如何將催化劑及其載體設計結合，使燃料電池鉑催化劑的電催化活性和耐久性可以獲得改善，並顯著節省成本，可視為作為探索取代碳質載體材料的部分努力。本論文主要是Magnéli氧化物擔載鉑催化劑的設計，合成和表徵工作。這對於延長質子交換膜燃料電池(PEMFC)使用壽命和保證可靠性，以及降低總生命週期的使用成本都具有重要意義。適當調控Magnéli氧化物載體具備相對高的導電性和高表面積，後者的特徵可讓鉑觸媒均勻分散和良好錨定於其載體上。
論文的第一部分工作強調“開發應用於氧氣還原反應之高比表面積Ti4O7載體材料”。分別使用PEG-400和葡萄糖還原前驅物，即乙醇鈦（IV）和氧化鈦（銳鈦礦）。結果表明：前者可以成功製備Ti4O7純相，而後者仍以金紅石為主。高比表面積達到135-160平方米/克。然而，因無定形碳仍殘留在所製備的Ti4O7中（約6-8重量％），限制了其在氧氣還原反應的實際應用。同時，在經過冷凍乾燥技術和氫還原之前先用食鹽水處理奈米結構二氧化鈦，則所獲得Ti4O7的表面積卻相當低（2 m2/g），仍不合適用於氧氣還原反應。因此，需要一種新的方法來解決此困境，以便在碳熱還原過程中，碳含量的增加和追求高表面積間的困境可以得到調和，使觸媒的催化活性和耐久性不致受到影響。
第二部分的工作是第一部分的直接延伸，但採取了不同的方法-“用於氧還原反應的抗腐蝕性二氧化鈦負載的有序金屬間鉑催化劑”。主要聚焦在氧化鈦載體上，原位形成結構有序鉑金屬間化合物。透過一個簡單的策略: 使用過硫酸銨（APS）作為氧化劑，經簡單的改質氧化聚合技術，利用聚苯胺在二氧化鈦上均勻沉積Pt。如此，還原TiO2載體和鉑奈米顆粒之間的強金屬載體相互作用（SMSI），方能被適當運用於電催化反應。電化學測量結果顯示，在相同鉑(Pt)載量的情況下，與現今常見的商用Pt/C（JM 20）觸媒相比，負載在氧化物上的鉑催化劑具有更好的催化活性和耐久性。鑒於觸媒表面的活性位址會因為吸附其他分子而導致失活的現象，實驗所觀察到活性和穩定性的提升，可歸因於相鄰鉑原子之間的距離和晶格參數的減小，幫助這些吸附分子容易脫附，釋放更多的活性位址。
第三部分為“氯化鈉介導有序金屬間鉑催化劑負載在Magnéli相氧化鈦於氧氣還原反應用”。這個部分利用即通過使材料尺寸奈米化，來提高單位體積表面原子數量。該策略不僅增加了表面能，而且降低了相變溫度，並且可在相對較低的溫度下使高溫相穩定。與之前需要高溫和更長反應時間的方法相比，本研究添加氯化鈉，在製備上有序的金屬間化合物Pt3Ti，以及Magnéli相氧化物如Ti3O5，確實可有效將降低處理溫度與縮短時間。但代價是會形成較大的粒子。因此，可透過控制升溫模式來兼顧相轉變與粒子成長。
在整個過程中，通過變化處理溫度及碳前驅物和銳鈦礦的比例，優化相關參數，同時亦進行金屬合金和Magnélii相氧化物的特徵鑑定。
電催化下碳擔載的鉑觸媒其電化學活性面積亦快速降低，但結構有序的金屬化合物在嚴苛的酸性環境下，可以表現出更好的耐受性。它們的電化學性能耐久性表現出顯著的改善，因此，極具潛力作為氧氣還原反應的非碳載體觸媒。
最後，論文的工作提供了製備貴金屬與非貴金屬合金化，以形成有序和耐腐蝕材料的方法，可以擴展到其他應用。

關鍵字: 氧氣還原反應、觸媒載體強交互作用、d-電子軌域空缺、金屬間化合物、Ti4O7、質子交換膜燃料電池

As part of tremendous efforts towards exploring stable alternatives for replacing the carbonaceous materials, engineering of both the catalysts and their supports towards more resilient platinum catalysts can potentially improve the activity and durability of the electrocatalysts for fuel cell catalysis and significant cost savings. This dissertation is mainly concerned with design, synthesis and characterization of oxide supported platinum catalyst. This is of great importance for both lengthening the operation life and at the same time ensuring the reliability, as well as reducing the cost in the life cycle of PEMFC. Well regulated Magnéli phase oxide support, provides various advantages in terms of conductivity and surface area. The later in particular opens the avenue for highly dispersed and well-anchored Pt catalyst particles over their respective support.
The first part of this work emphasized on “High surface area Ti4O7 support material for oxygen reduction reaction. PEG-400 and glucose respectively were used as reducing agents for precursors, namely, Ti (IV) ethoxide and titanium oxide (anatase). The results revealed that pure Ti4O7 phase was successfully fabricated in the former (PEG as reductant) while the later (glucose as reductant) still contains rutile as a dominant phase. High specific surface area was achieved ranging from 135 and 160 m2/g using PEG and Glucose as reductant respectively. Moreover, different ways of removing amorphous carbon residue (6-8 wt. %) in the attained Ti4O7 were also tested using various acid and base treatments. However, carbon residue still cannot be completely removed. Concurrently, sovlothermally prepared anatase precursor was also treated with NaCl before being subjected to freeze drying technology followed by hydrogen reduction at high temperature calcination. However, the acquired Ti4O7 is of limited surface area (2 m2g -1), which also deters its application towards ORR in fuel cell application.
The second part of this work is the immediate extension of the first but with a different approach for improvement.” It mainly focuses on the synthesis and characterization of structurally ordered intermetallic Pt3Ti, supported on oxygen deficient titanium oxide, which evolved in situ during the high temperature treatment. A simple strategy was developed to deposit Pt on TiO2 uniformly with polyaniline via a simple modified oxidative polymerization technique followed by high temperature calcination before oxide supported ordered intermetallic Pt3Ti was successfully fabricated.
The electrochemical measurement results indicated that the resulting electrocatalyst displayed highly enhanced specific activity (41.6 µA cm-2) as compared to Pt/C (JM 20) with value of 15.7 µA cm-2. The increase in electrocatalytic activity is ascribable to a change by geometric effects, which resulted from smaller lattice constant and shorter neighboring Pt-Pt bond length as compared to its fcc counterpart (as synthesized and Pt/C).
The stability test also revealed that the optimal catalyst has shown a gain of 16 % in terms of ECSA; while the commercial based catalyst lost 65 % of its original value, after 2000 potential cycles. This extraordinarily large stability in harsh acidic environment originates from remarkable thermodynamic stability of Pt3Ti due to its high heat of formation. Furthermore, since oxidation is the major deactivation mechanism during long-term operation, inclusion of titanium in the pt lattice raises the oxidation potential for platinum.
The third part is concerned with Sodium Chloride mediated transformation of titania towards Magnéli phase supported ordered intermetallic Pt3Ti. This section partly makes use of the fact that an increase of the number of surface atoms relative to the bulk would be achieved by minimizing the size of the particles down to the nanoscale. The strategy not only increasse the surface energy but also reduce the phase-transition temperatures and brings about stabilization of high-temperature phases at relatively lower temperatures. The structural analysis results disclosed that apart from ordered intermetallic Pt3Ti phase, the required Magneli phase oxides, such as Ti3O5, were also evolved at a shorter reaction time in the presence of NaCl. However, this costs rapid increase in Pt crystallite size (about 30 nm) even at lower temperature, (750 °C). Hence, an interplay between the merit (faster phase transformation) and demerit (rapid particle growth) have been sought by controlling the heating stage during the course of calcination. By employing two heating stages, the required oxide supported ordered intermetallic alloys, with smaller Pt crystallite size (about 12-18 nm) have been successfully synthesized when annealed at even higher temperature, 850-950 °C.
Optimizations of temperature were carried out in the entire works. Characterizations of the formation of Magneli phase oxides concurrently with these alloys, was investigated. The electrochemical measurement results demonstrate that the optimal catalyst has shown a specific activity of 38.6 µA cm-2, over twice that of commercial based catalyst. The optimal catalyst also demonstrated remarkable resistance against corrosion with only 5 % loss in terms of ECSA.
The current work provides feasible approach that can be extended to other technological applications by alloying precious metals with less precious ones to prepare more ordered and corrosion-resistant materials.
Keywords: ORR, SMSI, d-band vacancies, intermetallic compound, Ti4O7, PEMFCs

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