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Title: Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems

Abstract

Surface functionalization controls local environments and induces solvent-like effects at liquid–solid interfaces. We explored structure–property relationships between organic groups bound to pore surfaces of mesoporous silica nanoparticles and Stokes shifts of the adsorbed solvatochromic dye Prodan. Correlating shifts of the dye on the surfaces with its shifts in solvents resulted in a local polarity scale for functionalized pores. The scale was validated by studying the effects of pore polarity on quenching of Nile Red fluorescence and on the vibronic band structure of pyrene. Measurements were done in aqueous suspensions of porous particles, proving that the dielectric properties in the pores are different from the bulk solvent. The precise control of pore polarity was used to enhance the catalytic activity of TEMPO in the aerobic oxidation of furfuryl alcohol in water. Furthermore, an inverse relationship was found between pore polarity and activity of TEMPO in the pores, demonstrating that controlling the local polarity around an active site allows modulating the activity of nanoconfined catalysts.

Authors:
 [1];  [1];  [2];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1335034
Alternate Identifier(s):
OSTI ID: 1401218
Report Number(s):
IS-J-9153
Journal ID: ISSN 1439-4235
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 17; Journal Issue: 19; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecular environment; solvent effects; relative polarity; mesoporous materials; surface functionalization; confinement effects

Citation Formats

Singappuli-Arachchige, Dilini, Manzano, J. Sebastian, Sherman, Lindy M., and Slowing, Igor I. Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems. United States: N. p., 2016. Web. doi:10.1002/cphc.201600740.
Singappuli-Arachchige, Dilini, Manzano, J. Sebastian, Sherman, Lindy M., & Slowing, Igor I. Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems. United States. doi:10.1002/cphc.201600740.
Singappuli-Arachchige, Dilini, Manzano, J. Sebastian, Sherman, Lindy M., and Slowing, Igor I. Tue . "Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems". United States. doi:10.1002/cphc.201600740. https://www.osti.gov/servlets/purl/1335034.
@article{osti_1335034,
title = {Polarity control at interfaces: Quantifying pseudo-solvent effects in nano-confined systems},
author = {Singappuli-Arachchige, Dilini and Manzano, J. Sebastian and Sherman, Lindy M. and Slowing, Igor I.},
abstractNote = {Surface functionalization controls local environments and induces solvent-like effects at liquid–solid interfaces. We explored structure–property relationships between organic groups bound to pore surfaces of mesoporous silica nanoparticles and Stokes shifts of the adsorbed solvatochromic dye Prodan. Correlating shifts of the dye on the surfaces with its shifts in solvents resulted in a local polarity scale for functionalized pores. The scale was validated by studying the effects of pore polarity on quenching of Nile Red fluorescence and on the vibronic band structure of pyrene. Measurements were done in aqueous suspensions of porous particles, proving that the dielectric properties in the pores are different from the bulk solvent. The precise control of pore polarity was used to enhance the catalytic activity of TEMPO in the aerobic oxidation of furfuryl alcohol in water. Furthermore, an inverse relationship was found between pore polarity and activity of TEMPO in the pores, demonstrating that controlling the local polarity around an active site allows modulating the activity of nanoconfined catalysts.},
doi = {10.1002/cphc.201600740},
journal = {ChemPhysChem},
number = 19,
volume = 17,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

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