Alloy catalysts for fuel cell-based alcohol sensors
Zamanzad Ghavidel, Mohammadreza
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Direct ethanol fuel cells (DEFCs) are attractive from both economic and environmental standpoints for generating renewable energy and powering vehicles and portable electronic devices. The cost and performance of the DEFCs are mainly controlled by the Pt-base catalysts used at each electrode. In addition to energy conversion, DEFC technology is commonly employed in the fuel-cell based breath alcohol sensors (BrAS). BrAS is a device commonly used to measure blood alcohol concentration (BAC) and enforce drinking and driving laws. The BrAS is non-invasive and has a fast respond time. However, one of the most important drawback of the commercially available BrAS is the very high loading of Pt employed. One well-known and cost effective method to reduce the Pt loading is developing Pt-alloy catalysts. Recent studies have shown that Pt-transition metal alloy catalysts enhanced the electroactivity while decreasing the required loadings of the Pt catalysts. In this thesis, carbon supported Pt-Mn and Pt-Cu electrocatalysts were synthesized by different methods and the effects of heat treatment and structural modification on the ethanol oxidation reaction (EOR) activity, oxygen reduction reaction (ORR) activity and durability of these samples were thoroughly studied. Finally, the selected Pt-Mn and Pt-Cu samples with the highest EOR activity were examined in a prototype BrAS system and compared to the Pt/C and Pt3Sn/C commercial electrocatalysts. Studies on the Pt-Mn catalysts produced with and without additives indicate that adding trisodium citrate (SC) to the impregnation solution improved the particle dispersion, decreased particle sizes and reduced the time required for heat treatment. Further studies show that the optimum weight ratio of SC to the metal loading in the impregnation solution was 2:1 and optimum results achieved at pH lower than 4. In addition, powder X-ray diffraction (XRD) analyses indicate that the optimum heat treatment temperature was 700°C where a uniform ordered PtMn intermetallic phase was formed. Although the electrochemical active surface area (ECSA) decreased due to the heat treatment, the EOR activity of Pt-Mn samples was improved. Moreover, it was shown that the heat-treated samples prepared in the presence of SC showed superior the EOR activity compared to the samples made without SC. The Pt-Cu/C alloys were produced by three different methods: impregnation, impregnation in the presence of sodium citrate and microwave assisted polyol methods. These studies showed that the polyol method was the optimum method to produce the Pt-Cu alloy. The XRD analysis indicates that the heat treatment at 700 °C developed catalysts rich in the PtCu and PtCu3 ordered phases. The highest EOR activity was measured for the Pt-Cu/C-POL (sample made by the polyol method) and heat treated at 700°C for 1h. Comparing the EOR activity of the Pt-Cu and Pt-Mn samples also demonstrates that the heat treated Pt-Cu/C-POL sample showed higher EOR activity compared to the Pt-Mn samples. These results indicate that the benefits of thermally treating alloy nanoparticles could outweigh any activity losses that may occur due to the particle size growth and the ECSA loss. Besides, accelerated stress tests (ASTs) illustrate that the heat treatment improved the durability of the Pt-Mn and Pt-Cu samples. The durability and EOR activity of the heat treated Pt-Mn and Pt-Cu samples was similar or better than commercial samples. On the other hand, the ORR activity of Pt-Mn and Pt-Cu after the heat treatment was slightly lower than the commercial samples but the ORR activity loss can be compensated by the economic benefits from using the lower Pt loading. Finally, studying the alcohol sensing characteristic of different samples shows that the heat treated Pt-Mn and Pt-Cu catalysts could be used for the ethanol sensing. Additionally, among the different commercial samples tested for ethanol sensing, Pt-Sn/C showed the highest sensitivity but with slightly higher standard deviation. Further studies on the Pt- Cu/C and Pt-Mn/C samples indicate that the heat treatment improved the sensitivity of these samples and the highest normalized sensitivity among all the samples belonged to the Pt-Cu/C-POL (sample produced by polyol method) and heat treated at 700°C. It can be concluded that the heat treated Pt-Mn and Pt-Cu samples could be used as an alternative to replace Pt black in commercial sensors which would dramatically decrease the Pt loading. This could reduce the price and increase the sensitivity of commercial alcohol sensors.