期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 24, 页码 13463-13469出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103157
关键词
homogeneous photocatalysis; molecular catalysts; nickel; porphyrins; water oxidation
资金
- China Scholarship Council (CSC) [201706360150]
Finding photostable first-row transition metal-based molecular systems for photocatalytic water oxidation is a key step towards sustainable solar fuel production. Nickel(II) hydrophilic porphyrins have been discovered as molecular catalysts for this purpose, showing high turnover frequencies but with issues in the catalytic activity of the electron-poorest Ni-porphyrin.
Finding photostable, first-row transition metal-based molecular systems for photocatalytic water oxidation is a step towards sustainable solar fuel production. Herein, we discovered that nickel(II) hydrophilic porphyrins are molecular catalysts for photocatalytic water oxidation in neutral to acidic aqueous solutions using [Ru(bpy)(3)](2+) as photosensitizer and [S2O8](2-) as sacrificial electron acceptor. Electron-poorer Ni-porphyrins bearing 8 fluorine or 4 methylpyridinium substituents as electron-poorer porphyrins afforded 6-fold higher turnover frequencies (TOFs; ca. 0.65 min(-1)) than electron-richer analogues. However, the electron-poorest Ni-porphyrin bearing 16 fluorine substituents was photocatalytically inactive under such conditions, because the potential at which catalytic O-2 evolution starts was too high (+1.23 V vs. NHE) to be driven by the photochemically generated [Ru(bpy)(3)](3+). Critically, these Ni-porphyrin catalysts showed excellent stability in photocatalytic conditions, as a second photocatalytic run replenished with a new dose of photosensitizer, afforded only 1-3 % less O-2 than during the first photocatalytic run.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据