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Ion-Pair Behavior Between Polyoxometalates Anion and Alkali Metal Cation

Ye, Songtao
http://rave.ohiolink.edu/etdc/view?acc_num=akron1522253761785623

Abstract Details

2018, Master of Science, University of Akron, Polymer Science.
Ion-pair behavior describes the partial association of oppositely charged ions in electrolyte solutions. Previous study mainly focused on the ion-pair behavior between simple ions, such as ion pairing in NaCl solution as well as ion-pair interactions in supramolecular complexes and biological associations. However, very few attentions have been placed on the solution system with particle sizes in between. Recently, a group of well-defined, huge anionic cluster named polyoxometalates (POMs) have been synthesized and well characterized. The size of POMs is around nanometer scale, which is exactly between simple ions and large colloids. The solution behavior for POMs is much different form simple electrolyte solutions or large colloids. As a result, it is interesting to study the ion-pair behavior for POMs in solution. Herein, ion-pairs between Lacunary Keggin type POMs and alkali metal cations are investigated. The result showed that ion-pairs are formed between alkali cations and the “pocket” area on the surface of Lacunary Keggin type POMs – K7PW11O39. Electrostatic interaction and the entropy gain during the solvation shell lost were considered major driving forces during the ion-pair formation. Smaller alkali cations (e.g., Li+ and Na+) tended to form contact ion-pair (CIP) which result in an elevated enthalpy change measured by Isothermal Titration Calorimetry (ITC). Larger alkali cations (e.g., Rb+ and Cs+) favored a loose type of ion-pair – solvent separated ion-pair (2SIP) and solvent shared ion-pair (SIP). Size exclusion between the “pocket” area on K7PW11O39 POM surface and alkali cation also played a significant role in determining the ion-pair structure. Results were further confirmed by Nuclear Magnetic Resonance Spectroscopy (NMR).
Tianbo Liu (Advisor)
Miyoshi Toshikazu (Committee Member)
Polymers
Ion-pair

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Citations

  • Ye, S. (2018). Ion-Pair Behavior Between Polyoxometalates Anion and Alkali Metal Cation [Master's thesis, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1522253761785623

    APA Style (7th edition)

  • Ye, Songtao. Ion-Pair Behavior Between Polyoxometalates Anion and Alkali Metal Cation. 2018. University of Akron, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1522253761785623.

    MLA Style (8th edition)

  • Ye, Songtao. "Ion-Pair Behavior Between Polyoxometalates Anion and Alkali Metal Cation." Master's thesis, University of Akron, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=akron1522253761785623

    Chicago Manual of Style (17th edition)

akron1522253761785623
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This open access ETD is published by University of Akron and OhioLINK.