Author ORCID Identifier
https://orcid.org/0000-0002-6551-4673
Date of Award
2025
Document Type
Thesis (Ph.D.)
Department or Program
Chemistry
First Advisor
Katherine A. Mirica
Abstract
Conductive framework materials, namely metal─organic frameworks (MOFs) and covalent organic frameworks (COFs), are uniquely poised to serve as gaseous chemiresistive sensors. This dissertation systematically investigates the structure–property−performance relationships within these materials for the low-power, sensitive, and selective detection of toxic gases of biological and toxicological importance.
Chapter 1 highlights conductive framework materials as a burgeoning area of research for application in electronically transduced devices as chemiresistors. We present a logical compilation of work using novel framework materials design and synthesis to build highly tunable, processable, and versatile chemiresistors for the detection and differentiation of gases.
Chapter 2 introduces the use of hexahydroxytriphenylene-based MOFs for gas detection. The structure–property−performance relationships are investigated through comparative sensing, in conjunction with spectroscopic investigations. Mechanistic details are put forth to rationalize the incredible ability for the array to selectively detect and differentiate various mixtures of gases during dual analyte synchronous exposure.
Chapter 3 details the synthesis of novel phthalocyanine-based COFs for the detection and differentiation of gasotransmitters and ammonia for improved gas sensitivity compared to previous materials. We detail the fabrication of robust COF devices and their performance as chemiresistive sensors in dry and humid environments of nitrogen and air. This work improves upon the field in terms of sensor array performance, while also fundamentally probing these materials to deconvolute the mechanisms of material−analyte interactions.
Chapter 4 details the development and implementation of an educational experiment for students consisting of the synthesis and activation of a cyclodextrin MOF for passive CO2 detection and uptake. The experiment provides students with a practical and accessible introduction to fundamental chemical concepts and the principles of green chemistry.
The appendix puts forth preliminary data detailing the effect of metal center location and identity within a bimetallic MOF on the chemiresistive properties. Precise control over atomic composition and morphology is used to deconvolute chemiresistive properties.
Finally, a concluding chapter discusses the findings and implications of the dissertation work in the broader context of the field, summarizing the fundamental insights.
Recommended Citation
Benedetto, Georganna Christ, "Framework Material-Based Chemiresistive Arrays for the Detection and Differentiation of Toxic Gases" (2025). Dartmouth College Ph.D Dissertations. 380.
https://digitalcommons.dartmouth.edu/dissertations/380
