無論學術界亦或工業界，小分子烷類的碳氫鍵活化反應都佔據極其重要的地位。尤其甲烷和乙烷作為天然氣主要成分，若能通過碳氫活化反應將其部分氧化成醇、酮、醛、酸等高工業價值的化合物，將會具有極高的經濟及商業意義。近十年來已有相當一部分研究利用過氧化氫、氧氣搭配貴金屬催化劑成功進行甲烷的碳氫鍵活化反應，但絕大部分的製程都面臨同樣的挑戰：高溫或高壓、催化劑成本高昂、需要額外添加氧化劑。在本研究中將採取先前研究中探討過的反應策略：利用電化學中的析氧反應（OER）來產生具有高反應性金屬活化氧，從而再進行碳氫鍵活化反應。該方法可有效避免上述所有問題，唯一的困難是需要篩選出合適的催化劑。
　　金屬骨架材料（MOF）作為一種可導電的週期性孔洞材料，因其具備穩定的孔隙率、超高表面積和極佳的可調控性，是電化學催化材料的熱門選擇。實驗上證實，MOF材料在產氫反應（HER）、析氧反應（OER）以及氧氣還原反應（ORR）中都有顯著表現。本研究中篩選了二十種結構相似、更換中心金屬及取代基的一維金屬骨架材料，利用DFT計算，嘗試篩選出可對甲烷進行碳氫活化的催化劑。計算結果顯示，當配位金屬為Co，其四配體為S的催化材料儘管對甲烷碳氫鍵活化的反應性並不理想，但卻可在電位為1.23 VSHE以上、pH值在0.9～3.9的範圍內，成功以可接受的反應速率去活化乙烷的碳氫鍵。透過熱力學計算，可預期在後續的脱氫反應中可得到乙醛產物。該研究為該反應的催化領域提供了一條新的思路和可行的催化材料方向。

The C-H activation of light alkanes is important reaction whether in academia or industry. In particular, methane and ethane as the main components of natural gas. It will have extremely high economic and commercial significance while they can be partially oxidized to alcohols, ketones, aldehydes, acids and other high-industrial compounds. In the past ten years, there are some studies activating the C-H bond of methane by hydrogen peroxide and oxygen with precious metal catalysts successfully. However, most of the processes face the same challenges: high temperature or high pressure, high catalyst cost, and additional oxidizer. In this study, we adopted the reaction strategy discussed in the previous study, which is using the OER in electrochemistry to generate highly reactive metal-activated oxygen, and then proceed to the C-H activation. This method can effectively avoid all the above-mentioned problems. A suitable catalyst is the only difficulty.
There are a kind of conductive metal-organic frameworks (MOFs), which is popular choice for electrochemical catalytic materials. These MOFs have significant performance in HER, OER and ORR, which is confirmed by experimental reports. In this study, to replace the oxygen evolution reaction with thermodynamically more favorable and economically more profitable methane and ethane, electrochemical partial oxidation, we employed constant electrode potential density functional theory calculations to screen twenty 1D-MOFs containing heteroatom-substituted benzene as electrocatalysts. By computing the Pourbaix diagrams, O-H binding energies, and C-H activation barriers, we determined that none of these catalysts were able to activate methane, unfortunately. However, there is one was able to hydroxylate ethane to ethanol with facile kinetics, making it a promising electrocatalyst for natural gas oxidation.

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