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Why would you need to melt the urea to electrolyze it? I'm actually a little behind with my chemistry, but you can electrolyze NaCl (salt) when dissolved in water, without melting it. The basic requirement is that the solution contains ions. Now I must admit that I don't know the basic reactions of urea with water, but given that you can use urea as hydrogen source in fuel cells [1] I'd assume that it should work as hydrogen source in an electrolytic process since the basic reaction is somewhat similar.

[1] see https://en.wikipedia.org/wiki/Urea#Laboratory_uses

Edit: There are papers about direct electrolysis of urea

http://www.suttonfruit.com/pics/urea_electrolysis.pdf (I think its a copy of http://pubs.rsc.org/en/Content/ArticleLanding/2009/CC/b90597...)

http://etd.ohiolink.edu/send-pdf.cgi/Singh%20Deepika.pdf?ohi...

Now I don't know how legit they are, but seems ok to me.




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