Indeed, electrolytic smelting is around and is currently used to produce high purity iron.

There are a few engineering difficulties arising from the high temperatures required and the chemicals around.

And note that aluminum smelting also releases quite a lot of carbon dioxide for various reasons, one of them being consumption of the graphite electrodes.

1. https://en.wikipedia.org/wiki/Electrolytic_iron

2. https://www.newscientist.com/article/dn9878-electrolysis-may... (2006)

3. https://link.springer.com/article/10.1007/s10800-017-1143-5 (2018)