I use both. Pi-hole running in a docker container on one of my home servers which my gateway is configured to assign as the default DNS for all clients, and uBlock Origin on all my browsers to catch everything else.
Pihole is pretty good at catching ads on platforms that are not suited to browser based blockers (IoT devices, streaming boxes etc) but it isn’t perfect and is best used in conjunction with another solution.
Doesn’t need to be a “green energy paradise”, just a reasonably well connected first world country.
Take a look at Electricity Maps. Unless you live somewhere isolated or with very poorly developed grid infrastructure (or some central US states, apparently), you should see a non-trivial amount of electricity being generated by non-fossil fuels. For example, at the time of typing this 77% of the electricity I’m using is low-carbon and 50% of it is renewable.
That’s the kicker. EVs don’t have to rely on fossil fuels to operate (but they can make use of them depending on the grid infrastructure). ICE cars on the other hand are burning fuel wherever they go.
Walking or cycling will always be the least polluting means of getting around, but if you really need a car then you could do a lot worse than getting an electric one.