本篇論文利用傅立葉轉換紅外光譜(FTIR)與密度泛函理論計算，研究咪唑(C3N2H4)與4-咪唑甲酸(C3N2H3-COOH)在TiO2表面上的吸附結構，以及熱與光反應。探討這些分子與TiO2表面的作用，進而推導熱與光反應的路徑。
吸附計算顯示咪唑分子主要是以N原子和表面Ti原子進行鍵結，咪唑環的結構改變不大。在真空與無氧的反應系統中，低於200 ℃，此分子穩定吸附在表面，升高溫度後，吸附分子從表面脫離，沒有發生分解。有氧氣存在下，高於250 ℃，雜環開始分解，產生NCO(ad)、HCOO(ad)、CO2(g)、NH3(ad)。咪唑/TiO2於真空中照射325 nm紫外光後，在表面上產生環破裂後所形成的中間物，可能帶有共軛的C=C、C=N物種。於有氧情況下照光，由於表面上的中間物進一步被氧化分解，多了NCO(ad)、H2O(ad)、HCOO(ad)、CO2(g)、含C=O物種的生成。
4-咪唑甲酸於~35 ℃的TiO2上有兩種吸附型式: 完整的分子及斷OH基後形成的4-咪唑甲酸根。Rutile(110)的理論吸附計算顯示4-咪唑甲酸可以C=O的氧原子和環上的N與表面Ti離子作用，而4-咪唑甲酸根則是以COO和N接近表面Ti離子。分解性吸附的4-咪唑甲酸比完整吸附的分子穩定，能量差是~12.2 kcal mol-1。提高TiO2的溫度可促進4-咪唑甲酸的去質子化，高於200 ℃，4-咪唑甲酸根的分解產生了CO2(g)和咪唑分子。O2存在下，4-咪唑甲酸/TiO2於約高於250 ℃反應而生成NCO(ad)、HCOO(ad)、CO2(g)、NH3(ad)。4-咪唑甲酸/TiO2受325 nm光照可能引起開環的反應。

In this research, Fourier-transform infrared spectroscopy has been employed to study the adsorption and reactions of imidazole and 4-imidazolecarboxylic Acid on powdered TiO2. Imidazole is chemisorbed on TiO2 surface at 35 ℃ via its pyridine-type nitrogen atom. In vacuum, desorption of the surface imidazole occurs above ~200 ℃, without decomposition. However in O2, the imidazole reacts to form NCO(ad),HCOO(ad),CO2(g) and NH3(ad) at a temperature higher than ~200 ℃. With the light exposure at 325 nm, the aromatic ring of the imidazole on TiO2 may break, forming intermediates with conjugated C=N and C=C. In the presence of oxygen, other reaction products of NCO(ad),H2O(ad), HCOO(ad), CO2(g) and C=O containing species are generated from the photocatalytic decomposition of imidazole/TiO2.
At 35 ℃, 4-imidazole carboxylic acid can be molecularly and dissociatively adsorbed
On the TiO2 surface. The dissociative adsorption of the 4-imidazole carboxylic acid occurs by the OH bond cleavage, forming 4-imidazole carboxylate. The theoretical adsorption study on rutile(110) shows that 4-imidazole carboxylic acid is adsorbed on the surface via the interaction of the oxygen of C=O and the N in the aromatic ring with surface Ti ions. The 4-imidazole carboxylate is adsorbed via the COO and the N. Raising the surface temperature would promote the deprotonation of 4-imidazole carboxylic acid. Above ~200 ℃, the decomposition of 4-imidazolecarboxylate generates CO2 and imidazole. In the presence of O2, reaction of 4-imidazole carboxylic acid on TiO2 produces NCO(ad), HCOO(ad), CO2 and NH3 at a temperature higher than 250 ℃. Under photoirradiation at 325 nm, 4-imidazole carboxylic acid may dissociates via the breakage of the aromatic ring.

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