Hydrogen Generation by Hangman Metalloporphyrins
Hydrogen Generation by Hangman Metalloporphyrins
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DOI：
10.1021/ja202136y
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发表时间：
2011-06-15
影响因子：
15
通讯作者：
Nocera, Daniel G.
中科院分区：
文献类型：
--
作者：
Lee, Chang Hoon;Dogutan, Dilek K.;Nocera, Daniel G.
一种具有氧杂蒽骨架和羧酸悬挂基团的钴（II）Hangman卟啉催化苯甲酸和对甲苯磺酸在乙腈溶液中的电化学制氢。我们表明，（CoH）-H-II是专门参与从弱酸生成H-2。在较强的酸中，电化学观察到（CoH）-H-III物质，但在H-2产生发生之前，它仍然需要进一步还原为（CoH）-H-II。由于Hangman效应，H-2产生的过电位降低。
A cobalt(II) hangman porphyrin with a xanthene backbone and a carboxylic acid hanging group catalyzes the electrochemical production of hydrogen from benzoic and tosic acid in acetonitrile solutions. We show that (CoH)-H-II is exclusively involved in the generation of H-2 from weak acids. In a stronger acid, a (CoH)-H-III species is observed electrochemically, but it still needs to be further reduced to (CoH)-H-II before H-2 generation occurs. Overpotentials for H-2 generation are lowered as a result of the hangman effect.