Pushing the limits of the electrochemical window with pulse radiolysis in chloroform

Abstract

<p>We show that pulse radiolysis in chloroform enables the creation and study of radical cations beyond traditional electrochemical windows.</p>

Single Entity Behavior of CdSe Quantum Dot Aggregates During Photoelectrochemical Detection

“…Similar to the CH 3 CN case, for CHCl 3 the oxidation potential is ca. +3.2 V vs NHE (Bird et al, 2020), approximately 2 V more positive than the VB edge. The reduction potential for CHCl 3 has been reported to be ca.…”

How radiolysis impacts astatine speciation?

“…In addition, recent studies by using pulse radiolysis shown that if surrounded chloroform molecules participate with the CHCl +° the reaction ( 7) and ( 8) are more favorable (Bird et al, 2020):…”

Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations

“…19 The application of pulse radiolysis for measuring potentials of radical cations in organic solvents is less common due to the complex nature of solvent radiolysis. 20,21 In this work we have utilized the ability of 1,2-dichloroethane (DCE) to release the halide anion upon electron capture by a solvent molecule in the vicinity of radiolytically generated cations, e.g., from biphenyl (BP) molecules as shown in Scheme 1. The radiolysis of neat DCE has been thoroughly investigated in the past.…”

“…The pulse radiolysis approach has been widely used to determine numerous redox potentials of radical cations and anions in aqueous solutions in a wide potential range which extends beyond the electrochemical window of water . The application of pulse radiolysis for measuring potentials of radical cations in organic solvents is less common due to the complex nature of solvent radiolysis. , In this work we have utilized the ability of 1,2-dichloroethane (DCE) to release the halide anion upon electron capture by a solvent molecule in the vicinity of radiolytically generated cations, e.g., from biphenyl ( BP ) molecules as shown in Scheme . The radiolysis of neat DCE has been thoroughly investigated in the past. − During the initial ionization, electrons are ejected from solvent molecules forming radical cations and energetic nonsolvated electrons which propagate through the solvent medium away from positively charged species.…”