Nickel(III) reduction in electrolysis?

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Discussion Overview

The discussion revolves around the electrolysis of nickel oxides, specifically the reduction of Nickel(III) ions (Ni3+) compared to Nickel(II) ions (Ni2+). Participants explore the implications of using Nickel Oxide (NiO) versus Nickel(III) oxide (Ni2O3) in the context of electrolysis, with a focus on the chemical behavior and potential outcomes of the reduction process.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant expresses curiosity about the reduction of Ni3+ ions and references a reaction involving the reduction of Ni3+ to Ni2+ in two steps.
  • Another participant suggests that NiO is insoluble and proposes using a soluble salt like NiCl2 instead, while expressing doubt about the presence of nickel(III) oxide.
  • A third participant clarifies that their goal is not nickel plating but rather to create nucleation sites using nickel particles, confirming the use of black nickel oxide (Ni(III)).
  • A later reply raises concerns about the kinetics of the reduction process, noting that the standard reduction potential may not account for kinetic barriers that could affect the outcome.
  • Participants discuss the importance of following established recipes for electrolysis and suggest that alternative methods may exist for producing nickel nanoparticles.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the best approach for the electrolysis involving Ni3+. There are competing views on the feasibility and methods for achieving the desired results, with uncertainty regarding the kinetics of the reduction process.

Contextual Notes

Limitations include the potential presence of kinetic barriers in the reduction of Ni(III) to Ni(II), the dependence on the specific electrolyte composition, and the lack of clarity on the exact nature of the nickel oxide being used.

Latsabb
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I ordered in chemicals for doing some electrolysis work, one of which was Nickel Oxide. I didnt think to check if it was NiO, or Ni2O3. I was supposed to be using NiO for the Ni2+ ions, but I am curious how this would work out with Ni3+ ions? Will Ni3+ still reduce in the same manner as Ni2+? I was digging through some previous work, and saw a couple of places using 2Ni3+ + 2e- -> 2Ni2+, which made me think that it would reduce and plate in two steps. First going from 3+ to 2+, and then plating on.

Does anyone know? Normally I would just give it a shot, but the rest of the electrolyte composition is too expensive for me to try and toss for no reason.
 
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Are you following a recipe for this electrolysis? NiO is pretty insoluble. If I were doing nickel electroplating (and not following a recipe), I'd start with a soluble salt like NiCl2. To answer your question, I doubt you have nickel(III) oxide; it's pretty rare. But if you can get nickel ions into solution, and if your voltage is high enough, the Ni3+ will eventually reduce just like Ni2+. But unless you're following a recipe, I'd be inclined to try something other than nickel oxide.
 
This isn't for nickel plating as such, and the low solubility is the key, as I need the electrode covered in particles of nickel, not a layer. The nickel is for nucleation sites of a further reaction. And yes, it is Ni(III), black nickel oxide.
 
I see. Well, most of my original comment still applies. I don't know what the kinetics of reduction of Ni(III) to Ni(II) is, so I can't say for certain whether you'll get the desired results. The standard reduction potential will only take you so far. If there's a kinetic barrier, the reduction will require an overpotential which is highly dependent on everything going on in the electrolysis bath. If you're following a recipe, I'd say stick to it (especially if it's from the primary literature--it might not be so easily reproducible otherwise). If you're trying to make something like Ni nanoparticles, there are probably other ways to go about doing that which are easier. I'm not sure how much help you're going to get unless you're much more specific about what you're trying to do.
 

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