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Author: Subject: Preventing anode deterioration during electrolysis?
Electra
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[*] posted on 26-2-2014 at 16:02
Preventing anode deterioration during electrolysis?


Under what conditions do anodes deteriorate/dissolve into solution? I wish to plate an electrode with a metal for catalytic purposes, how do I prevent this anode from dissolving into the solution during the oxidation of an organic compound?

I understand that if there is a salt in the anolyte that the anode can complex with, then it may form the M-Salt, but does this reaction happen at all if there is an organic compound dissolved in the solution?
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Zyklon-A
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[*] posted on 26-2-2014 at 16:24


What metal are you plating, and what material are you plating it on?



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Electra
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[*] posted on 26-2-2014 at 17:16


I was planning to plate Vanadium onto Copper due to coppers wide availability. If this doesn't turn out to be effective, I can plate something on top of the copper, and then plate the Vanadium on that.... any suggestions? I don't think the plating will be an issue, but rather preventing the anode from falling apart.
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hissingnoise
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[*] posted on 27-2-2014 at 08:25


Vanadium is not catalytically active and its pentoxide effectively catalyses the oxidation of SO2 only when it presents a large surface area to the action of the reducer!

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macckone
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[*] posted on 27-2-2014 at 09:53


Titanium is a good metal for plating onto.
It is readily available.

http://www.metalliferous.com/Base-Metal/departments/3186/

A local camping store will likely have cookware and utensils
made of titanium for a reasonable price as well.

http://www.rei.com/product/660002/snow-peak-titanium-spork

316L Stainless steel is resistant to many compounds and can be
used in some circumstances.

I would test copper in the acid that you will be using before
plating vandium or vandium oxide onto it. Bases generally
will not attack low reactivity metals (excluding aluminum)
aggressively. Evolved gases during the electrolysis are another
matter and highly variable.
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papaya
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[*] posted on 27-2-2014 at 11:03


If you speak about basic solutions (NaOH, etc) then nickel(or thick Ni plating) will do well both as anode and cathode provided that halides (chlorides, bromides,..) are not present.
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macckone
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[*] posted on 1-3-2014 at 20:36


Quote: Originally posted by papaya  
If you speak about basic solutions (NaOH, etc) then nickel(or thick Ni plating) will do well both as anode and cathode provided that halides (chlorides, bromides,..) are not present.


Nickel forms a protective layer with fluorides.
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hissingnoise
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[*] posted on 2-3-2014 at 04:33


I've certainly never heard of anyone attempting vanadium plating!

The OP may have discarded the idea . . .

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Electra
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[*] posted on 9-3-2014 at 23:19


I have not abandoned this project :).

Vanadium has a lot of interesting catalytic properties that have yet to be explored, that I tend to explore. Not only electrocatalytic use as a cathode but its use as an anode as well if I find a way to prevent it from falling apart in solution.

[Edited on 10-3-2014 by Electra]
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hissingnoise
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[*] posted on 10-3-2014 at 04:36


Quote:

Vanadium has a lot of interesting catalytic properties that have yet to be explored, that I tend to explore.


There are no such data in lit. that I've seen, so you may be poised to 'break new ground' . . . ?


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Electra
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[*] posted on 11-3-2014 at 16:58


Quote: Originally posted by hissingnoise  
Quote:

Vanadium has a lot of interesting catalytic properties that have yet to be explored, that I tend to explore.


There are no such data in lit. that I've seen, so you may be poised to 'break new ground' . . . ?



Depends what you mean by literature. If you are referring to research papers published by universities and similar organizations, then you are not looking hard enough because there are thousands of papers on vanadium being used for different purposes. I've spent a lot of hours(at least 300 hours) researching vanadium :S, this includes reading chinese papers that have not been translated into english yet.

It has tons of unique catalytic properties. Besides the obvious industrial use of its product for sulphuric acid, because of Vanadiums unique oxophilic properties, single-electron transitions and single-oxygen bearing oxidation states, it can allow for single oxygen oxidation of activated compounds. Vanadium is one of the few transition metals that can catalyze 99%+ yields of [activated] alkanes to alcohols(with inhibitors) and aldehydes, without over oxidation to the carboxylic acids. Overoxidation can occur but usually only in extreme unstable conditions such as very high pressures and temperatures. Vanadium also can self-oxidize in air, allowing the above reactions to occur with just using air/oxygen as the oxidizer, making it very economic for industrial processes.

Vanadium (V) ions oxidize alcohols to aldehydes at room temperature with simple stirring, using H2O2 as an oxidant. This conversion can also be done without an oxygen donor if performed in a room that has air, although, longer reaction times are required.

Vanadiums use as an electrocatalyst in redox cycles is very well documented. Vanadium, along with Cerium, are regenerated by anodes insitu to oxidize alkanes and alcohols to aldehydes very efficiently; electrons from the anodes act to activate various stable alkanes. As an anode, it can perform the above reactions by not only using electrons to activate alkanes, but by oxidizing water and taking its oxygens for the oxidations from the water itself. Just as electrocatalytic hydrogenations can occur at Pt/Ni/Pd/Ru/Co cathodes with using water(split in reduction) as the hydride source, electrocatalytic oxidations can be performed at the respective anodes. The above transition metals have been used for electrocatalytic oxidations but anodes of Pt and Pd can be too activating and easily push past the aldehyde. The biggest obstacle here is that the anode has potential to fall apart, while cathodes do not.


As a cathode I wish to experiment with Vanadiums oxophilic properties. Vanadium not only can adsorb hydrides and act as a hydrogenation catalyst and hydrogen storage source(greater than any other transition metal), but vanadium has an unusual attraction to oxygen. Vanadium can activate oxygen based bonds. This means as a cathode there is a great possibility that vanadium can easily hydrogenate carboxylic acids, aldehydes, and alcohols to alkanes, with using water as the hydride source. Zinc (and other metals) are also very oxophilic, but vanadium moreso, and zinc has been used in clemmensen reductions for taking aldehydes to alkanes.

Pt and Pd cathodes are already known to be able to perform hydrogenolysis on alcohols especially under the right conditions, taking alcohols to alkanes. Vanadium cathodes could possibly do something similar except by an oxophilic mechanism, unlike Pt/Pd.

[Edited on 12-3-2014 by Electra]
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hissingnoise
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[*] posted on 12-3-2014 at 06:09


Quote:
It has tons of unique catalytic properties.


Riiight! We know its compounds find use in various catalyses but it seems we'll just have to take your word that it's active in the elemental state?
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[*] posted on 11-8-2019 at 12:17


Electra,
I know this is an old thread, but have you had any success plating vanadium?
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