Nosaka Atsuko Y, Nishino Junichi, Fujiwara Toshimichi, Ikegami Takahisa, Yagi Hiromasa, Akutsu Hideo, Nosaka Yoshio
Department of Chemistry, Nagaoka University of Technology, Nagaoka 940-2188, Japan.
J Phys Chem B. 2006 Apr 27;110(16):8380-5. doi: 10.1021/jp060894v.
The effects of thermal treatments on the rehydration process and photocatalytic activity were investigated by 1H NMR spectroscopy for six anatase abundant TiO2 photocatalysts with different properties. Acetic acid and benzoic acid were employed for photodecomposition in aqueous suspension. After the calcinations at 973 K, physisorbed water layers recovered relatively fast for P25, F4, and AMT-600 (shorter than 24 h) with no significant enhancement of the photocatalytic decomposition. On the other hand, for ST-01, UV-100, and AMT-100, the recovery was very slow (longer than 1 week) and only partially reversible, and the photocatalytic decomposition was considerably enhanced but retarded with rehydration. In the presence of adsorbed water, the binding of a carboxyl group of the molecules with adsorbed water is considered to compete with the direct adsorption on the surface, which reduces the amount of the direct adsorption and results in the reduction in the photocatalytic efficiency. In addition, the photocatalytic decomposition of benzoic acid with an aromatic ring was much faster in all of the TiO2 aqueous suspensions and more enhanced for the fully dehydroxylated TiO2 than that of acetic acid. These results suggest that the most efficient photocatalytic sites should be the hydrophobic sites on the TiO2 surface. The difference among the rehydration rates of different TiO2 is discussed in terms of thermally induced changes of surface morphology.
通过1H NMR光谱研究了热处理对六种具有不同性质的富含锐钛矿的TiO2光催化剂的再水化过程和光催化活性的影响。在水悬浮液中使用乙酸和苯甲酸进行光分解。在973 K煅烧后,P25、F4和AMT - 600的物理吸附水层恢复相对较快(短于24小时),光催化分解没有显著增强。另一方面,对于ST - 01、UV - 100和AMT - 100,恢复非常缓慢(长于1周)且仅部分可逆,光催化分解显著增强但随着再水化而受到抑制。在存在吸附水的情况下,分子的羧基与吸附水的结合被认为与在表面的直接吸附竞争,这减少了直接吸附的量并导致光催化效率降低。此外,在所有TiO2水悬浮液中,具有芳环的苯甲酸的光催化分解要快得多,并且对于完全脱羟基的TiO2比乙酸的光催化分解增强得更多。这些结果表明,最有效的光催化位点应该是TiO2表面的疏水位点。从表面形态的热诱导变化方面讨论了不同TiO2再水化速率的差异。