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Electromotive Force02:36

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Electricity is generated by either electrons or ions flowing through a solution or a conducting medium. This flow of electrons or specifically electrical charge is defined as an electric current. When electrons move through a wire, they generate an electric current. It can be recalled  that in a redox reaction, electrons are lost and gained. In the spontaneous redox reaction of zinc  with copper, when zinc is immersed in a copper ion solution, a transfer of electrons from one...
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On comparing the reactivity of silver and lead, it is observed that the two ionic species, Ag+ (aq) and Pb2+ (aq), show a difference in their redox reactivity towards copper: the silver ion undergoes spontaneous reduction, while the lead ion does not. This relative redox activity can be easily quantified in electrochemical cells by a property called cell potential. This property is commonly known as cell voltage in electrochemistry, and it is a measure of the energy which accompanies the charge...
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Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
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Controlled-potential coulometry, also known as potentiostatic coulometry, employs a three-electrode system in which the working electrode's potential is precisely regulated using a potentiostat. Platinum working electrodes are utilized for positive potentials, while mercury pool electrodes are favored for extremely negative potentials. The platinum counter electrode is separated from the analyte using a membrane or salt bridge to avoid interference in the analysis.
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A concentration cell is a type of a  voltaic cell constructed by connecting two almost identical half-cells, both based on the same half-reaction and using the same electrode, differing only in the concentration of one redox species. A concentration cell's potential, therefore, is determined only by the concentration difference of the particular redox species.
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Plasmoelectric Potential in Plasmon-Mediated Electrochemistry.

Weihui Ou1,2,3,4,5, Yulong Fan6, Junda Shen6,4

  • 1School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou510006, China.

Nano Letters
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Summary

Plasmon-mediated electrochemistry benefits from plasmoelectric potential, a key factor alongside hot electrons and heating. This study quantifies these contributions, showing plasmoelectric potential dominates under specific conditions for improved electrocatalyst design.

Keywords:
PMCRhot carrierplasmoelectric effectsurface plasmonthermal effect

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Area of Science:

  • Surface Plasmon Resonance
  • Electrocatalysis
  • Photochemistry

Background:

  • Plasmon-mediated reactions enhance yield and selectivity.
  • Surface plasmon decay generates energetic charge carriers and heat, improving reactions.
  • The role of plasmoelectric potential in these reactions is under-explored.

Purpose of the Study:

  • To investigate the contribution of plasmoelectric potential in plasmon-mediated electrochemistry.
  • To develop a method for quantifying the effects of plasmoelectric potential, hot electrons, and photothermal heating.
  • To elucidate the mechanisms underlying plasmon-mediated electroreduction of oxygen.

Main Methods:

  • Utilized a plasmonic silver electrode for oxygen electroreduction.
  • Developed a quantitative method to differentiate plasmoelectric potential, hot electron, and photothermal contributions.
  • Employed short-wavelength illumination and moderate electrode bias.

Main Results:

  • Identified plasmoelectric potential as a significant contributor to plasmon-mediated electrochemistry.
  • Quantified the distinct roles of plasmoelectric potential, hot electrons, and photothermal heating.
  • Demonstrated that plasmoelectric potential is the dominant nonthermal factor under tested conditions.

Conclusions:

  • Plasmoelectric potential is a crucial, previously underestimated factor in plasmon-mediated electrochemistry.
  • The developed quantification method enables precise analysis of contributing factors.
  • Findings facilitate the design of high-performance plasmonic electrocatalysts.