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Electrodeposition01:08

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Electrodeposition is a technique used to separate an analyte from interferents by electrochemical processes. Here, the analyte is a metal ion that can be deposited on an electrode immersed in the sample solution. The electrochemical setup consists of an anode and a cathode. When an electric current is applied to the setup, oxidation occurs at the anode. At the cathode, which consists of a large metal surface, metal ions undergo reduction and deposit onto the surface.
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In a galvanic cell, the electrical work is done by a redox system on its surroundings as electrons produced by the spontaneous redox reactions are transferred through an external circuit. Alternatively, an external circuit does work on a redox system by imposing a voltage sufficient to drive an otherwise nonspontaneous reaction in a process known as electrolysis. For instance, recharging a battery involves the use of an external power source to drive the spontaneous (discharge) cell reaction in...
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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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Transpassive Metal Dissolution vs. Oxygen Evolution Reaction: Implication for Alloy Stability and Electrocatalysis.

Annica Wetzel1,2, Daniel Morell1, Marcus von der Au1

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Summary

Multi-principal element alloys (MPEAs) show unexpected metal dissolution during oxygen evolution reactions (OER) in acidic conditions. This highlights the need to quantify metal ion release for accurate catalyst efficiency assessment.

Keywords:
Cyclic potentiodynamic polarizationMetal dissolutionMulti-principal element alloysOxygen evolution reactionScanning electrochemical microscopy (SECM)

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Corrosion Science

Background:

  • Multi-principal element alloys (MPEAs) offer tunable properties for electrochemical applications.
  • Their stability across various pH ranges is a key advantage.
  • However, their behavior under specific reaction conditions requires detailed investigation.

Purpose of the Study:

  • To investigate the concurrent occurrence of metal dissolution and oxygen evolution reaction (OER) in an equimolar CrCoNi alloy.
  • To develop and apply a characterization scheme to differentiate OER contributions from alloy dissolution.
  • To understand the mechanism of transpassive metal dissolution in MPEAs.

Main Methods:

  • Scanning electrochemical microscopy (SECM) for OER onset detection.
  • Inductively coupled-mass spectrometry (ICP-MS) and UV/Vis spectrometry for quantitative metal ion analysis.
  • In situ electrochemical atomic force microscopy (EC-AFM) to observe surface morphology changes.

Main Results:

  • Significant metal dissolution of CrCoNi alloy was observed during OER in a corrosive electrolyte (0.1 M NaCl, pH 2) in the transpassive region.
  • SECM, ICP-MS, and UV/Vis spectrometry successfully delineated OER and alloy dissolution.
  • EC-AFM revealed intergranular corrosion as the dominant mechanism for transpassive dissolution.

Conclusions:

  • Transpassive dissolution of MPEAs during OER can occur without obvious corrosion indicators.
  • Accurate assessment of OER catalysts requires quantification of released metal ions.
  • Metal ion release can negatively impact electrolyzer efficiency and reactor component integrity.