Keywords

Graphite intercalation compounds, Hydrogen as fuel, Layer structure (Solids), Manganese, Porphyrins

Abstract

The strength and success of the hydrogen economy relies heavily on the storage of hydrogen. Storage systems in which hydrogen is sequestered in a solid material have been shown to be advantageous over storage of hydrogen as a liquid or compressed gas. Many different types of materials have been investigated, yet the desired capacity and uptake/release characteristics required for implementation have not been reached. In this work, porphyrin aggregates were investigated as a new type of material for hydrogen storage. The building blocks of the aggregates are porphyrin molecules that are planar and can assume a face to face arrangement that is also known as H-aggregation. The H-aggregates were formed in solution, upon mixing of aqueous solutions of two different porphyrins, one carrying positively charged and the other one carrying negatively charged functional groups. The cationic porphyrin used was meso-tetra(4- N,N,N-trimethylanilinium) porphine (TAP) and it was combined with four different anionic porphyrins, meso-tetra(4-sulfonatophenyl)porphine (TPPS), meso-tetra(4-carboxyphenyl) porphine (TCPP), Cu(II) meso-tetra(4-carboxyphenyl) porphine, and Fe(III) meso-tetra(4- carboxyphenyl) porphine. The force of attraction that held two oppositely charged porphyrin molecules together was electrostatic attraction between the peripheral groups. Solid state aggregates were successfully isolated either by solvent evaporation or by centrifuging and freeze drying. TCPP-TAP and Cu(II)TCPP-TAP aggregates were shown to interact with hydrogen starting from 150 °C up to 250 °C. The uptake capacity was about 1 weight %. Although this value is very low, this is the first observation of porphyrin aggregates absorbing hydrogen. This opened the way for further research to improve hydrogen absorption properties of these iv materials, as well as other materials based on this model. Two other materials that are also based on planar building blocks were selected to serve as a comparison to the porphyrin aggregates. The first of those materials was metal intercalated graphite compounds. In such compounds, a metal atom is placed between the layers of graphene that make up the graphite. Lithium, calcium and lanthanum were selected in this study. Theoretical hydrogen capacity was calculated for each material based on the hydriding of the metal atoms only. The fraction of that theoretical hydrogen capacity actually displayed by each material increased from La to Ca to Li containing graphite. The weight % hydrogen observed for these materials varied between 0.60 and 2.0 %. The other material tested for comparison was KxMnO2, a layered structure of MnO2 that contained the K atoms in between oxygen layers. The hydrogen capacity of the KxMnO2 samples was similar to the other materials tested in the study, slightly above 1 weight %. This work has shown that porphyrin aggregates, carbon based and manganese dioxide based materials are excellent model materials for hydrogen storage. All three materials absorb hydrogen. Porphyrin aggregates have the potential to exhibit adjustable hydrogen uptake and release temperatures owing to their structure that could interact with an external electric or magnetic field. In the layered materials, it is possible to alter interlayer spacing and the particular intercalates to potentially produce a material with an exceptionally large hydrogen capacity. As a result, these materials can have significant impact on the use of hydrogen as an energy carrier.

Notes

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Graduation Date

2011

Semester

Spring

Advisor

Hampton, Michael D.

Degree

Doctor of Philosophy (Ph.D.)

College

College of Sciences

Department

Chemistry

Format

application/pdf

Identifier

CFE0003752

URL

http://purl.fcla.edu/fcla/etd/CFE0003752

Language

English

Length of Campus-only Access

None

Access Status

Doctoral Dissertation (Open Access)

Subjects

Dissertations, Academic -- Sciences, Sciences -- Dissertations, Academic

Included in

Chemistry Commons

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