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Photo- and Electrocatalytic Hydrogen Production Using Valence Isomers of N2S2-Type Nickel Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-09-22 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01244 Satoshi Inoue 1 , Manabu Mitsuhashi 1 , Takeshi Ono 1 , Yin-Nan Yan 1 , Yusuke Kataoka 2 , Makoto Handa 2 , Tatsuya Kawamoto 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-09-22 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01244 Satoshi Inoue 1 , Manabu Mitsuhashi 1 , Takeshi Ono 1 , Yin-Nan Yan 1 , Yusuke Kataoka 2 , Makoto Handa 2 , Tatsuya Kawamoto 1
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Three Schiff-base-type nickel(II) complexes (1a–3a) and the corresponding noninnocent-type complexes (1b–3b) were synthesized, and the equilibria between these valence isomers were observed in tetrahydrofuran (THF) at room temperature. The electronic state of the noninnocent-type nickel complex was also confirmed by isolation of the one-electron-reduced species. The catalytic ability for the photogeneration of hydrogen from water was examined about 1a–3a and 1b–3b in the presence of a photosensitizer and a sacrificial electron donor. Then, a Schiff-base-type complex with chlorine atoms (2a) and a noninnocent-type complex with methyl groups (3b) on the pendant phenyl rings being present as the minor species in THF exhibited high activity of over 400 turnover numbers. The dynamic light scattering and transmission electron microscopy measurements suggested the formation of NiSx-like aggregate species under photocatalytic conditions. The electrocatalytic activities of the nickel complexes for hydrogen production were also investigated, and a plausible reaction mechanism was proposed on the basis of a combined electrochemical and density functional theory study.
中文翻译：
N 2 S 2型镍配合物的价态异构体的光催化和电催化制氢
合成了三种席夫碱型镍（II）配合物（1a - 3a）和相应的非清纯型配合物（1b - 3b），并在室温下在四氢呋喃（THF）中观察到这些价异构体之间的平衡。非纯型镍络合物的电子状态也通过单电子还原物种的分离得到证实。在存在光敏剂和牺牲电子供体的情况下，检查了大约1a - 3a和1b - 3b对从水中光生氢的催化能力。然后，形成具有氯原子的席夫碱型络合物（2a）和在苯环上作为甲基的次要物种而在苯基侧链上带有甲基（3b）的非清白型络合物表现出超过400个转换数的高活性。动态光散射和透射电子显微镜测量表明在光催化条件下形成了NiS x样聚集体。还研究了镍配合物对产氢的电催化活性，并在电化学和密度泛函理论相结合的基础上提出了合理的反应机理。
更新日期：2017-09-22
中文翻译：
N 2 S 2型镍配合物的价态异构体的光催化和电催化制氢
合成了三种席夫碱型镍（II）配合物（1a - 3a）和相应的非清纯型配合物（1b - 3b），并在室温下在四氢呋喃（THF）中观察到这些价异构体之间的平衡。非纯型镍络合物的电子状态也通过单电子还原物种的分离得到证实。在存在光敏剂和牺牲电子供体的情况下，检查了大约1a - 3a和1b - 3b对从水中光生氢的催化能力。然后，形成具有氯原子的席夫碱型络合物（2a）和在苯环上作为甲基的次要物种而在苯基侧链上带有甲基（3b）的非清白型络合物表现出超过400个转换数的高活性。动态光散射和透射电子显微镜测量表明在光催化条件下形成了NiS x样聚集体。还研究了镍配合物对产氢的电催化活性，并在电化学和密度泛函理论相结合的基础上提出了合理的反应机理。
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