Ultrafast Intercalation Enabled by Strong Solvent–Host Interactions: Understanding Solvent Effect at the Atomic Level

Journal Article · · Angewandte Chemie
 [1];  [1];  [1];  [2];  [3];  [1]; ORCiD logo [1]
  1. Materials Science and Engineering Program and Department of Mechanical Engineering The University of Texas at Austin Austin TX 78712 USA
  2. Materials Science and Engineering Program and Department of Mechanical Engineering The University of Texas at Austin Austin TX 78712 USA, International Iberian Nanotechnology Laboratory Braga 4715-330 Portugal
  3. International Iberian Nanotechnology Laboratory Braga 4715-330 Portugal, Mechanical Engineering Department and IDMEC Instituto Superior Técnico University of Lisbon Av. Rovisco Pais Lisboa 1049-001 Portugal
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Abstract Solvents play an essential role in many areas of chemistry and is the cornerstone of understanding reactivity in solution‐phase reactions. Solvent effects have been widely observed in intercalation reactions; however, understanding of the influence of solvents on the thermodynamics and kinetics remains largely elusive in intercalation chemistry. Now, the solvent‐dependent kinetics of ferrocene intercalation into a layered vanadyl phosphate (VOPO 4 ⋅2 H 2 O) host is presented, with a special focus on primary alcohols. From methanol to 1‐hexnaol, the intercalation rate peaks in 1‐propanol (80 times faster than the slowest case in methanol). Similar kinetics of exfoliation are also found in these solvents without ferrocene. The correlation between intercalation and exfoliation is understood at atomic level by DFT calculations, which reveal the role of pre‐intercalated solvent molecules play in intralayer interactions, interlayer expansion, and layer sliding.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0019019
OSTI ID:
1570507
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 48 Vol. 131; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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