The Application of Soft Chemical Reactions to Inorganic Layered Materials and the Characterization of the Thermodynamics using Isothermal Titration Calorimetry
Open Access
- Author:
- Rosas, Alyssa
- Graduate Program:
- Chemistry
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- January 15, 2021
- Committee Members:
- Thomas E Mallouk, Dissertation Advisor/Co-Advisor
Thomas E Mallouk, Committee Chair/Co-Chair
Raymond Edward Schaak, Committee Member
Miriam Arak Freedman, Committee Member
Mauricio Terrones, Outside Member
Philip C Bevilacqua, Program Head/Chair - Keywords:
- soft chemistry
inorganic layered materials
two-dimensional materials
layered
materials
isothermal titration calorimetry
titanate
niobate
mxene - Abstract:
- Soft chemistry has been used since the 1970’s to convert easy-to-prepare materials into ones that are more difficult to synthesize directly. In this dissertation, soft chemistry is used to design new materials, and transform existing ones into materials with increased functionality. Numerous techniques have been employed throughout this dissertation in order to gain a full fundamental understanding on the products of these soft chemical reactions and the thermodynamics that govern them. In Chapter 2, soft chemistry was used to design a synthetic route to a newly high-charge bearing two-dimensional nanosheets in order to follow up on a greater study of the optical responsed of this material in a strong magnetic field. Unilamellar exfoliated nanosheets prepared from the parent compound, K0.8Ti1.6Zn0.4O4 were successfully synthesized, with optimal sythetic conditions described In Chapter 3, soft chemistry was used to investigate the swelling behavior of MXenes as a way to understand why exfoliation onto unilamellar nanosheets is difficult to acheieve. In addition, the pillaring of MXenes using Al13 Keggin ions as the pillaring agent was also explored through intercalation and aggregation of products of crystal attrition. The highest loading of the pillaring agent was achieved through the crystal attrition route. Cross-sectional TEM imaging was used to gain preliminary insights on the possible layer stacking defects and interlayer cross-bonding in order to gain a better understanding as to why exfoliation on these materials is difficult to realize. In Chapter 4, isothermal titration calorimetry was successfully employed to quantify, for the first time, the thermodynamic parameters of basic soft chemical reactions of exfoliation, intercalation, and restacking applied to a layered niobate under wet synthetic conditions. This foundational study has also demonstrated the use of isothermal titration calorimetry as a powerful tool in studying soft chemical reactions applied to inorganic layered materials in aqueous conditions, and paved the way for future more complex reactions applied to inorganic layered materials to be further studied.