直接甲醇燃料電池用鈀-碳-鐵合金觸媒之開發及其特性研究

Development and Characterization of Pd-C-Fe Electrocatalysts Used in Direct Methanol Fuel Cells

葉雲傑(Yun-Chieh Yeh)

指導教授 ： 劉如熹

國立臺灣大學/理學院/化學研究所/碩士(2008年)

https://doi.org/10.6342/NTU.2008.00121

摘要

目前全球能源需求日益提升，於取得能源同時對於環境之威脅亦相
對提升，有鑑於此，目前世界各國正極力投入燃料電池相關研究藉以
開發新型之綠色能源。
燃料電池乃藉化學反應以產生電能，其中電化學觸媒於燃料分解反
應中扮演不可或缺之角色。傳統甲醇燃料電池用觸媒乃為鉑金屬及其
相關合金粒子並使用不同碳材做為載體以增加該觸媒之催化效能，然
而鉑金屬價格高昂、蘊藏量短少且於操作過程中具甲醇毒化之缺點，
此對該觸媒之普及無疑為一大威脅，因此，非鉑觸媒之發展以逐漸受
到重視。據目前文獻指出鈀金屬觸媒具高抗甲醇毒化特性，該特性對
於甲醇燃料電池壽命之延長具相當之助益；為提升鈀金屬之催化活
性，於鈀金屬中參雜不同之過渡金屬乃為一有效之方法，然而對於電
化學活性提升之現象目前仍未有一正確之機制提出。
本研究以含浸法製備PdCFe/C 觸媒，並以X 光吸收光譜進行樣品
結構分析以建立觸媒合成機制；觸媒氧氣還原活性及甲醇穿透測試方
面乃以循環伏安電位儀進行測試，並配合理論計算以建立氧氣於還原
過程中之行為；由於觸媒於酸性電解質下操作觸媒粒子及碳材將因酸
蝕作用而流失，有鑑於此，本研究分別以含浸法及逐滴添加法還原金
單層(Au monolayer)於PdCFe/C 表層以期觸媒抗酸能力之提升並以感應
偶合電漿原子吸收光譜儀測試觸媒抗酸能力，由研究結果顯示，藉金
原子層之保護，觸媒抗酸能力得以提升顯示其為一有效保護觸媒並延
長期使用壽命之方式。

關鍵字

X光吸收光譜 ； 非鉑觸媒 ； 鈀碳鐵 ； 直接甲醇燃料電池

並列摘要

With global energy demand growth and human impacts on the
environment, to raise the requirements of each country on fuel cell research
and development is increasing.
A fuel cell is a device that generates electricity by a chemical reaction.
With the help of electrocatalyst, efficient decomposition of fuel could be
ultized. Platinum and its alloys supported on different kind of carbon
supports were used as traditional electrocatalyst in direct methanol fuel
cells (DMFCs). However, the high cost and the limited abundance are
showing potential threat for further application in real life. Moreover,
platinum-based catalyst suffered serious methanol-poisonoing problem
during cell operation. In this regard, non-platinum catalyst has received a
great attention during these years. Recent research has shown that Pd-based
catalyst has higher tolerance to methanol than Pt-based catalyst. It may
generate higher operational efficiency and can prolong the operation period
to the DMFCs. Most of recent investigations on Pd-based catalyst focus on
how alloying effect between Pd and other kinds of transition metals
affected the catalytic efficiency. However, the real reason for the
improvement of catalytic efficiency to these Pd-M alloy (M= transition
metal) is so far not fully understood.
In the present thesis, PdCFe/C electrocatalyst was facilitated by
impregnation method. X-ray absorption spectroscopy (XAS) was applied
for the structural investigations. The electrochemical behaviours towards
oxygen reduction reaction (ORR) and the methanol crossover effect were
studied by cyclic voltammery (CV). The formation mechanism of PdCFe/C
electrocatalyst and its catalytic activity were facilitated by above studies
and theoretical calculations. The corrosion of electrocatalysts and damage
of carbon support are commonly occuring during the operation of fuel cells.
To increase the acid tolerance and prolong the life time of electrocatalyst,
Au monolayer was deposited on the surface of PdCFe/C by modified
impregnation (IM) method and drop-by-drop (DBD) method. To perform
the acid tolerance test, the Inductively couple plasma- atomic emission
spectroscopy (ICP-AES) was applied. Based on ICP-AES test results, the
suppression of metal leaching was observed. It has also been proved that
the Au deposition method is the effective method for catalyst protection
during the cell operation under acid electrolytic conditions.

並列關鍵字

PdCFe ； non-platinum electrocatalyst ； X-ray absorption spectroscopy ； DMFCs

參考文獻

42. 李志甫，同步輻射在觸媒化學上的應用(一)，民93.

9. Cheng, L. C.; Hong, M. F.; Lee, M. S. J. Technol. 2007, 22, 71.

11. Schultz, T.; Beasher, R. Chem. Eng. Technol. 2001, 24, 12.

12. Hogarth, C. M. P.; Hards, G. A. Platinum Metals Rev. 1996, 40, 150.

13. Toda, T.; Igarashi, H.; Uchida, H.; Watanabe M. J. Electrochem. Soc.