This dissertation the syntheses of Pt-based binary and ternary alloy electrocatalysts using the transition metals of Co and Ni are presented. These electrocatalysts were synthesised by an impregnation-reduction procedure at high temperature whereby Pt supported on carbon, (Pt/C (40 percent), was impregnated with the various metal and mixtures thereof and reduced at high temperatures in a H2 atmosphere. The procedure was also designed in such a way so as to prevent the oxidation of the support material (carbon black) during the alloy formation. The resultant nanoparticles (9-12 nm) of Pt3Co/C, Pt3Ni/C and Pt3Co0.5Ni0.5/C were also subjected to a post treatment procedure by acid washing (denoted AW) to produce electrocatalysts of Pt3Co/C-AW, Pt3Ni/C-AW and Pt3Co0.5Ni0.5/C-AW to study the effect of acid treatment on these electrocatalysts. The synthesised electrocatalysts were then characterised by a number of physical and electrochemical techniques and compared to that of commercial Pt/C (Pt/C-JM, HiSpec 4000) as well as Pt/C catalysts (Pt/C-900 and Pt/C-900-AW) treated under the same conditions used for the alloy synthesis. The electrocatalysts were then used to fabricate MEAs that were loaded into commercial single test cells and characterised by means of polarisation curves and Electrochemical Impedance Spectroscopy (EIS). The extensive physical characterisation included Powder X-Ray Diffraction (PXRD) analysis, Transmission Electron Microscopy (TEM), elemental analysis by Energy Dispersive Spectroscopy (EDS) and metal loading by Thermo-Gravimetric Analysis (TGA). These studies showed that Pt-based alloy electrocatalysts were successfully synthesised with particle sizes ranging from 9 - 12 nm, within their respective atomic ratios and whereby no significant loss of carbon support occurred. This indicated that significant sintering or electrocatalyst particles occurred when compared to that of the starting Pt/C catalyst (3 – 4 nm). From the combined results of the physical characterisation procedures, it was also shown that leaching as a result of acid washing was catalyst dependent with Ni containing catalysts showing a significant degree of leaching compared to that of Co containing catalysts. Electrochemical characterisation in terms of Electrochemical Active Surface Area (ECSA) by Cyclic Voltammetry (CV) and ORR activity by Rotating Disc Electrode (RDE) analysis revealed that a significant decrease in the ECSA resulted from the increase in particle size and this had a major influence on the ORR activity. Furthermore it was found that a significant improvement in the ORR activity was achieved by the synthesis of Pt-based alloys. It was also found that catalytic properties of the acid washed electrocatalysts were substantially different from that of non-acid washed electrocatalysts. The experimental data confirmed that it was possibly to achieve better catalytic performance as compared to that of Pt/C at a lower material cost when Pt is alloyed with base transition metals. The trend observed from the ORR activity studies by RDE was successfully repeated in the in-situ fuel cell testing in terms of mass activity of the electrocatalysts. Of the electrocatalysts studied under „real‟ fuel cell conditions Pt/C-JM had the best performance compared to the others, with the ternary Pt3Co0.5Ni0.5/C showing better catalytic performance compared to the Pt3Co/C electrocatalyst. This was found to be due to a higher charge transfer resistance observed in Pt3Co/C as compared to that of Pt3Co0.5Ni0.5/C which was similar than that of the commercial Pt/C-JM catalyst with both Pt3Co/C and Pt3Co0.5Ni0.5/C-AW having similar but higher ohmic resistances than that of Pt/C-JM as determined by electrochemical impedance spectroscopy. The results showed that a great potential exist to improve the catalytic performance of low temperature PEM fuel electrocatalysts at a reduced cost as compared to that of pure Pt provided a method of controlling the particle size was established.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:nmmu/vital:10428 |
| Date | January 2012 |
| Creators | Mohamed, Rhiyaad |
| Publisher | Nelson Mandela Metropolitan University, Faculty of Science |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis, Masters, MSc |
| Format | x, 111 leaves, pdf |
| Rights | Nelson Mandela Metropolitan University |
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