Galvani Potential-Dependent Single Collision/Fusion Impacts at Liquid/Liquid Interface: Faradic or Capacitive?

Liu, Cheng; Ma, Yamin; Xu, Zhao‐Dong; You, Yongtao; Bai, Silan; Nan, Junmin; Wang, Lishi

doi:10.1021/acs.jpcb.2c05741

Cited by 3 publications

(1 citation statement)

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“…To investigate the interaction between a droplet and an electrode surface, stabilized droplets and well-defined model systems are needed. Using room temperature ionic liquid (RTIL) as the surfactant is a good way to stabilize the emulsion since the cation and anion of RTIL could be adjustable for the required amphiphilicity and surfactancy, together with the biocompatibility and environmental friendliness. , The most studied droplets are emulsions in SEE. ,− Deng’s group suggested the shape changes of oil emulsions landing on the electrode and proposed four collision mechanisms by employing fast-scan cyclic voltammetry and monitoring the phase angle of the current. , It is known that the ET at the emulsion–electrode interface is coupled with ion transfer (IT) at the oil/water interface or oil/RTIL interface. The IT thermodynamics has also been revealed in Deng’s reports, , however, the ET kinetics, the dynamic emulsion–electrode interaction, and the relationship between the two still remain unknown.…”

Section: Introductionmentioning

confidence: 99%

Impact of Surface Chemistry on Emulsion–Electrode Interactions and Electron-Transfer Kinetics in the Single-Entity Electrochemistry

Du,

Zhang,

Meng

et al. 2024

Anal. Chem.

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Single-entity electrochemistry (SEE) provides powerful means to track a single particle, single cell, and even single molecule from the nano to microscale. The electrode serves as not only the detector of collision but also the surface supplier in SEE, and the fundamental understanding of the electrode surface chemistry on the dynamic particle−electrode interactions and electrochemical responses of a single particle still remains unexplored, particularly for soft particles. Herein, dynamic interactions of microemulsions and the interaction-controlled electron-transfer (ET) kinetics are studied employing SEE and fluorescence spectroscopy. The o/w-type nitrobenzene emulsions were prepared with the surfactant-type room temperature ionic liquids (RTILs). Biased the electrode potential for the reduction of 7,7,8,8-tetracyanoquinodimethane within emulsions, it is surprising to see the distinct collision current signals on the carbon fiber ultramicroelectrode (C UME) and Au ultramicroelectrode (Au UME) in the late stage of chronoamperometric measurements. Theoretical understanding was made to determine the ET kinetics behind the disparate current signals. It is believed that the electrode surface chemistry, i.e., the surface energy, has a great influence on the dynamic emulsion− electrode interactions and ET kinetics. On the hydrophilic surface of Au UME, emulsions tend to decompose/detach from the electrode surface immediately after colliding. In contrast, on the lipophilic surface of C UME with lower surface energy, a layer of oil phase accumulated by the coalescence of emulsions and the migration of the precedent colliding emulsions, which would serve as a barrier to block ET via tunneling as manifested by the gradual slowdown of ET rate and the reduced collision frequency in the late stage of measurement. The impacts of the emulsion size and amphiphilicity of RTILs on the C UME-emulsion interactions and ET kinetics were also investigated.

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