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標題: 還原奈米白金顆粒於含鐵氫氧基磷灰石多孔微米球應用於燃料電池觸媒
Nano-sized Pt particles reduced on iron contained hydroxyapatite porous microspheres as catalysts for fuel cells
作者: 白乃夙
Nai-Su Pai
關鍵字: 質子交換膜燃料電池;直接甲醇燃料電池;氧氣還原反應;含鐵磷酸鈣鹽;白金觸媒;PEMFC;DMFC;oxygen reduction reaction (ORR);iron contented hydroxyapatite;platinum catalysts
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Proton-exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) are electrochemical conversion devices that can produce electricity at high fuel efficiencies, and Pt the excellent and major catalyst in them, is too expensive to be developed for a commercial applications widely. Before the fuel cells become practical for wide-scale consumer use, two technological problems must be solved. 1. the activity of electrodes must be improved to increase efficiency, then the amount of platinum catalyst in electrodes could be lowered to reduce the cost of devices. 2. poisoning effects of CO on Pt catalysts should be removed.
In recent years, Hydroxyapatite (HAp), Ca10(PO4)6(OH)2, the major component in human hard tissue been applied to orthopedic and dental bioceramics, has also become a new support of heavy metal ions for a novel catalyst and presented the superior chemical and thermal stability by using ion exchange, such as iron contained hydroxyapatite. The voltammograms of hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), and oxygen reduction reaction (ORR) in acid solutions depending on three low-index planes of Pt are investigated in recent years. The result indicate that Pt (1 1 0) facet is more active than (1 1 1) and (1 0 0) ones. Therefore, how to prepare nano-sized Pt with (1 1 0) facet becomes a very important issue in this field.
In this study, the porous HAp microspheres prepared by wet-chemical method with diameter around 25 μm are partially exchanged with ferrous ions to form iron contained hydroxyapatite (FeHAp) on which Pt ions in H2PtCl6 solution are reduced to form Pt/FeHAp catalyst and finally mixed with carbon blacks to derive Pt/FeHAp/C catalysts. The particle size of Pt supported on FeHAp (Pt/FeHAp) is around 3.2 nm. They exhibit the characteristics of Pt (1 1 0) facet with a sharp desorption peak at -0.109 V (vs. Ag/AgCl), the electrochemical surface area (ECSA) ranging from 73 to 224 m2 g-1 with little CO poisoning effect on Pt, and the mass activity ranging from 6.88 to 28.99 A gPt-1 in methanol oxidation reaction (MOR) at 0.4 V (vs. Ag/AgCl). Besides, Pt/FeHAp reveals the lower onset potential in CO stripping than Pt/C. In ORR, the Pt/FeHAp/C catalysts also reveal the characteristics of Pt (1 1 0) facet with little hydrogen peroxide in the oxygen activity reaction, the Tafel slopes ranging from -68 to -240 mV dec-1. Besides, Pt/FeHAp reveals the higher onset potential in ORR than Pt/C. These better performances of Pt/FeHAp/C catalysts in HOR, MOR and ORR, compared with Pt/C, are related to the Pt (1 1 0) facet, the content of Fe, and the coexistence of Pt0 and Pt2+ in Pt/FeHAp. Besides, a model with computer motion picture simulation depicting why Pt (1 1 0) facet could be coherent on FeHAp (2 1 10) is also presented to rationalize the electrochemical characteristics of cyclic voltammetry.

質子交換膜燃料電池(proton exchange membrane fuel cells, PEMFC)與直接甲醇燃料電池(direct methanol fuel cells, DMFC)係高效能地將燃料直接轉換成電能的裝置,所用的電極觸媒主要以白金為活性成分,因為白金具有優越的化學催化性與穩定性因此常做為膜電極觸媒,但因白金成本太高以至於無法普及化。在廣泛使用前,有兩個技術性問題必須克服:1.電化學活性必須大幅提昇以減少白金使用量,降低產品成本;2.一氧化碳毒化白金的現象必須排除。
氫氧基磷灰石(Hydroxyapatite, HAp)是人體硬組織的主要組成,已應用於骨科和牙科生物陶瓷, HAp也可應用於金屬離子交換,形成新穎的觸媒例如含鐵(Fe(III))氫氧基磷灰石,此類型觸媒具有優越的化學穩定性與熱安定性,並且可提升其觸媒效應。另一方面文獻指出在白金的主要三個低指數晶面(low-index plane)中,針對酸性溶液中的產氫反應(hydrogen evolution reaction, HER)、氫氣氧化反應(hydrogen oxidation reaction, HOR),及氧氣還原反應(oxygen reduction reaction, ORR)皆以Pt(1 1 0)晶面表現出最高的活性。因此如何開發奈米級Pt(1 1 0)薄膜,以降低白金用量,發揮白金最大效應,將成為此領域中一項熱門議題。
本研究利用濕式合成法製備大小約為25 μm的磷酸鈣鹽微米球,利用鐵離子交換法後得到含鐵氫氧基磷灰石(FeHAp)作為觸媒載體,並將奈米白金(Pt)還原於其上形成Pt / FeHAp,再與碳黑(C)混合,得到Pt / FeHAp / C,其白金顆粒大小平均為3.2 nm。循環伏安圖(Cyclic Voltammetry)顯示其氫氣脫附反應峯在-0.109 V (vs. Ag/AgCl)係Pt (1 1 0)晶面之特性反應峯,其電化學活性表面積為73 - 224 m2 g-1;在甲醇氧化反應(methanol oxidation reaction, MOR),其質量活性為6.88 - 28.99 A gPt-1,(0.4 V vs. Ag/AgCl)且無CO毒化現象,同時Pt/FeHAp/C具有較低的起始電位。在氧氣還原反應中,Pt/FeHAp/C也呈現出Pt(1 1 0)晶面的特徵;比商用觸媒(Pt/C)產生較少的雙氧水,其塔佛斜率(Tafel slopes)為 -68 至 -240 mV dec-1,除此之外Pt/FeHAp/C也具有較高的起始電位。Pt/ FeHAp/ C與商用觸媒(Pt / C)相較之下,無論在HOR, MOR, 或ORR均具有較好的表現,這些優異的性能應與Pt/ FeHAp當中的Pt(1 1 0)晶面表現、鐵的含量,以及白金價數(Pt0, Pt2+)相關聯。同時利用電腦動畫模擬描述還原的奈米Pt薄膜為何能以(1 1 0)晶面與FeHAp(2 1 10)晶面契合,合理解釋循環伏安法的電化學性能具Pt(1 1 0)晶面的特殊表現。
其他識別: U0005-1001201416523900
Rights: 同意授權瀏覽/列印電子全文服務,2017-01-15起公開。
Appears in Collections:材料科學與工程學系

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