Co2 in a PCP rifle

Yes it's perfectly fine to do. Common Buna-N O-rings, which is the type you'll find in almost every production PCP rifle, contain CO2 well. You only need polyurethane for a location like a removable end cap because CO2 swells most types of O-rings which would prevent you from being able to reinstall it after swapping a cartridge, but of course there are no cartridges in this scenario so it's a moot point.

And since CO2 produces only about 850psi at 70F, you'll need to back off your hammer spring tension if your rifle is currently set up to operate at typical PCP pressures of 1500 - 3000psi. Otherwise it will consume a tremendous amount of CO2. That's not only wasteful but it aggravates the chilling effect which causes the pressure to gradually drop and the velocity will be affected.