電催化分解水產氫可以將電能轉為氫氣之化學能儲存，補足再生能源如太陽能、風力發電等發電不穩定之缺點。其產物氫氣純度高，且具有高能量密度(120 MJ/kg)、壓縮後易於儲存、不產生碳排放等優點，被視為一具有永續性之產氫技術。電解水產氫之技術已發展數十年，但仍有持續進步之空間。例如目前電解水之電能消耗占了總成本之一半以上，若要降低耗電量，則需使用過電位極低的電極材料。然而，目前標竿電極仍為貴重金屬如Pt、IrO2、RuO2等價昂、稀少之材料，在大規模應用時較難降低生產成本。於此，數十年來不同的電極材料不斷地發展，但在電性表現以及長效性上仍尚未顯著地超越貴金屬電極。
金屬有機架構 (Metal Organic Frameworks，MOFs)之合成技術以及應用在近年來開始蓬勃發展，被視為一新興的催化材料，且在許多領域皆已有出色的表現。其主要由各種過渡金屬離子中心藉由有機配體分子連結，具有多變的結構以及可調控的金屬中心，有助於實際催化能力的提升。然而，大部分金屬有機架構材料之導電性皆極差(約10-10 S m-1)，故在早期被發展出來時並沒有太多應用於電化學領域中，且多數研究者也只是將其作為合成其它金屬氧化物、磷化物等之前驅物。此實驗並不將其進行高溫鍛燒，而是將鐵鎳雙金屬有機架構FeNi(BDC)(DMF,F)直接成長於導電泡沫鎳基材並進行電催化OER、HER，省去為了製成電極而加入不導電之黏合劑(binder)的步驟，同時以泡沫鎳的孔洞性質及導電性提升MOF複合材料本身之催化能力。
在經過反應物鐵鎳比例的調控並進行物質鑑定後，我們可得到一OER能力最適化之鐵鎳比例區間，表現優秀的OER、HER以及全電解水能力，也具有與近年文獻相比之下優異的高電流密度長效性。此FeNi(BDC)(DMF,F)/NF在OER表現方面，僅需227 mV之過電位即可達到電流密度60 mA cm−2，HER方面則僅需160 mV之過電位即可達到電流密度10 mA cm−2。在高電流密度(400 mA cm-2)下，亦有突出的表現，產氫以及產氧過電位分別為348和252 mV。全電解水表現方面，在達到電流密度10以及400 mA cm−2分別只需 1.58以及1.9 V之槽電壓(cell voltage)，勝過所比較用之標竿電極對Pt-C/NF//IrO2/NF。長效性測試方面，此實驗以全電解水定電壓測試方法，證明此FeNi(BDC)(DMF,F)/NF電極對在30小時高電流密度(初始電流為400 mA cm−2)下電流僅衰退10%左右，且長效性後SEM、XPS、OER、HER催化能力皆無明顯改變，具有足夠的化學穩定性以及機械強度。以氣相層析儀(GC)分析實際產生氫氣以及氧氣量後，證實此電極之OER及HER法拉第效率接近於100%，具有實際應用之價值。

Energy storage is an indispensable part of the green energy infrastructure. It is particularly critical to tackle the detrimental issues of unreliability and intermittency associated with renewable energies. Among the many approaches developed/under development, hydrogen production from renewable energy driven electrolytic water splitting, storing excessive off-peak electricity generated by renewable energies in the form of chemical energy, has drawn a great deal of re-surging research attention in recent years. However, the popular benchmark electrocatalysts for the OER and HER such as IrO2 and Pt/C still suffer from the high cost, Earth-scarcity, and unsatisfactory long-term stability under high current densities. As a result, it is critical to develop high efficiency non-noble metal based, cost-effective and durable electrocatalysts.
Metal organic frameworks (MOFs), possessing versatile catalytic activities, remarkable structural diversity, high surface areas and tunable pore sizes, have been applied to a wide range of applications including chemical sensing, supercapacitor, and gas storage in recent years. Nevertheless, because of their low electrical conductivities (about 10-10 S m-1), only very few MOFs have been directly used as efficient electrocatalysts for the OER and HER. More often, they are utilized as the precursors to derive carbonaceous materials carrying metal or metal-based electrocatalysts through high temperature thermal treatments with potential drawbacks. In this research, the bi-metallic metal organic frameworks, FeNi(BDC)(DMF,F), was grown in-situ on conductive substrates without high temperature treatments and non-conductive binder, showing outstanding electrocatalytic performances toward the OER and HER along with excellent stability at high current densities.
In this study, the adequately modulated FeNi(BDC)(DMF,F)/NF electrode delivered current densities of 60 and 400 mA cm-2 at ultralow overpotentials of 227 and 252 mV, respectively toward the OER, with an ultralow Tafel slope of 37.4 mV dec-1 achieved. Moreover, if serving as a bifunctional electrode, it required only 1.58 and 1.90 V to achieve the current densities of 10 and 400 mA cm-2, respectively for overall water splitting, which is even superior to the pairing of the two benchmark electrodes, Pt-C/NF//IrO2/NF. The stability of the electrodes was also excellent, experiencing only minor chronoamperometric decay after a continuous operation at 400 mA cm−2 for 30 hours. The success may be attributed to the MOF/substrate synergistic effects between the FeNi(BDC)(DMF,F) and the conductive macroporous nickel foam, the inter-molecular synergistic effects between the two constituent MOF phases, and the intra-molecular synergistic effects between the FeO6 and NiO6 clusters of the Fe-rich FeNi(BDC)(DMF,F). Exploration and utilization of the hierarchical synergistic effects proves to be a simple and an effective way to develop ultrahigh performance electrocatalysts.

目錄
摘要 i
Abstract iii
致謝 v
總目錄 vi
圖目錄 viii
表目錄 xi
第一章 緒論 1
1-1 前言 1
1-2 電解水反應機制 2
1-2.1 HER反應機制 3
1-2.2 OER反應機制 4
1-2.3過電位Ƞ及塔佛斜率Tafel slope 6
1-2.4 Turnover frequency (TOF)計算 7
1-3 電解水實驗原理 9
1-3.1 電解液 9
1-3.2 對電極 9
1-3.3 參考電極 10
1-4 OER、HER觸媒現況及條件 11
1-5 金屬有機架構 12
1-5.1 相對穩定之MOF結構--- Carboxylate-based MOF 14
1-5.2 相對穩定之MOF結構--- Azolate-based MOF 17
1-5-3 以金屬活性點位置分類MOF 19
1-6 實驗動機 21
第二章 文獻回顧 23
2-1 以MOF作為前驅物之材料於OER應用 23
2-2 以MOF作為前驅物之材料於HER應用 30
2-3 以導電金屬為基底之複合材料於電解水應用 37
2-4 直接以MOF作為催化中心於OER、HER之應用 44
第三章 實驗步驟 52
3-1實驗藥品 52
3-2實驗器材 53
3-3分析儀器 53
3-4 電極製備 55
3-4.1 泡沫鎳基材之前處理 55
3-4.2 水熱法之原位(in-situ)成長金屬有機架構於泡沫鎳基材 56
3-4.3 水熱法之bulk MOF粉末製備 56
3-4.4 以黏合劑將bulk MOF粉末製備於空白石墨電極 57
3-4.5 以黏合劑將標竿電極IrO2及Pt-C及bulk MOF粉末製備於泡沫鎳基材電極 57
3-5電化學量測 57
3-5.1 三極式系統OER、HER量測 57
3-5.2 二極式系統全電解水量測 58
3-5.3 Electrochemical Active Surface Area (ECSA) 58
3-5.4 Electrochemical Impedance Spectroscopy (EIS) 59
3-5.5 長效性測試 59
第四章 結果與討論 60
4-1 金屬有機架構於泡沫鎳基材上之形貌及粉末元素含量鑑定 60
4-2 各成分金屬有機架構之結構鑑定 64
4-3 各成分金屬有機架構於泡沫鎳基材之OER電性測試 70
4-4 金屬有機架構於泡沫鎳基材與標竿電極之OER電性比較 74
4-5 各成分金屬有機架構於泡沫鎳基材之HER電性測試 76
4-6 金屬有機架構於泡沫鎳基材之全電解水性能及長效性測試結果 77
4-7 金屬有機架構於泡沫鎳基材之協同效應討論 82
第五章 結論 85
參考文獻 86

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