Adsorption and Reactions on TiO2: Comparison of N,N-Dimethylformamide and Dimethylamine

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• 作者：Jong-Liang Lin ; Yu-Cheng Lin ; Bo-Chiuan Lin ; Po-Chih Lai ; Tzu-En Chien ; Szu-Hui Li ; Yu-Feng Lin
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：September 4, 2014
• 年：2014
• 卷：118
• 期：35
• 页码：20291-20297
• 全文大小：457K
• ISSN：1932-7455

文摘

Fourier transform infrared spectroscopy has been employed to study the adsorption and reactions of N,N-dimethylformamide (DMF) and dimethylamine (DMA) on powdered TiO₂. DMF can be adsorbed in molecular form with the carbonyl interacting with the surface Lewis site (Ti⁴⁺) or in dissociative form of OCN(CH₃)₂. Theoretical adsorption study of rutile (110) points out that the C* and O atoms of OC*N(CH₃)₂ are bonded at a two-fold-coordinated O site and a five-fold-coordinated Ti site, respectively. The thermal products of DMF/TiO₂ are found to be CO and DMA. Photochemical reaction of DMF on TiO₂ in O₂ generates CO₂, HCOO, and NCO. O₂ participates in the reaction with its oxygen atoms incorporated into the three products. DMA can be adsorbed in molecular form and imine species on TiO₂. Photoirradiation of DMA/TiO₂ in O₂ generates CO₂, HCOO, NCO, and imine species. Interestingly, DMF and OCN(CH₃)₂ are produced after postirradiation thermal treatment of DMA on TiO₂, possibly from the reaction between residual DMA and HCOO photoproduct.