質子交換膜燃料電池(Proton Exchange Membrane Fuel Cell, PEMFC) 在減碳環境的發展中備受期待且極具發展潛力，尤其在交通運輸方面。PEMFC陰極的氧還原反應(Oxygen Reduction Reaction, ORR)有Pt/C、PtCo/C等傳統Pt基礎的合金電催化劑，同時組合製備成奈米籠、奈米線、八面體等結構可具有優秀的電化學活性。然而摻入的過渡金屬容易在酸性環境中溶解，這讓觸媒的耐久性仍然是有待解決的問題。同樣的情況在氮摻雜碳載體的單原子金屬催化劑M-N-C(M=metal)中遭遇，也與耐酸性低的過渡金屬相關。
本研究藉由濕浸漬法將前驅物WCl6與商業Pt/C結合，製備出亞奈米等級的W修飾Pt奈米顆粒，成為更具電化學耐久性的W-Pt/C介金屬電催化劑。考量到W具備高熔點的熱穩定性質，在與商業Pt/C的熱處理過程中包覆部分Pt奈米顆粒以及阻止顆粒間的移動，抑制了金屬觸媒燒結。在氧還原反應中，W提高了Pt/C催化劑在酸性環境的電化學耐久性。透過電化學實驗、TEM以及拉曼光譜的觀察，可以得知W的摻入提升了碳載體的抗腐蝕能力。
本研究使用旋轉圓盤電極(Rotating-Disk Electrode, RDE)的半電池電化學檢測，在加速壓力實驗(Accelerated Stress Test, AST)當中經歷30,000循環測試後，W-Pt/C的ORR活性損失為31.4%，商業Pt/C的損失則為51.6%。

Proton Exchange Membrane Fuel Cell (PEMFC) is highly anticipated and has great development potential in the development of a carbon reduction technology, especially in transportation. The Oxygen Reduction Reaction (ORR) as PEMFC cathode has traditional Pt-based alloy electrocatalysts such as Pt/C and PtCo/C which can be combined to prepare nanocages, nanowires, octahedral or other structures with excellent ORR electrochemical activity. However, the added transition metals are easily dissolved in an acidic environment, which makes the durability of the catalyst still a problem to be solved. The same situation is encountered in the nitrogen-doped carbon-supported single-atomic metal catalyst M-N-C (M=metal), which is also related to transition metals with low acid resistance.
In this study, the precursor WCl6 was combined with commercial Pt/C by a wet impregnation method to prepare sub-nanometer scales W-modified Pt nanoparticles, which became a more electrochemically durable W-Pt/C intermetallic electrocatalyst. Considering that W has a high melting point and thermal stability, it coats part of the Pt nanoparticle and prevents the movement of particles during the heat treatment with commercial Pt/C, thereby inhibiting the sintering of the metal catalyst. In the oxygen reduction reaction, W improves the electrochemical durability of the Pt/C catalyst in an acidic environment. Through electrochemical experiments, TEM and Raman spectroscopy observations, it can be known that the incorporation of W improves the corrosion resistance of the carbon support.
In this study, a rotating disk electrode (RDE) half-cell electrochemical detection was used. After 30,000 cycles of testing in the accelerated stress test (AST), the ORR activity loss of W-Pt/C was 31.4%, the loss of commercial Pt/C is 51.6%.

摘要 I
ABSTRACT II
目錄 IV
圖目錄 VI
表目錄 IX
一、緒論 1
1.1 前言 1
1.2 質子交換膜燃料電池(PEMFC) 2
1.2.1 簡介 2
1.2.2 氧還原反應(Oxygen Reduction Reaction, ORR) 4
1.3 基於PT的 ORR電催化劑 5
1.4 非貴金屬ORR電催化劑 7
1.5 研究動機 8
二、文獻回顧 9
2.1 概述 9
2.2 PT合金的ORR奈米電催化劑 9
2.3 PT/C為基礎的ORR奈米電催化劑降解 18
2.3.1 Pt降解 18
2.3.2 碳載體腐蝕 23
三、實驗方法與儀器 29
3.1 實驗藥品 29
3.2 實驗器材 29
3.3 分析儀器 30
3.4 旋轉圓盤電極(ROTATING DISK ELECTRODE, RDE) 30
3.5 實驗流程 31
3.5.1 W-Pt/C製備 31
3.5.2 製備電極 33
3.5.3 半電池架設 35
3.5.4 電化學分析實驗 36
四、結果與討論 39
4.1 W-PT/C產物分析 39
4.2 電化學分析 48
4.3 AST後的EOL-電催化劑分析 52
五、結論 56
六、未來工作 57
致謝 58
參考文獻 59

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