臺灣博碩士論文加值系統

本研究以實驗室先前開發的鉑奈米溶膠觸媒(Pt sols)進行AuCl3(aq)沈積改質，製作Au修飾的Pt顆粒，並探討金的添加對燃料電池陰極白氧氣還原反應的活性與安定性影響。雙金屬觸媒顆粒係以甲醇-citrate系統製作2-3 nm的單顆Pt奈米顆粒，再於室溫下添加不同量的AuCl3經過8小時可製備出4-5 nm的PtAu雙金屬觸媒。TEM分析顯示添加AuCl3後經不同的時間攪拌後，所得PtAuxML顆粒有逐漸變大的趨勢，可推論Au還原在Pt顆粒表面上。藉由XANES分析得知sols溶液的Pt L3-edge white line上升，由Pt還原態偏向氧化態，顯示有PtAu的氧化還原作用，XPS則顯示乾燥後奈米顆粒的Pt金屬價態帶有微小的負電荷，顯示Pt-Au間有電子轉移作用。XRD分析則顯示可能具有的合金結構。電化學實驗結果顯示，隨Au添加攪拌時間增加，所得PtAuxML奈米雙金屬的電化學活性面積及ORR特徵活性有提升的趨勢，但對於ORR反應的觸媒穩定性並無顯著的提升效果，而CO剝除實驗顯示Au添加觸媒可使CO氧化峰提早，可見PtAu奈米雙金屬顆粒可改善燃料電池效能及增加活性。

Platinum nanoparticles of 2 - 3 nm were modified by depositing submonolyaer Au. The effect of Au deposition on the activities and stability of Pt nanoparticles were examined for the cathodic oxygen reduction and the CO oxidation reactions.
The deposition using AuCl3 was carried out at 298 K in the methanol-citrate system containing the preformed Pt sol. TEM analysis indicated that the PtAu nanoparticles increased in size with agitation time after addition of AuCl3 and PtAu of 4 – 5 nm size were found after 8 h of agitation. An increase in the white line intensity of Pt L3-edge x-ray absorbance over the PtAu sols suggests that Au deposition may occur via redox reactions. On the other hand, XPS analysis indicated slight increase in Pt electron density in the PtAu collected over carbon support. This suggests charge transfer from Au to Pt. XRD data indicated that PtAu alloy nanoparticles were obtained.
Electrochemical analysis indicated slight increase in per-gram electrochemical active area and per-gram oxygen reduction activity with increase of agitation time after Au addition. However, no significant change in the specific oxygen reduction activity was found. The PtAu showed better CO oxidation activity than the unmodified Pt sols, indicated by the lower onset potential during CO stripping experiments. The results of this study indicated that submonolayer Au deposition can improve the electrochemical activities of Pt catalysts for both the oxygen reduction reaction and the CO oxidation in acidic electrolyte.

摘要....I
Abstract....II
目錄....III
圖索引....V
表目錄....VIII
第一章 緒論....1
1.1 前言....1
1.2 燃料電池....1
1.2.1 燃料電池的種類....2
1.2.2 燃料電池的工作原理....3
1.3 文獻回顧....5
1.3.1 燃料電池電極觸媒難題....5
1.3.2 雙金屬觸媒在燃料電池電極反應的應用....6
1.3.3 雙金屬奈米顆粒觸媒製備....11
1.4 旋轉圓盤電極於電化學反應的應用....12
1.5 分析氧氣還原的方法....18
1.6 實驗目的與方法....23
第二章 實驗設備與方法....25
2.1 藥品與儀器設備....25
2.1.1 藥品....25
2.1.2 氣體....26
2.1.3 儀器....26
2.2 實驗方法....27
2.2.1 奈米溶膠顆粒製備....27
2.2.1.1 鉑奈米溶膠金屬顆粒製備....27
2.2.1.2 PtAu雙金屬奈米顆粒製備....27
2.2.2 材料鑑定分析....31
2.2.2.1 X光粉末繞射(X-Ray Diffraction, XRD)分析....31
2.2.2.2 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM)分析....31
2.2.2.3 X光吸收光譜(X-ray absorption spectrum, XAS)分析....32
2.2.2.4 X-射線光電子能譜儀(X-Ray Photoelectron Spectroscopy, XPS)分析....32
2.2.2.5 紫外-可見光(UV-vis)分析方法....33
2.2.3 電化學實驗方式....33
2.2.3.1 觸媒性能的量測....33
2.2.3.2 電化學實驗數據分析....35
第三章 結果與討論....37
3.1 PtAu雙金屬奈米觸媒的製備與結構鑑定....37
3.1.1 PtAu雙金屬奈米顆粒製備....37
3.1.2 XRD分析....47
3.1.3 XPS分析....51
3.1.4 XANES分析....54
3.1.5 TEM分析與EDS分析....56
3.2 電化學特性量測....65
3.2.1 氧氣還原陰極反應....65
3.2.1.1 鉑奈米溶膠系統....65
3.2.1.2 PtAu雙金屬奈米顆粒溶膠....68
3.2.1.3 不同反應時間下的PtAu雙金屬奈米顆粒溶膠....72
3.2.2 穩定性....79
3.2.2.1 PtAu雙金屬奈米顆粒溶膠....79
3.2.2.2 不同反應時間下的PtAu雙金屬奈米顆粒溶膠....83
3.2.3 CO氧化反應....89
3.2.3.1 PtAu雙金屬奈米顆粒的不同攪拌時間....89
第四章 結論....99
參考文獻....101
附錄A....105
附錄B 不同方法製得PtAu雙金屬奈米顆粒....106
附錄C 置換導電性高分子安定劑的Pt sols特性分析....110

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