Zhen Fangchen, Percevault Lucie, Paquin Ludovic, Limanton Emmanuelle, Lagrost Corinne, Hapiot Philippe
Univ Rennes , CNRS, ISCR - UMR 6226 , F-35000 Rennes , France.
J Phys Chem B. 2020 Feb 13;124(6):1025-1032. doi: 10.1021/acs.jpcb.9b09022. Epub 2020 Feb 4.
Electron transfer (ET) kinetic rate constants in Ethaline (1:2 choline chloride + ethylene glycol) have been measured for two common redox couples (ferrocene/ferrocenium and ferrocyanide/ferricyanide) on a glassy carbon electrode and compared with ET kinetics in ionic liquids and classical organic solvents in the same conditions (acetonitrile and water). Particular care has been taken to treat ohmic drop in DES. For both couples, we found that ET rate constants are just a little lower than those measured in classical solvents (around 50% or less). These results contrast with ET rates in ionic liquids where electron transfers are considerably slower (100 times lower). Data are discussed as a function of the solvent relaxation time using Marcus Theory for an adiabatic electron transfer.
在玻碳电极上，已测量了两种常见氧化还原电对（二茂铁/二茂铁鎓和亚铁氰化物/铁氰化物）在乙aline（1:2氯化胆碱+乙二醇）中的电子转移（ET）动力学速率常数，并与相同条件下离子液体和经典有机溶剂（乙腈和水）中的ET动力学进行了比较。在处理深共熔溶剂中的欧姆降时格外小心。对于这两种电对，我们发现ET速率常数仅比在经典溶剂中测得的略低（约低50%或更低）。这些结果与离子液体中的ET速率形成对比，在离子液体中电子转移要慢得多（低100倍）。使用绝热电子转移的马库斯理论，根据溶剂弛豫时间对数据进行了讨论。
