近年來，由於一氧化碳中毒及溫室效應所導致全球暖化的問題，使得一氧化碳(CO)和二氧化碳(CO2)的轉化反應受到了廣泛討論。過去的研究已報導，這些反應可在貴金屬表面上發生進行低溫催化反應。另外據文獻報導，二氧化銥是個對甲烷活化和OER反應具有良好催化活性的催化劑。因此，本文採用密度泛函理論(DFT)針對一氧化碳氧化和二氧化碳重組反應於二氧化銥(110)表面上之反應機構進行探討。
在一氧化碳氧化方面，我們研究了三種不同的機制：朗謬-辛歇伍德(L-H)、埃利-里迪爾(E-R)和馬爾斯-范克里弗倫(MvK)機制。在L-H機制中，我們發現在有或無氧氣直接分解的條件下，反應之速率決定步驟分別是C-O偶合反應以及二氧化碳脫附反應。在E-R機制中，我們計算發現各反應步驟的活化很小，二氧化碳和碳酸都是可以形成的產物。然而，因為CO2在二氧化銥(110)表面上的脫附能很大，因而其脫附反應在E-R機制中仍然是困難的，E-R機制中之速率決定步驟也是二氧化碳脫附反應。此外，因為MvK機制中的反應活化能皆大於L-H或E-R機制中的活化能，故MvK機制在二氧化銥(110)表面上進行的可能性比較小。最後，我們通過分子動力學模擬觀察到當溫度增加到400 K後，二氧化碳可以脫離表面，這個結果顯示了CO2與二氧化銥(110)表面具有很強的結合能力。所以，這個結果也顯示了一氧化碳氧化的反應性乃受制於二氧化銥(110)表面上二氧化碳的脫附反應。
在二氧化碳重組反應中，二氧化碳和甲烷在二氧化銥(110)表面上具有足夠大的吸附能，因此它們無法脫附，並能夠彼此反應。經過計算一系列活化能低於0.80 eV的轉化反應後，我們發現在二氧化銥(110)表面上會形成一氧化碳和甲醛共吸附，但由於一氧化碳和甲醛的脫附能很大，它們只能在高溫下才能脫離表面。故此我們亦考慮了一氧化碳和甲醛的碳-碳耦合反應並發現他們的耦合活化能很小。同樣在經過一系列活化能均低於1.00eV的轉化反應之後，一氧化碳和甲醛會在二氧化銥(110)表面上產生乙烯酮。乙烯酮在二氧化銥(110)上的脫附能皆小於一氧化碳和甲醛，表示乙烯酮能夠在相對低溫下進行脫附。因此乙烯酮的形成也可能是在二氧化碳重組反應中另一種途徑。最後歸納利用甲烷進行二氧化碳之重組反應中，有兩種可能的高價值化學產品產生：甲醛或乙烯酮。我們的結果也顯示前者可能在較高溫度下形成，而後者可以在較低溫度下獲得。我們預測二氧化銥(110)表面將成為溫室氣體重整生產高價值化學品的優秀新型催化劑。

Recently, the conversion of carbon monoxide (CO) and carbon dioxide (CO2) has been extensively discussed due to their influence for human’s lives and the environment, such as CO poisoning as well as the global warming issues from the greenhouse effect. Several studies have been reported that these reactions occurred on the surface of noble metals have high catalytic activity at low temperatures. Besides, iridium oxide has been reported to possess good catalytic activity towards methane activation and OER. Thus, in this thesis, density functional theory (DFT) is used to calculate the reaction mechanism of CO oxidation and CO2 reforming on IrO2 (110) surface.
In terms of CO oxidation, we investigated the CO oxidation via three different mechanisms: Langmuir-Hinshelwood (LH), Eley-Rideal (ER) and Mars-Van Krevelen (MvK) mechanisms. In the L-H mechanism, we found that the rate-determining steps are C-O coupling and CO2 desorption in the condition with or without O2 direct decomposition, respectively. In the E-R mechanism, both CO2 and CO3 formation are possible routes due to small reaction barriers. However, the CO2 desorption is still difficult due to its large desorption energy on IrO2 (110) surface so that the rate-determined step is CO2 desorption in E-R mechanism. In addition, the reaction barriers in MvK mechanism are larger than that in either L-H or E-R mechanism, and thus the MvK is a less possible mechanism on IrO2(110) surface. Furthermore, by using the MD simulation, we observed that CO2 can desorb after increasing to 400 K, indicating that CO2 has a strong binding ability to IrO2(110) surface. Therefore, this result also suggests that the reactivity of CO oxidation is controlled by the desorption of CO2 on IrO2(110) surface.
In CO2 reforming reaction, CO2 and CH4 have large enough adsorption energy on IrO2 (110) surface to avoid the desorption of them. After a series of conversion reaction steps with energy barriers being lower than 0.80 eV, we found that it can form the CO and CH2O on IrO2 (110). However, the desorption energies of CO and CH2O are large which can only desorb at high temperature. Hence, we also consider the C-C coupling of CO and CH2O and found the coupling barrier is small. After a series of conversion reaction steps with energy barriers being lower than 1.00 eV, it can produce the ethenone on IrO2 (110) surface. The desorption energy of ethenone is smaller than that of CO and CH2O on IrO2 (110) surface. Therefore, the ethenone formation is another possible pathway for CO2 reforming reaction. In the reaction of CO2 reforming by CH4, there are two possible high-value chemicals products: formaldehyde or ethenone. Our results suggest that the former might form at a higher temperature while the latter could obtain at the lower one. We predict that IrO2 (110) surface will be an excellent novel catalyst for the greenhouse gas reforming to produce high-value chemicals.

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