研究生: |
角順平 Shun-ping Chiao |
---|---|
論文名稱: |
摻鐵硒化釕黃鐵礦相觸媒對氧還原反應催化作用 Electrocatalysis of Iron-Substituted RuSe2 Pyrites toward Oxygen Reduction Reaction |
指導教授: |
蔡大翔
Dah-Shyang Tsai |
口試委員: |
萬本儒
Ben-Zu Wan 林昇佃 Shawn D. Lin 戴龑 Yian Tai |
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: | 2009 |
畢業學年度: | 97 |
語文別: | 中文 |
論文頁數: | 116 |
中文關鍵詞: | 硒化釕觸媒 、氧還原反應 、陰極觸媒 、觸媒穩定性 、甲醇容忍性 、選擇性 |
外文關鍵詞: | Ruthenium selenide catalyst, Oxygen reduction reaction, Cathode catalyst, Catalyst stability, Methanol tolerance, Selectivity |
相關次數: | 點閱:540 下載:0 |
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(Ru,Fe)Sex/C氧還原反應觸媒的合成分成兩步驟進行,首先混合羰基釕與羰基鐵分散於碳黑上,接著進行固態硒化反應。我們先前的研究發現,經由氫退火處理合成出耐久性黃鐵礦結構RuSe2/C觸媒具有相當不錯的氧還原活性與甲醇容忍性,且H2O2產率小於2%。本論文研究探討摻過渡金屬Fe希望增加RuSe2/C的氧還原活性,降低Ru金屬的負載量與成本,改變氫退火溫度、Ru/Fe原子比例、以及Se/(Ru+Fe)原子比例,藉由XRD、EDX與TEM的分析了解觸媒的結構、元素組成、晶格常數與粒徑大小,而電化學特性則使用旋轉(環)盤電極測試陰極氧還原反應之行為,探討觸媒對氧還原反應催化作用。
在400oC氫退火處理下表現出良好的氧還原活性,為最適之處理溫度。黃鐵礦相(Ru,Fe)Se2/C觸媒最高鐵含量比例約為50%,晶格常數會隨著鐵含量增加而減少。氧還原活性則會隨著鐵含量增加而有明顯的增加,此外黃鐵礦相(Ru,Fe)Se2/C具有良好的甲醇容忍性與低H2O2的產率,其中(Ru0.54Fe0.46)Se1.94/C展現最佳的氧還原活性與商用Pt/C觸媒(Johnson-Matthey)在電流密度1 mA cm-2下差0.07V。在典型陰極操作電位0.4~0.6V下,黃鐵礦相(Ru,Fe)Se2/C觸媒H2O2產率會隨著鐵含量比例增加而增加,但H2O2百分比皆小於2.5%。進一步改變不同Se/(Ru+Fe)原子比例, 觸媒活性會隨著Se含量減少而下降,但不影響H2O2的產率。(Ru,Fe)Se2/C觸媒穩定性介於耐久性RuSe2/C與參考文獻上作法熱裂解十二羰基釕RuSecluster/C 觸媒之間。
(Ru,Fe)Sex/C catalysts for oxygen reduction reaction (ORR) have been synthesized in two consecutive steps, in which a powder mixture of carbonyl ruthenium and iron loaded on the carbon black was prepared first, followed by selenization in hydrogen annealing at 300~500°C with excess selenium. Our previous works indicate that hydrogen annealing produced a durable RuSe2/C catalyst with pyrite structure and lasting catalytic activity toward ORR, also less than 2% yield in H2O2. In this study, iron has been substituted for ruthenium to reduce its noble metal loading and the materials cost. The catalyst structure and composition were characterized by X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) analysis. The electrochemical activity was measured using a rotating ring-disk electrode R(R)DE.
The hydrogen annealing temperature of 400°C is optimum in terms of ORR activity. The maximum iron content of (Ru,Fe)Se2 catalyst of pyrite structure is around 50 %. Excess iron in the precursor will be carried away by hydrogen. The pyrite lattice constant of (Ru,Fe)Se2 catalyst decreases with increasing iron content. When the ORR activity is expressed as current per unit area, the activity increases somewhat with increasing iron content. If the ORR activity is expressed as current per unit Ru mass, the activity is enhanced significantly. Meanwhile, the (Ru,Fe)Se2/C catalyst demonstrates excellent methanol tolerance and low yield in H2O2. For instance, the catalyst of (Ru0.54Fe0.46)Se1.94/C exhibits the highest ORR activity, which presents a potential difference of 0.07 V in comparison with a commercial Pt/C catalyst (Johnson-Matthey) at 1 mA cm-2 current. The H2O2 yield is <2.5% in 0.4~0.6 V, which is slightly higher than that of RuSe2/C catalyst. On further decreasing the Se/(Ru+Fe) ratio, the catalytic activity decreases. But doesn’t influence the H2O2 yield. The stability of (Ru,Fe)Se2/C catalyst is also between the durable RuSe2/C catalyst and the the RuSecluster/C catalyst prepared by thermolysis of Ru3(CO)12.
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