A WATER-SOLUBLE COBALT SULFIDE SUPERATOM FOR FLOW BATTERY APPLICATIONS AND CRYSTALLINE FRAMEWORK SYNTHESIS

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Freeman, M. (2019). A WATER-SOLUBLE COBALT SULFIDE SUPERATOM FOR FLOW BATTERY APPLICATIONS AND CRYSTALLINE FRAMEWORK SYNTHESIS. Unc Charlotte Electronic Theses And Dissertations.
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Abstract

Metal sulfide clusters are attractive components for flow batteries owing to the abundance of their constituent atoms and their tunable size, solubility, and redox properties. We prepared an atomically precise cobalt sulfide cluster, Co6S8(PTA)6•4HCl (PTA = 1,3,5-triaza-7-phosphaadamantane) (1), in a single step using low-cost precursors and water solubilizing phosphine ligands. Compound 1 represents the first structurally characterized, water-soluble cobalt-sulfide cluster. Remarkably, cluster 1 undergoes two electrochemically reversible oxidations in aqueous solutions and is stable in air. The first redox process is chemically reversible during charge–discharge experiments using a static cell and aqueous solutions of NaCl. An aqueous cell comprising methyl viologen (MV2+) as the anolyte and an anion exchange membrane provides an operating Vcell = 0.63 V.Additionally, cluster 1 was used as a preformed metalloligand in the synthesis of a novel coordination solid. Heating a 1:2 mixture Co6S8(PTA)6•4HCl and CuI in a solution of acetonitrile/water under solvothermal conditions leads to the formation of dark black crystals. The resulting three-dimensional framework (2) contains three distinct cluster constituents (2[Co6S8(PTA)6•H+]•2[Cu4I4]•[Cu4I62-]) and exhibits reversible redox behavior in the solid state. Framework 2 was structurally characterized using single crystal X-ray diffraction and powder X-ray diffraction. The UV-Vis diffuse reflectance spectrum of framework 2 was measured and used to calculate the band gap (1.98 eV) based on the Kubelka-Munk function.

Details
Author

Freeman, Matthew

Title

A WATER-SOLUBLE COBALT SULFIDE SUPERATOM FOR FLOW BATTERY APPLICATIONS AND CRYSTALLINE FRAMEWORK SYNTHESIS

Physical Description

1 online resource (107 pages) : PDF

Date

2019

Degree Granting Institution

University of North Carolina at Charlotte

Abstract

Metal sulfide clusters are attractive components for flow batteries owing to the abundance of their constituent atoms and their tunable size, solubility, and redox properties. We prepared an atomically precise cobalt sulfide cluster, Co6S8(PTA)6•4HCl (PTA = 1,3,5-triaza-7-phosphaadamantane) (1), in a single step using low-cost precursors and water solubilizing phosphine ligands. Compound 1 represents the first structurally characterized, water-soluble cobalt-sulfide cluster. Remarkably, cluster 1 undergoes two electrochemically reversible oxidations in aqueous solutions and is stable in air. The first redox process is chemically reversible during charge–discharge experiments using a static cell and aqueous solutions of NaCl. An aqueous cell comprising methyl viologen (MV2+) as the anolyte and an anion exchange membrane provides an operating Vcell = 0.63 V.Additionally, cluster 1 was used as a preformed metalloligand in the synthesis of a novel coordination solid. Heating a 1:2 mixture Co6S8(PTA)6•4HCl and CuI in a solution of acetonitrile/water under solvothermal conditions leads to the formation of dark black crystals. The resulting three-dimensional framework (2) contains three distinct cluster constituents (2[Co6S8(PTA)6•H+]•2[Cu4I4]•[Cu4I62-]) and exhibits reversible redox behavior in the solid state. Framework 2 was structurally characterized using single crystal X-ray diffraction and powder X-ray diffraction. The UV-Vis diffuse reflectance spectrum of framework 2 was measured and used to calculate the band gap (1.98 eV) based on the Kubelka-Munk function.

Genre

masters theses

Subjects--Topics

Chemistry

Degree

M.S.

Keywords

Clusters
Copper
Framework
Metal Chalcogenide
Redox Flow Batteries
Superatom

Subject Area

Chemistry

Advisor(s)

Bejger, Christopher

Committee Members

Smith, Stuart
Merkert, Bernadette
Rabinovich, Daniel

Degree Note

Thesis (M.S.)--University of North Carolina at Charlotte, 2019.

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Rights Holder Information

Copyright is held by the author unless otherwise indicated.

Identifier

Freeman_uncc_0694N_12202

Permalink

http://hdl.handle.net/20.500.13093/etd:2605