Document Detail


Use of ferrocenyl surfactants of varying chain lengths to study electron transfer reactions in native montmorillonite clay.
MedLine Citation:
PMID:  15575277     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
A series of ferrocenyl surfactants was tested as model compounds to study electron transfer reactions involving structural Fe(III) in clay minerals. The surfactants contain trimethylammonium headgroups, ferrocene tail groups, and intervening hydrocarbon chain lengths of one, six, or 11 carbons. Two factors considered to be decisive for electron transfer were addressed: (1) physical access of the surfactant ferrocene to the reactive sites through hexagonal holes in the clay lattice by X-ray diffraction (XRD) and small-angle X-ray scattering (SAXS) and (2) thermodynamic favorability of the overall oxidation/reduction reaction based on experimentally determined oxidation/reduction potentials. In suspensions of clay with the longer chain surfactants, (ferrocenylhexyl)trimethylammonim (FHTMA+) and (ferrocenylundecyl)trimethylammonium (FUTMA+), where electron transfer may be expected to be favored by both factors, physical accessibility, and thermodynamic favorability, ferroecene oxidation was observed by diffuse reflectance infrared spectroscopy (DRIFT), ultraviolet-visible spectroscopy (UV-vis), and visual color changes. In contrast, the shorter chain length surfactant, (ferrocenylmethyl)trimethylammonium (FMTMA+), did not participate in electron transfer with the clay, as substantiated by UV-vis and no visible color changes. Rigid conformation and/or higher oxidation/reduction potential than clay Fe can accountforthe lack of reaction. The utility and limitations of using these surfactants as model compounds is discussed.
Authors:
Carla Swearingen; Jun Wu; Joseph Stucki; Alanah Fitch
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Environmental science & technology     Volume:  38     ISSN:  0013-936X     ISO Abbreviation:  Environ. Sci. Technol.     Publication Date:  2004 Nov 
Date Detail:
Created Date:  2004-12-03     Completed Date:  2005-03-07     Revised Date:  2006-11-15    
Medline Journal Info:
Nlm Unique ID:  0213155     Medline TA:  Environ Sci Technol     Country:  United States    
Other Details:
Languages:  eng     Pagination:  5598-603     Citation Subset:  IM    
Affiliation:
Department of Chemistry, Loyola University Chicago, Chicago, Illinois 60626, USA. cswearin@uiuc.edu
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MeSH Terms
Descriptor/Qualifier:
Aluminum Silicates
Animals
Bentonite / chemistry*
Electron Transport
Ferrous Compounds / chemistry*
Minerals / chemistry
Models, Molecular
Oxidation-Reduction
Spectrophotometry, Infrared
Spectrophotometry, Ultraviolet
Surface-Active Agents / chemistry*
Thermodynamics
X-Ray Diffraction
Chemical
Reg. No./Substance:
0/Aluminum Silicates; 0/Ferrous Compounds; 0/Minerals; 0/Surface-Active Agents; 102-54-5/ferrocene; 1302-78-9/Bentonite; 1302-87-0/clay

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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