摘 要
本研究以改良直接甲醇燃料電池陽極觸媒為主要的研究課題。由於過去的研究成果顯示：在相同的金屬含量的條件下，採用多次含浸法所製得的觸媒電極的活性，明顯地比採用傳統一次含浸法所製成者好，而且若同時將碳奈米管(CNT)與碳黑(XC-72)以各一半的比例混合，含浸鉑與釕所製得的觸媒，其性能更佳。所以在此後續研究中，我們以改變碳材為主要的研究方向，除碳黑外，也使用中孔洞碳材(MC)，並研究不同碳材之孔洞型態與添加碳奈米管的效應。
結果顯示：以碳黑和中孔洞碳材為擔体，在相同的金屬含量的條件下，使用不同還原劑、前驅物之含浸濃度製備含Pt 10 wt % 之 Pt-Ru/C觸媒時，觸媒上Pt-Ru金屬微粒之粒徑、分散度皆會不同，進而影響到觸媒孔徑分佈、表面積(分佈)。觸媒孔徑分佈、表面積(分佈)對於觸媒催化甲醇氧化之活性有待進一步研究。多次含浸時由於金屬前驅物濃度較小，使觸媒上Pt-Ru金屬微粒之粒徑明顯下降，分散度與對甲醇氧化之電催化活性也有顯著的提升。採用多次臨濕含浸法製備電極觸媒時，含浸次數較多者之活性較佳。直接以商用碳黑、中孔洞碳材為擔体，經三次含浸製得10 wt % 之Pt-Ru/XC-72、Pt-Ru/MC觸媒，於相同條件下對甲醇之電催化活性可達E-TEK 20 wt % Pt-Ru/C商用觸媒的 95%、90%。
在含Pt 10 wt % 的 Pt-Ru/XC與Pt-Ru/MC中添加碳奈米管或含Pt 10 wt %的 Pt-Ru/CNT，可提高整體觸媒的活性。最佳添加量，前者為 5 wt %，後者為20 wt %，兩種觸媒的活性皆接近於E-TEK 20 wt % Pt-Ru/C商用觸媒。而20 wt % 之Pt-Ru/XC-72、Pt-Ru/MC各添加5 wt %與20 wt %之 CNT(含浸20 wt % Pt-Ru)混合製成觸媒之效能則較E-TEK提升20 % 與10% 。
在不同碳材中添加碳奈米管或已含浸Pt與Ru之碳奈米管時，除需考慮導電度、直徑、長度及捲曲程度外，亦需考量碳材本身之粒徑、孔徑分佈與表面積分佈。在後續研究中，將針對這些因素予以實驗探討。本研究成果也可應用到以氫氫為燃料之質子交換膜燃料電池 (PEMFC)。

Abstract

The main object of this study is to improve the performance of the anode catalyst in direct methanol fuel cell. The previous investigation reveals that with the same metal loading on carbon black, the performance of of the catalyst prepared by multiple impregnation for electrocatalytic oxidation of methanol is obviously better than that by single impregnation, and when the mixture of carbon black and carbon nanotube with a ratio of 1:1 was used as the support for Pt-Ru/C, the catalyst has the best electrocatalytic activity. In this succeeding work, four kinds of carbon materials were used as the supports for Pt-Ru/C, including carbon black(XC-72), mesoporous carbon(MC) and two different types of carbon nanotubes(CNT), the effect of pore structures of these carbon materials and the addition of CNT to XC-72 and MC on the
performance of Pt-Ru/C catalysts were investigated.

Experimental results reveal that when preparing 10wt% Pt-Ru/C with carbon black and mesoporous carbon as the supports, using the different reducting agents and concentrations of precursor would result in different Pt-Ru particles sizes and dispersion on carbon materials, in turn, would affect the surface area and pore size distribution of catalysts. However, their effects on the electrochemical performance should be further investigated. When the catalyst was prepared by multiple impregnation, because of the low precursor concentration, the size of Pt-Ru particles would be smaller and hence the dispersion of Pt-Ru particles and electrochemical performance would be better. Pt-Ru/XC and Pt-Ru/MC catalysts with 10 wt % Pt prepared by carbon black and mesoporous carbon as the support and by three-time impregnation have higher electrocataltytic activity for methanol oxidation. Their activities are about 95% and 90% of that of the commercial catalyst E-TEK
(with 20 wt % Pt), respectively.
Adding CNT or CNT(10), [CNT(x) represents CNT containing X wt % of Pt] to Pt-Ru/XC and Pt-Ru/MC would also improve the electrochemical performance. The optimum adding amounts of CNT(10) are 5 wt % for the former and 20 wt % for the latter. Their electrochemical performances are almost the same as that of E-TEK. The addition of 5 wt % and 20 wt % CNT(20) to Pt-Ru/XC and Pt-Ru/MC catalysts (both containing 20 wt % ) would give activities 20 % and 10 % higher than that of E-TEK Pt-Ru/C
catalyst containing 20 wt % Pt, respectively.

When CNT or CNT with loaded Pt-Ru will be added to Pt-Ru/carbon catalyst, electrical conductivity, diameter, length and entanglement of carbon nanotubes should be considered first. Besides, the particle size, surface area and pore size distribution of the carbon support are also important factors. In further studies, we will focus on those factors to elucidate how they affect the electrochemical performance. Note that the results obtained in the present study can be also applied to the proton exchange membrane fuel cell (PEMFC) with hydrogen as the feed.

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