本文探討了在能源議題中重要的二氧化碳還原成多碳產物與氮氣產氨之電化學還原路徑與方式。
為了建立碳中和的能量循環，開發能將二氧化碳還原為至少兩個碳原子之多碳產物的電催化劑十分的重要。該過程將至少需要兩個單碳中間體以進行碳-碳耦合反應。銅(110)表面能將大量的二氧化碳還原為多碳產物(法拉第效率高於65%)，因此在本研究中，使用恆定電極電位密度泛函理論計算來得知銅(110)上二氧化碳電化學還原(CO2ER)的主要碳-碳耦合途徑。透過研究CO2ER轉化為甲烷的反應機構，確定* CO和* CH為高濃度的單碳物種，因其進行氫化反應時的活化能較高。基於該結果，選擇了包含至少一種高濃度單碳中間體的26個碳-碳耦合反應進行研究，確定了在銅(110)上形成多碳產物最重要的因素，也探討了表面的擴張與壓縮對此反應的影響。
氨(NH3)是製作肥料所需之硝酸鹽的主要成分之一。適度、合理的施氮肥有助於植物生長，增加糧食產量和提高作物品質，因此氨的製備顯得格外重要。目前世界上主要以哈伯法(the Haber-Bosch process)製氨，但其有著需在高溫高壓下進行反應、哈伯法工廠建造成本昂貴、以及排放溫室氣體副產物等缺點。本研究設計一共面構形釕(0001)催化氮氣電還原反應。在氮氮鍵斷鍵方面，本系統解決其在單層材料表面上的巨大活化能，直接藉著兩層表面使氮氣以垂直的方式吸附直接斷鍵。在氫化反應方面，各步驟的活化能也十分容易進行，使氮氣電化學還原反應更有效率。本研究成功將氮氣電還原反應與共面構形釕(0001)結合，是一個劃時代氨的創新製程，不僅改善現有哈伯法的問題，亦符合了綠色化學的原則，其影響極大。

In this study, CO2 electrochemical reduction (CO2ER) on Cu(110) and N2 electrochemical reduction (N2ER) on co-facial Ru(0001) were investigated.
To establish a carbon-neutral energy cycle, it is very important to develop an electrocatalyst that can reduce CO2 into at least two carbon atoms products (C2+). This process will require at least two C1 intermediates for C-C coupling reactions. Cu(110) can reduce a large amount of CO2 to C2+ products (Faradaic efficiency is higher than 65%). Therefore, in this study, constant electrode potential density functional theory calculations are used to know the main C-C coupling pathway for CO2 electrochemical reduction (CO2ER) on Cu(110). Through studying the reaction mechanism of CO2ER to methane, we determined that *CO and *CH are the high concentration C1 species because of their higher barriers during hydrogenation. Based on this result, 26 C-C coupling reactions containing at least one high-concentration C1 intermediate were selected for further discussion. The most important factors for the formation of C2+ products on Cu(110) were comfirmed, and the influence of strain of these reactions was also investigated.
Ammonia (NH3) plays one of the most crucial role in the nitrates formation which is needed for the fertilizer. The Haber-Bosch process is the major process to synthesize ammonia. However, it requires enormous amounts of energy (2% for the world supply), extreme conditions and generates green house gases byproduct. In this work, we used quantum mechanics to design a co-facial Ru(0001) to catalyze N2 electrochemical reduction (N2ER) more effciently, and report the detailed free energy surfaces and kinetic barriers for the whole reaction. The distance 4.6 Å of co-facial Ru(0001) was found to possess the best catalytic efficiency with the lowest free energy barrier in the NN cleavage pathway. The co-facial Ru(0001) adsorbs the nitrogen vertically and directly cleaves the bond. The nitrogen atom can be further hydrogenated to form NH3. It reduces the free energy barriers for NN cleavage and the hydrogenation process is facile. Our theoretical investigation suggested co-facial Ru(0001) improves the N2ER.

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