- Title
- Synthesis and characterization of binary and ternary palladium alloys for use as alternative counter electrode catalysts in dye sensitized solar cells
- Creator
- Zingwe, Nyengerai Hillary
- Subject
- Electrocatalysis Chemistry
- Date Issued
- 2020
- Date
- 2020
- Type
- Thesis
- Type
- Doctoral
- Type
- PhD (Chemistry)
- Identifier
- http://hdl.handle.net/10353/18513
- Identifier
- vital:42580
- Description
- The dye sensitized solar cell counter electrode facilitates the regeneration of the dye molecules thereby ensuring the provision of higher sunlight to electricity conversion efficiency. The standard platinum electrode suffers from low efficiency due to corrosion by the redox mediator as well as being extremely expensive due to high demand. As an alternative this research study illustrates the efforts undertaken to replace the standard platinum counter electrode with palladium alloy counter electrodes. Application of palladium alloys ensures sustenance of high catalytic activity by palladium which is as effective as platinum. Although palladium is equally as expensive as platinum, its application in the form of alloys minimizes the amount required to produce an effective counter electrode to 0.001-0.004 moles thereby ensuring the provision of high efficiency at a lower cost. Furthermore, charge transfer from the other alloyed elements to the palladium atom increases active sites leading to higher catalytic activity than platinum. Additionally, changes in crystal structure due to alloying enhances resistance to corrosion thus enabling the longevity of the alloy counter electrode in the electrolyte ___________________________________________________________________________ Electrochemical analysis was conducted to determine the catalytic functionality of the developed alloys in cobalt, ferrocene and iodine redox mediators. The binary (PdNi-reduced graphene oxide (rGO) and PdCo-rGO) and ternary (PdNiCo-rGO) palladium alloys were fabricated via a hydrothermal method. In order to determine the composition which could provide the maximum activity, optimization was conducted through variation of the molar ratios of the precursor solutions. The properties of the synthesized palladium alloys were determined using various techniques including x-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The developed alloys were observed to comprise of palladium, nickel, cobalt, and carbon atoms. The particles were spherical in nature for all the unsupported alloys with the carbon supported alloys exhibiting spherical particle wholly surrounded by graphene sheets. Cyclic voltammetry and electrochemical impedance spectroscopy analysis showed that the carbon supported alloys PdNi-rGO, PdCo-rGO and PdNiCo-rGO produced the highest catalytic activities due to the synergy between their respective alloys and the incorporated reduced graphene oxide. The high catalytic effectiveness of these alloys yielded power conversion efficiency in the order PdNiCo-rGO (9.01) > PdNi-rGO (8.4.%) > PdCo-rGO (6.56%) > Pt (5.7%) which were better than the platinum efficiency in the cobalt redox mediator. The higher efficiency in the cobalt redox mediator relative to the iodine electrolyte illustrates that they are viable alternatives to the, corrosive and volatile iodine. Obtained results show that, the high recombination rates between the photogenerated electrons and the oxidized dye molecule which have been reported to reduce power conversion efficiency in one electron redox mediators did not affect the performance of the cell. However, these higher recombination rates affected the ferrocene electrolyte leading to extremely poor efficiency metrics. The obtained results indicated that reduced graphene oxide supported PdNi-rGO, PdNiCo-rGO as well as the unsupported PdNi3 alloys could successfully be implemented as substitutes to the platinum counter electrode in dye sensitized solar cells. The application of the palladium alloys is vital for improving stability and power conversion efficiency, as well as reducing cost.
- Format
- 168 leaves
- Format
- Publisher
- University of Fort Hare
- Publisher
- Faculty of Science and Agriculture
- Language
- English
- Rights
- University of Fort Hare
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UFH Department of Chemistry
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