研究生: |
趙余亘 Yu-Hsuan Chao |
---|---|
論文名稱: |
氮摻雜碳及硒化鈷氧還原電化學觸媒 Nitrogen-doped carbon and cobalt selenide electrocatalysts for oxygen reduction reaction |
指導教授: |
蔡大翔
Dah-Shyang Tsai |
口試委員: |
陳燿騰
Yaw-Terng Chern 江志強 Jyh-Chiang Jiang 林秀麗 Hsiu-Li Lin |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2011 |
畢業學年度: | 99 |
語文別: | 中文 |
論文頁數: | 132 |
中文關鍵詞: | 氮摻雜碳 、硒化鈷 、氧氣還原反應 |
外文關鍵詞: | N-doped carbon, CoSe2, Oxygen Reduction Reaction |
相關次數: | 點閱:375 下載:0 |
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PEMFC轉化效率高、啟動時間短且乾淨無污染。具有極大潛力作為未來替代能源。但其商業化的阻礙為低耐用度與高成本。而目前研究指出,氮摻雜碳觸媒(N-doped Carbon)與硒化鈷觸媒(CoSe2)雖其活性與穩定性均與白金仍有著差距,但低廉的價格仍讓其有潛力取代白金觸媒的替代品。而本研究將會詳細探討此兩種觸媒其合成方式與分析測試。
以乙二胺-甲醛系統,並摻入鐵鈷金屬輔助,在硝酸預處理過的碳黑上進行縮合反應,並進行高溫熱處理後以溼球磨法打散團聚而得到最後的氮摻雜碳觸媒。由旋轉環盤電極進行電化學測試:線性掃描伏安法測試(LSV)測量其氧氣還原活性,啟動電位為0.831 V (vs. NHE)、半波電位為0.667 V (vs. NHE)。而進行1000圈循環伏安法測試穩定度後,比較半波電位的衰退為0.031V。而過氧化氫的產率最高為3.7%。由元素分析儀精確定出氮含量為5.09 wt%;XPS分析顯示系統中為四種主要氮-碳鍵結:40.28% 之pyridinic-N、 24.80% 之pyrrolic-N,與剩下比例之quarternary-N與pyridinic oxide;拉曼光譜由ID/IG為1.05,預測石墨碳邊角面上的扭曲結構,最後由TEM觀察觸媒的表面型態。
採用羰基鈷與過量的硒作搭配並承載於氮摻雜碳上,進行熱處理得到氮摻雜碳負載硒化鈷觸媒。最佳觸媒之啟動電位為0.792 V (vs. NHE)、半波電位為0.711 V (vs. NHE)。而進行1000圈循環伏安法測試穩定度後,可發現硒化鈷的穩定性不佳,在高電位酸性溶液下可能溶解剝落,比較半波電位的衰退為0.067 V。而過氧化氫的最高產率也將提高為6.4%;而由XRD可鑑定CoSe2為尺寸 21 nm的斜方相與28-29 nm的立方相共存。
Proton exchange membrane fuel cell (PEMFC), a high energy efficient and environmentally friendly system, is considered to be a future power supplier. The major barriers for PEMFC commercialization are high cost and insufficient cycle life, which mainly arise from the platinum-based catalysts of limited supply. N-doped carbon and non-noble metal chalcogenides are potentially substitutes for platinum catalysts, although their activities are less than platinum.
In this investigation, we attempt to promote the activity of cobalt selenide with N-doped carbon. We coated cobalt and iron doped ethylenediamine–formaldehyde chelate complexes on Vulcan support. The N-doped carbon catalyst was subsequently synthesized by heat treatment and wet ball-mill to break down aggregations.The optimal catalyst of N-doped carbon demonstrates an onset potential 0.831 V (vs. NHE), half-wave potential (E1/2) 0.667 V (vs. NHE) when reducing saturated oxygen in 0.5 M H2SO4, measured with the rotating disk voltammetry. It has excellent stability, showing only 0.031V E1/2 decay after 1000 cycles. It also generated less than 3.7% H2O2, accompanying oxygen reduction. This N-doped carbon catalyst contains 5.09 wt% nitrogen, measured with elemental analysis. XPS analysis reveals four types of nitrogen sites. Among them, the pyridinic-N site occupies 40.28%, the pyrrolic-N site takes up 24.80%, and the quarternary-N and pyridinic oxide make up the rest. Raman results indicate a moderate distortion of the graphitized edge, with ID/IG 1.05. TEM shows the morphology of the catalyst.
The catalyst activity is improved when cobalt selenium (CoSe2) is integrated with N-doped carbon properly, even though the activity improvement and the stability of this compound catalyst are much less than the catalyst of RuSe2 and N-doped carbon that our group synthesized previously. One salient feature of CoSe2 and N-doped carbon is its relatively low material cost.The best compound catalyst exhibits an onset potential 0.792 V (vs. NHE), half-wave potential (E1/2) 0.711 V (vs. NHE) on oxygen reduction. However, CoSe2 seems unable to withstand the 1000 CV cycles of stability test, the compound catalyst shows a 0.067 V E1/2 decay after 1000 cycles. It also shows a higher H2O2 yield 6.4%. Two crystalline phases are found in CoSe2 catalyst, including the 21 nm particles of orthorhombic phase and the 28-29 nm particles of cubic phase.
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