A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers

Presented by: Cisco Jimenez

Overview
What are we studying? Why? Why is it important? Background information. Approaches and methods used to investigate. Data Conclusions. Future research.

Acknowledgements.

Super-Ultra-Brief and Also Short History of Fuel Cells

The phenomenon behind fuel cells was discovered in 1800, and the first attempts to engineer useable cells were made in 1889.

First fuel cells were designed by William Grove, but were more curiosity than practical.
First practical fuel cell ran on pure hydrogen, and was developed by Francis T. Bacon. A fuel-cell powered tractor was built in 1959. Honda develops and markets the first fuel cell powered cars in 2002.

Why arent we using fuel cells now?!?

Portability vs. efficiency.
Hydrogen fuel source.

Low reaction rates.

Renewable Energy
PEM Fuel Cells. High energy conversion efficiency. Minimal environmental impact.

How do

+ Fuel H

Cells Work?

Effective PEM Fuel Cells

High proton selectivity. Extended chemical and thermal stability. High H+ conductivity under low humidity conditions.

Effective Membranes
Perfluorosulfonic acid (PFSA) ionomers. Most widely used PEM is Nafion, by DuPont. Polytetrafluoroethylene (PTFE) backbone.

Functional group side chains vary by brand/type.

Approaches Used
High-Level Calculations performed: Energetically preferred optimized geometries. Proton dissociation. Hydrogen bonding behavior. Binding energies. Partial atomic charges. All calculations performed via Gaussian 09.

Geometry Optimizations
Geometry optimization over all degrees of freedom, without symmetry constraints. Hartree-Fock theory with 6-31G** split valence basis set. Resulting structures optimized with Beckes threeparameter functional, i.e. B3LYP DFT.

These results further refined by expanding the employed basis set to 6-311G**.
Done once without water, and then again with 5 water molecules, added one at a time in varying positions.

Sample Optimization

Other Calculations
Vibrational Frequencies Zero Point Energies Boys and Bernardi counterpoise (CP) CP corrected energies.

Binding energies.
All systems, each hydration level.

Results & Discussion

First pair: fully fluorinated sulfonyl amide. Structures modeled in a variety of positions.

We are interested in the dissociation tendencies of the imide Hydrogen.

Data for Imine Comparison 1

Second Pair: Partially fluorinated sulfonyl imides. Structures modeled in a variety of positions. We are again interested in the dissociation tendencies of the imide Hydrogen. Different functional groups were substituted at one end of each sulfonyl imide. Less e- withdrawing groups, less charge stabilization.

Data for Imine Comparison 2

Final comparison: pToluene vs sPEEK. Aromatic sulfonic acid ionomers.

Structures modeled in a variety of positions.

No longer looking at an imine hydrogen. Examining also the importance of the extended backbone in proton dissociation and binding energy.

Data for Comparison 3

Summary
Minimum energy conformations similar up to four water molecules for all structures.

Spontaneous dissociation occurred after addition of 3 water molecules in sulfonyl imides, 4 in sPEEK.
Solvent-separated ion pair configuration involving an Eigen cation and 4 water molecules was energetically preferred. Greater ability of conjugate base to bear negative charge as hydrogen dissociates impacts energy. sPEEK backbone makes inconsequential contribution to dissociation and binding energies. It is likely that Eigen and Zundel cations are important in the structural diffusion transfer of protons at low levels of hydration in materials of this type.

So What??
The presence of multiple interacting acidic groups and dynamic configurational changes and bond length fluctuations strongly influence proton mobility and the nature and state of the acidic protons. BEWARE: This study takes only a VERY small portion of the system in question into account. There are undoubtedly many other factors influencing proton migration in the media. Our goal was to explore how specific ionomer chemistry affects proton dissociation within the primary hydration of the acidic group.

Future Research.
Scale up the modeling to include a larger system.
More waters. Multiple functional groups. Inclusion of portions of hydrophobic backbone.

Invoke more complicated basis sets for better accuracy.

More data on charge-bearing electron-withdrawing groups and their ability to facilitate proton dissociation.

Acknowledgements
Jeffrey K Clark II Stephen J Paddison

Michael Eikerling
Michel Dupuis Thomas A Zawodzinski Jr. Dept. of Chemical & Biomolecular Engineering, University of Knoxville. Dept. of Chemistry, Simon Fraser University Chemical and Materials Science Division, Pacific Northwest National Laboratory, Richland Washington.

FIN