A Half-Reaction Alternative to Water Oxidation: Chloride Oxidation to Chlorine Catalyzed by Silver Ion
文献类型：期刊论文
| 作者 | Du, Jialei1; Chen, Zuofeng1; Chen, Chuncheng2; Meyer, Thomas J.3 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2015-03-11 |
| 卷号 | 137期号:9页码:3193-3196 |
| 英文摘要 | Chloride oxidation to chlorine is a potential alternative to water oxidation to oxygen as a solar fuels half-reaction. Ag(I) is potentially an oxidative catalyst but is inhibited by the high potentials for accessing the Ag(II/I) and Ag(III/II) couples. We report here that the complex ions AgCl2- and AgCl32- form in concentrated Cl- solutions, avoiding AgCl precipitation and providing access to the higher oxidation states by delocalizing the oxidative charge over the Cl- ligands. Catalysis is homogeneous and occurs at high rates and low overpotentials (10 mV at the onset) with mu M Ag(I). Catalysis is enhanced in D2O as solvent, with a significant H2O/D2O inverse kinetic isotope effect of 0.25. The results of computational studies suggest that Cl- oxidation occurs by 1e- oxidation of AgCl32- to AgCl3- at a decreased potential, followed by Cl- coordination, presumably to form AgCl42- as an intermediate. Adding a second Cl- results in redox potential leveling, with further oxidation to {AgCl2(Cl-2)}(-) followed by Cl-2 release. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/28438]  |
| 专题 | 化学研究所_光化学实验室 |
| 作者单位 | 1.Tongji Univ, Dept Chem, Shanghai Key Lab Chem Assessment & Sustainabil, Shanghai 200092, Peoples R China 2.Chinese Acad Sci, Inst Chem, Key Lab Photochem, Beijing 100190, Peoples R China 3.Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA |
| 推荐引用方式 GB/T 7714 | Du, Jialei,Chen, Zuofeng,Chen, Chuncheng,et al. A Half-Reaction Alternative to Water Oxidation: Chloride Oxidation to Chlorine Catalyzed by Silver Ion[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015,137(9):3193-3196. |
| APA | Du, Jialei,Chen, Zuofeng,Chen, Chuncheng,&Meyer, Thomas J..(2015).A Half-Reaction Alternative to Water Oxidation: Chloride Oxidation to Chlorine Catalyzed by Silver Ion.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,137(9),3193-3196. |
| MLA | Du, Jialei,et al."A Half-Reaction Alternative to Water Oxidation: Chloride Oxidation to Chlorine Catalyzed by Silver Ion".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 137.9(2015):3193-3196. |
入库方式： OAI收割
来源：化学研究所
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