Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(II) complex.
Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(II) complex.
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DOI：
10.1039/c2cp41207a
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发表时间：
2012-07-21
期刊：
影响因子：
--
通讯作者：
Fukuzumi S
中科院分区：
文献类型：
--
作者：
Yamada Y;Maeda K;Ohkubo K;Karlin KD;Fukuzumi S
在乙腈中分子氧光催化氧化对二甲苯的反应中，加入[{三(2-吡甲基)胺}-CuII](ClO4)2([(Tmpa)CuII]2+)可以显著提高有机光催化剂9-甲基甲基-10-甲基吖啶离子(ACR+-MES)的催化稳定性。在没有有机配体的情况下，加入Cu(ClO4)2不能观察到这样的改善。在反应溶液中加入[(Tmpa)Cu2+]2+，得到的Ton比不加入[(Tmpa)CuII]2+时的Ton高11倍以上。在光催化氧化过程中，在没有[(Tmpa)CuII]2+的情况下，可以观察到化学计量的过氧化氢的生成，而在有[(Tmpa)CuII]2+的情况下，生成的过氧化氢要少得多。为了检测中间体，通过激光闪光光解测试研究了其光催化机理。在203K的丙腈溶液中，UV-Vis光谱监测到O2·−与[(Tmpa)CuII]2+的反应表明生成了[{(Tmpa)CuII}2O2]2+，这一转变对O2整体4电子还原为水是关键的，也是观察到的ACr+-MES催化持久性提高的关键。
The catalytic durability of an organic photocatalyst, 9-mesityl-10-methyl acridinium ion (Acr+–Mes), has been dramatically improved by the addition of [{tris(2-pyridylmethyl)amine}-CuII](ClO4)2 ([(tmpa)CuII]2+) in the photocatalytic oxygenation of p-xylene by molecular oxygen in acetonitrile. Such an improvement is not observed by the addition of Cu(ClO4)2 in the absence of organic ligands. The addition of [(tmpa)Cu]2+ in the reaction solution resulted in more than an 11 times higher turnover number (TON) compared with the TON obtained without [(tmpa)CuII]2+. In the photocatalytic oxygenation, a stoichiometric amount of H2O2 formation was observed in the absence of [(tmpa)CuII]2+, however, much less H2O2 formation was observed in the presence of [(tmpa)CuII]2+. The photocatalytic mechanism was investigated by laser flash photolysis measurements in order to detect intermediates. The reaction of O2˙− with [(tmpa)CuII]2+ monitored by UV-vis spectroscopy in propionitrile at 203 K suggested formation of [{(tmpa)CuII}2O2]2+, a transformation which is crucial for the overall 4-electron reduction of molecular O2 to water, and a key in the observed improvement in the catalytic durability of Acr+–Mes.
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影响因子：
3.2
作者：
Fukuzumi, S
通讯作者：
Fukuzumi, S
影响因子：
15
作者：
Fukuzumi S;Kotani H;Lucas HR;Doi K;Suenobu T;Peterson RL;Karlin KD
通讯作者：
Karlin KD
影响因子：
15
作者：
Fukuzumi, S;Suenobu, T;Ito, O
通讯作者：
Ito, O
影响因子：
15
作者：
Fukuzumi, S;Patz, M;Itoh, S
通讯作者：
Itoh, S
DOI：
10.1039/c39890000816
发表时间：
1989-07-01
影响因子：
--
作者：
FUKUZUMI, S;TANII, K;TANAKA, T
通讯作者：
TANAKA, T