Dr. Lynnette D. Madsen
DMR Division of Materials Research
MPS Directorate for Mathematical & Physical Sciences
Start Date:
August 15, 2002
Expires:
July 31, 2007 (Estimated)
Awarded Amount to Date:
$1106000
Investigator(s):
Stephen Rankin srankin@engr.uky.edu (Principal Investigator)
Barbara Knutson (Co-Principal Investigator) Hans-Joachim Lehmler (Co-Principal Investigator)
Sponsor:
University of Kentucky Research Foundation
201 Kinkead Hall
Lexington, KY 40506 859/257-9420
NSF Program(s):
EXP PROG TO STIM COMP RES, CERAMICS, SOLID STATE & MATERIALS CHEMIS, NANOSCALE: INTRDISCPL RESRCH T, CHEMICAL & BIOLOGICAL SEPAR
Field Application(s):
0106000 Materials Research
Program Reference Code(s):
AMPP, 9251, 9162, 9161, 9150, 1674, 1589
Program Element Code(s):
9150, 1774, 1762, 1674, 1417
ABSTRACT
This interdisciplinary research team will address using a new class of structure directing agents, fluorinated surfactants, for the design of ordered nanoporous metal oxides and organic-inorganic hybrid materials. Fluorinated surfactants provide a novel platform for both templating of and recovery from ordered porous materials because they assemble more readily than hydrocarbon surfactants, form stable phases of low interfacial curvature, and are both hydrophobic and lipophobic. Departing from a traditional technique based on hydrocarbon surfactants we will first systematically explore the effects of fluorinated surfactant structure on the templating of porous silica. With a goal of designing surfactant-templated nanostructures with more tightly controlled pore architecture, this project will integrate molecular simulations, fluorinated surfactant synthesis, phase characterization, and materials synthesis techniques. We also will exploit the selective solubility of fluorinated species in low surface tension fluids (such as supercritical carbon dioxide) to enhance template recovery from nanoporous ceramics. Because fluorinated surfactants can be extracted under mild conditions, their use is expected to improve methods of synthesizing organic-inorganic hybrid materials with nanostructured pores.
The co-assembly of molecular precursors allows the synthesis of nanostructured ceramics that approach the functionality and efficiency of biological materials. "Functionalizing" the pore walls with selected molecular fragments further enhances the potential of these inorganic materials for catalysts, separation materials, sensors and miniaturized diagnostic devices. The synergistic approach to the research and educational activities of this project will advance the fluorosurfactant-based design of new nanosystems by molecular templating and organic functionalization.
This proposal was submitted in response to the solicitation "Nanoscale Science and Engineering" (NSF 01-157). The award is jointly supported through two directorates at NSF: (i) Mathematical and Physical Sciences (Division of Materials Research in the Ceramics and Solid-State Chemistry programs) and (ii) Engineering (Division of Design, Manufacture and Industrial Innovation in the Nanomanufacturing program).
PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH
B. Tan, A. Dozier, H.J. Lehmler, B.L. Knutson and S.E. Rankin. "Elongated Silica Particles with Mesh Phase Mesopore Structure by Fluorosurfactant Templating," Langmuir, v.20, 2004, p. 6981.
B. Tan, H.J. Lehmler, S.M. Vyas, B.L. Knutson and S.E. Rankin. "Controlling Nanopore Size and Shape by Fluorosurfactant Templating of Silica," Chemistry of Materials, v.17, 2005, p. 916.
Bing Tan and Stephen E. Rankin. "Interfacial Alignment Mechanism of Forming Spherical Silica with Radially Oriented Nanopores," Journal of Physical Chemistry B, v.108, 2004, p. 20122.
Bing Tan and Stephen E. Rankin. "Dual Latex/Surfactant Templating of Hollow Spherical Silica Particles with Ordered Mesoporous Shells," Langmuir, v.21, 2005, p. 8180.
Bing Tan, Hans-Joachim Lehmler, Sandhya M. Vyas, Barbara L. Knutson, and Stephen E. Rankin. "Large- and small-nanopore silica prepared with a short-chain cationic fluorinated surfactant," Nanotechnology, v.16, 2005, p. S502.
Bing Tan, Sandhya M. Vyas, Hans J. Lehmler, Barbara L. Knutson and Stephen E. Rankin. "Fluorinated Surfactant-Templated Synthesis of Hollow Silica Particles with a Single Layer of Mesopores in their Shells," Advanced Materials, v.17, 2005, p. 2368.
Bing Tan, Sandyha M. Vyas, Hans J. Lehmler, Barbara L. Knutson and Stephen E. Rankin. "Unusual Dependence of Particle Architecture on Surfactant Concentration in Partially Fluorinated Decylpyridinium Templated Silica," Journal of Physical Chemistry B, v.109, 2005, p. 23225.
Ghosh, K; Vyas, SM; Lehmler, HJ; Rankin, SE; Knutson, BL. "Tailoring porous silica films through supercritical carbon dioxide processing of fluorinated surfactant templates," JOURNAL OF PHYSICAL CHEMISTRY B, v.111, 2007, p. 363-370.
Gifty Osei-Prempeh, Hans J. Lehmler, Barbara L. Knutson and Stephen E. Rankin. "Fluorinated Surfactant Templating Of Vinyl-Functionalized Nanoporous Silica," Microporous and Mesoporous Materials, v.85, 2005, p. 16.
H.-J. Lehmler and P.M. Bummer. "Mixing behavior of 10-(perfluorohexyl)-decanol and DPPC," Colloids and Surfaces B, v.44, 2005, p. 74.
H.-J. Lehmler, P.M. Bummer. "Interaction of a partially fluorinated long-chain nicotinate with dipalmitoylphosphatidylcholine," Journal of Lipid Research, v.46, 2005, p. 2415.
H.-J. Lehmler, W. Xie, G. D. Bothun, P. M. Bummer, B. L. Knutson. "Mixing of Perfluorooctanesulfonic Acid (PFOS) Potassium Salt with Dipalmitoyl Phosphatidylcholine (DPPC)," Colloids and Surfaces B: Biointerfaces, v.51, 2006, p. 25.
Kaustav Ghosh, Hans J. Lehmler, Stephen E. Rankin, and Barbara L. Knutson. "Supercritical Carbon Dioxide Processing of Fluorinated Surfactant Templated Mesoporous Silica Thin Films," Langmuir, v.21, 2005, p. 6145.
M. Arora, P.M. Bummer and H.-J. Lehmler. "Interaction of a partially fluorinated heptadecanoic acid with diacyl phosphatidylcholines of varying chain length," Langmuir, v.19, 2003, p. 8843.
Rong Xing and Stephen E. Rankin. "Three Stage Multilayer Formation Kinetics During Adsorption of an Anionic Fluorinated Surfactant on Germanium 1. Concentration Effects," Journal of Physical Chemistry B, v.110, 2006, p. 295.
Rong Xing and Stephen E. Rankin. "Reactive Pore Expansion During Ammonia Vapor Post-Treatment of Ordered Mesoporous Silica Prepared with Mixed Glucopyranoside and Cationic Surfactants," Microporous and Mesoporous Materials, v.108, 2008, p. 65.
Rong Xing and Stephen E. Rankin. "Use of the Ternary Phase Diagram of a Mixed Cationic / Glucopyranoside Surfactant System to Predict Mesostructured Silica Synthesis," Journal of Colloid and Interface Science, v.316, 2007, p. 930.
S.E. Rankin, B. Tan, H.J. Lehmler, K.P. Hindman and B.L. Knutson. "Well-Ordered Mesoporous Silica Prepared by Fluorinated Surfactant Templating," Microporous and Mesoporous Materials, v.73, 2004, p. 197.
S.M. Vyas, J. Turánek, P. Knötigová, A. Kasná, V. Kvardová, V. Koganti, S.E. Rankin, B.L. Knutson, H.-J. Lehmler. "Synthesis and biocompatibility evaluation of partially fluorinated pyridinium bromides," New Journal of Chemistry, v.30, 2006, p. 944.
Tan, B; Vyas, SM; Lehmer, HJ; Knutson, BL; Rankin, SE. "Synthesis of inorganic and organic-inorganic hybrid hollow particles using a cationic surfactant with a partially fluorinated tail," ADVANCED FUNCTIONAL MATERIALS, v.17, 2007, p. 2500-2508.
Venkat R. Koganti and Stephen E. Rankin. "Synthesis of Surfactant-Templated Silica Films with Orthogonally Aligned Hexagonal Mesophase," Journal of Physical Chemistry B, v.109, 2005, p. 3279.
Xie, W; Kania-Korwel, I; Bummer, PM; Lehmler, HJ. "Effect of potassium perfluorooetanesulfonate, perfluorooctanoate and octanesulfonate on the phase transition of dipalmitoylphosphatidylcholine (DPPC) bilayers," BIOCHIMICA ET BIOPHYSICA ACTA-BIOMEMBRANES, v.1768, 2007, p. 1299-1308.
Y.W. Kho, D.C. Conrad and B.L. Knutson. "Phase Behavior of CO2-Expanded Fluorinated Microemulsions," Langmuir, v.20, 2004, p. 2590.
