ORCID Identifier(s)

ORCID 0009-0004-0019-5095

Graduation Semester and Year

Summer 2024

Language

English

Document Type

Thesis

Degree Name

Master of Science in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Krishnan Rajeshwar

Second Advisor

Rasika Dias

Third Advisor

Frederick M. MacDonnell

Abstract

Dolerophanite Cu2OSO4 is a rare mineral found almost exclusively in the fumaroles of volcano systems and is sensitive to temperature and humidity conditions. It has a monoclinic C2/m crystal structure characterized by two-dimensional layers composed of sulfate anions dispersed amongst copper (II) oxide backbones. There has been recent interest in dolerophanite due to the magnetic properties of its Kagome-like lattice as well as its potential use as a photocatalyst or Li-ion battery electrode. Literature on the material however has been limited by the available synthesis strategies. As such, this thesis work presents a novel strategy to produce dolerophanite through a time- and energy-efficient solution combustion synthesis methodology.

Physical analysis provided a comparison of dolerophanite samples prepared by ceramic method and solution combustion synthesis. Thermogravimetric analysis and differential scanning calorimetry were performed to better understand the thermal stability of dolerophanite. Kissinger first-order kinetics model was used to estimate the activation energy for the thermal decomposition of dolerophanite to copper (II) oxide and to copper (I) oxide. Suggested mechanistic pathways were presented for these decompositions. Kubelka-Munk transformation of the Tauc equation allowed diffuse reflectance data to estimate both direct and indirect optical bandgaps. Density functional theory calculations provided computational evidence for the experimentally observed bandgaps. Fourier transform infrared spectroscopy and Raman spectral data were used to characterize dolerophanite via the nuances in its Cu­–O and its S–O bonding framework.

Finally, suggested further experimentation to explore modifications to the solution combustion synthesis as well as potential avenues to explore the applications of dolerophanite were discussed.

Keywords

Chemistry, Solid state chemistry, Solution combustion synthesis, Materials, Physical chemistry, Materials chemistry, Dolerophanite, Copper (ii) oxide sulfate, Fumarolic minerals

Disciplines

Analytical Chemistry | Chemistry | Inorganic Chemistry | Materials Chemistry | Physical Chemistry

License

Creative Commons Attribution 4.0 International License
This work is licensed under a Creative Commons Attribution 4.0 International License.

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