Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation
文献类型：期刊论文
| 作者 | Li, ZJ; Zhan F(展飞); Zhan, F; Xiao, HY; Zhang, XY; Kong, QY; Fan, XB; Liu, WQ; Huang, MY; Huang, C |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY LETTERS
 |
| 出版日期 | 2016 |
| 卷号 | 7期号:24页码:5253-5258 |
| DOI | 10.1021/acs.jpclett.6b02479 |
| 通讯作者 | 陶冶 |
| 文献子类 | 期刊论文 |
| 英文摘要 | X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [Ru-II(bpy)(3)]Cl-2 center dot 6H(2)O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([Co-II(DPA-Bpy)Cl]Cl) as the precatalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 +/- 0.03 angstrom. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand pi back bonding greatly stabilizes the penta-coordinated Co(I) intermediate, which provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure-function relationship of cobalt-based molecular catalysts. |
| WOS关键词 | AQUEOUS-SOLUTION ; COBALT COMPLEX ; POLYPYRIDYL CATALYSTS ; WATER ; REDUCTION ; PATHWAYS ; COBALOXIME ; MECHANISM ; DYNAMICS ; SYSTEM |
| 语种 | 英语 |
| WOS记录号 | WOS:000390087000046 |
| 源URL | [http://ir.ihep.ac.cn/handle/311005/260359]  |
| 专题 | 高能物理研究所_多学科研究中心 |
| 作者单位 | 中国科学院高能物理研究所 |
| 推荐引用方式 GB/T 7714 | Li, ZJ,Zhan F,Zhan, F,et al. Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation[J]. JOURNAL OF PHYSICAL CHEMISTRY LETTERS,2016,7(24):5253-5258. |
| APA | Li, ZJ.,展飞.,Zhan, F.,Xiao, HY.,Zhang, XY.,...&陶冶.(2016).Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation.JOURNAL OF PHYSICAL CHEMISTRY LETTERS,7(24),5253-5258. |
| MLA | Li, ZJ,et al."Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation".JOURNAL OF PHYSICAL CHEMISTRY LETTERS 7.24(2016):5253-5258. |
入库方式： OAI收割
来源：高能物理研究所
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