摘要

為了設計出有效轉化甲烷的催化劑，研究甲烷在金屬簇表面上的化學性質是一種可以選擇的解決方案。在本論文中，採用了密度泛函理論研究甲烷在Pt4金屬簇、Ir4金屬簇及Ir13金屬簇修飾於硼氮摻雜石墨烯表面上的吸附、分解和可能的偶聯反應。在催化甲烷轉化時需要活化及可能分離的過程，Pt4金屬簇、Ir4金屬簇及Ir13金屬簇修飾於硼氮摻雜石墨烯表面針對甲烷的脫氫反應具有較高的催化活性。首先，先研究了Pt4金屬簇、Ir4金屬簇及Ir13金屬簇在硼氮摻雜石墨烯表面上最穩定的結構及碳氫化合物的吸附能。另外我們也藉由電子密度差異等值線圖和態密度討論金屬團簇和吸附物間的相互作用，發現甲烷透過agostic相互作用在金屬團簇上進行分子性吸附。接著並研究甲烷在所有表面上的脫氫反應。結果顯示在低溫條件下，甲烷活化在Pt4金屬簇上比在Pt4金屬簇上更容易以及在熱力學上更適合，且其第一步的脫氫反應也被發現具有低動力學屏障(0.17eV)和高吸附能(-0.58eV)，這表明了甲烷分解比直接脫附更容易；第二及第三步脫氫反應則分別是在Pt4金屬簇以及Pt4金屬簇於硼氮摻雜石墨烯表面上的速率決定步驟。此外，為了除去沉積在表面上的碳，氧氣會解離性吸附在兩金屬簇上並將碳氧化成二氧化碳，氫原子重組來產生氫氣也被考慮在兩個金屬簇上，結果證實在溫和的溫度條件下可以形成氫氣並且可以容易地從表面脫附。

甲烷的活化和抑制後續脫氫進而研究偶聯反應被認為是潛在催化劑設計中最重要的過程。在本研究中，我們預測Ir13金屬簇可以有效地活化甲烷並促進碳-碳偶聯反應，在銥金屬簇上，頂部位置被認為是甲烷最穩定的吸附位置且具有-0.45eV的吸附能，甲烷以0.16eV較低活化能障被活化、反應熱為-0.54eV，這是最容易的步驟並且在熱力學上最適合的且可能在低溫條件下發生；第四步脫氫反應為速率決定步驟，其在Ir13金屬簇上脫氫反應中需較高活化能障(1.24eV)，碳-碳偶聯反應已經被研究透過控制反應溫度來抑制甲烷後續脫氫反應。基於計算結果，在Ir13金屬簇上甲烷選擇性脫氫成甲基之後再形成乙烷具有較低動力學屏障，此外，氫氣的生成也被考慮在金屬簇上且發現是可行的

另外，我們發現在Ir13金屬簇上，甲烷在低氧覆蓋率比高氧覆蓋率具有更高的吸附能和分解時更低的活化能障，結果顯示甲烷在低氧覆蓋下的吸附能為-0.44 eV，第二步脫氫反應為速率決定步驟(1.24 eV)且低於高氧覆蓋率下，因此，通過控制反應溫度，甲基和亞甲基物質是在Ir13金屬簇上氧預覆蓋中最豐富的物質，並且考慮了碳-氧偶聯反應。基於密度泛函理論的計算，在低氧覆蓋率下形成具有較低活化能障的甲醇和甲醛，此外，氫原子的再結合也被考慮並證實可以在表面上形成氫氣。因此，低氧預覆蓋在Ir13金屬簇修飾於硼氮摻雜石墨烯表面上是大有可為的催化劑且用於將甲烷選擇性轉化為甲醇、甲醛和氫氣的產生。

Abstract

To design an efficient catalyst for methane conversion, studying the chemical nature of methane on metal cluster surface is an alternative solution. Catalytic conversion of methane requires processes such as activation and possibly dissociation. Boron nitrogen co-doped graphene surface decorated by Irand Pt cluster exhibited higher catalytic activity for dehydrogenation of methane. In this thesis, we have investigated adsorption, dissociation of methane and possibly the coupling reactions on boron nitrogen co-doped graphene surface decorated by Ir4 cluster, Pt4 cluster and Ir13 cluster using density functional theory (DFT) methods. The most stable adsorption configuration and adsorption energies of CHX (0-4) on boron nitrogen co-doped graphene surface decorated by Ir4 cluster, Pt4 cluster and Ir13 cluster have been investigated. Moreover, the interactions between the surface and adsorbate discussed by the electron density difference contour plot (EDD) and density of sates (DOS). Methane molecularly adsorbs on the surface through agostic interactions anddehydrogenation of methaneinall surfaces have been also studied via precursor mediated mechanism. The result reveals that activation of methane on BNG-Ir4 cluster, which occurs at low temperature condition, is more facile and thermodynamically favorable than that of BNG-Pt4 cluster. The first dehydrogenation step of methane on BNG-Ir4 cluster has been found to have low kinetic barrier (0.17 eV) and high adsorption energy of methane (-0.58 eV), indicating easier methane dissociation than direct desorption. The third and the second dehydrogenation step is the rate determining step on BNG-Ir4 cluster and BNG-Pt4 cluster, respectively.
The results reveals that the coupling barriers of CH3/CH3 and CH2/CH2 on BNG-Ir4 cluster are 1.23 eV and 0.64 eV, respectively, indicating that the formation of ethane and ethylene is possible on BNG-Ir4 cluster. However, the desorption energies of ethane and ethylene are 0.53 eV and 2.00 eV, where the desorption of ethylene is very difficult on BNG-Ir4 cluster. Thus by controlling the reaction temperatures, producing of ethane is possible on BNG-Ir4 cluster.Furthermore, recombination of hydrogen to produce hydrogen molecule has been considered on both clusters and the result confirms that hydrogen molecule can be formed on BNG-Ir4 clusterand BNG-Pt4 cluster at mild temperature conditions and can easily be desorbed from the surface.
In the present study, we predict that BNG-Ir13 cluster can efficiently activate methane and promote the C-C coupling reactions. Top site of Ir on BNG-Ir13 cluster is considered as the most stable adsorption site of methane with the stable adsorption energy of -0.45 eV. Methane is activated with lower activation energy barrier of 0.16 eV and the reaction energy is -0.54 eV. It is the most facile step and is thermodynamically favorable, which is likely to occur at low temperature conditions. By controlling the reaction temperature, which inhibit further dehydrogenation of methane, the C-C coupling reactions have been studied on BNG-Ir13 cluster. Based on the DFT calculations, selective conversion of methane and self-coupling reactions of methyl formed ethane with a lower kinetic barrier, which is likely to occur on BNG-Ir13 cluster.
Furthermore, we found out low oxygen coverage of BNG-Ir13 cluster has higher adsorption energy of methane and lower activation energy barrier of methane dissociation throughout the calculations compared to high oxygen coverage of BNG-Ir13 cluster. The result reveals that the adsorption energy of methane in low oxygen coverage of BNG-Ir13 cluster is -0.44 eV and the second dehydrogenation of methane is the rate determining step (1.24 eV), which is lower than that of high oxygen coverage of BNG-Ir13 cluster. As a result, by controlling the reaction temperature, CH3 and CH2 species are the most abundant species in oxygen pre-covered BNG-Ir13 cluster and the C-O coupling reactions have been considered. Based on the DFT calculations, methanol and formaldehyde are formed with lower activation energy barrier in low oxygen coverage of BNG-Ir13 cluster (BNG-Ir13O cluster) and can be occurred at moderate temperature conditions compared to high oxygen coverage of BNG-Ir13 cluster. Low oxygen pre-covered BNG-Ir13 cluster is a promising catalyst for selective conversion of methane to methanol, formaldehyde and production of hydrogen.

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