Graduation Year
2019
Document Type
Dissertation
Degree
Ph.D.
Degree Name
Doctor of Philosophy (Ph.D.)
Degree Granting Department
Chemistry
Major Professor
Shengqian Ma, Ph.D.
Committee Member
Julie Harmon, Ph.D.
Committee Member
Jianfeng Cai, Ph.D.
Committee Member
Arash Takshi, Ph.D.
Keywords
Zeolitic-Imidazolate Frameworks, Electrocatalysis, Oxygen Reduction, Hydrogen Evolution
Abstract
Rapid industrial globalization and technological development and energy consumption across the globe has significantly increased in response to mounting energy needs. The necessity for alternative and sustainable energy conversion devices has become apparent with the growth of energy utilization. In recent years, many research efforts have been made in the development of low-cost, efficient, environmentally friendly energy conversion devices. One type of energy conversion device, polymer electrolyte membrane fuel cells (PEMFCs), uses hydrogen oxidation at the anode and oxygen reduction at the cathode, with a solid-state proton conducting membrane between to generate energy with water as a by-product. PEMFCs use Nafion®, a sulfonated fluoropolymer-copolymer for proton transport; however, temperature restraints and the need for hydration limits the efficacy of this polymer. Moreover, the kinetics of oxygen reduction (ORR) are significantly slower at the cathode than the anode. Platinum is currently the industry standard, but these materials have limited resources, are expensive, and can be sensitive to carbon monoxide poisoning. Platinum is also the preferred catalyst for hydrogen evolution reactions (HER)—critical electrochemical reactions at the cathode for water splitting applications for the generation of hydrogen.
Metal-Organic Frameworks (MOFs) have been explored for proton conductivity and as electrode catalysts. The tunability of metal ions and organic linkers both in situ and post-synthesis allows for the targeted design of specific surface areas and topologies while fine tuning selective functionality. Furthermore, due to morphology retention upon pyrolysis, MOFs are good platforms for logical design both pre- and post- carbonization. Taking advantage of the amendable design, along with tunable porosity and growth in controlled dimensions, this work explores the modification of a zinc based MOF as a possible candidate for proton conduction, as well modification of zinc, cobalt, and iron based MOFs for ORR catalysis.
Post-synthetic modification was employed as a technique to oxidize the imidazolate ligand to include carboxylic acid functionality of a zinc based MOF. Proton conductivity generally arises from the mobility of the charge carriers present (i.e. carboxylates and phosphates). The incorporation of Brønsted acidity by way of free carboxylates is often challenging, as these are generally sites of coordination in the framework. Herein, we report the successful augmentation of Brønsted acidity with retention of framework crystallinity in a robust MOF.
Additionally, the effects of metal content and carbonization temperature of MOFs were explored for ORR and HER. Cobalt and iron were doped either pre- or post-synthesis and carbonized in an inert atmosphere at various temperatures to generate MOF-derived carbons with catalytically active centers without the need for additional support. Carbons with parent MOFs containing moderate amounts of cobalt doping in a bimetallic Co/Zn MOF, or carbons that contained no zinc in the parent material, showed excellent electrocatalytic performance for ORR when carbonized at temperatures just at or above the boiling point of zinc. Zinc based MOFs were doped with various amounts of iron post-synthesis and prior to carbonization in an inert atmosphere. The formation of iron nanoflakes and nanorods on the surface of these carbons generated from the pyrolysis of these iron doped MOFs yielded high surface areas and outstanding electrochemical performance for ORR in both acidic and alkaline media. Likewise, excellent HER catalysis was exhibited by the MOF-derived carbon matrix with the highest iron loading pre-carbonization and more disperse nanorods.
Not only does the amenability of MOFs make them a good platform for the direct inclusion of essential electrochemically active moieties, but it also allows for more targeted, nuanced, and rational design of materials needed to enhance proton conduction and electrochemical performance, particularly in cases on non-precious metal electrocatalysts where mechanisms are often not well-understood.
Scholar Commons Citation
Williams, Kia, "Metal-Organic Frameworks and MOF-derived Carbon Materials for Fuel Cell Applications" (2017). USF Tampa Graduate Theses and Dissertations.
https://digitalcommons.usf.edu/etd/7452
