There is a cec library that should be compatibly with raspberry pi OS. I have not used it personally but here is a tutorial that might help: pimylifeup.com/raspberrypi-hdmi-cec/ This might require some custom scripting, what were you hoping to accomplish?
basically, no. Volumio is purposely compiled with a specific pared-down kernel + drivers to optimise audio processing, and isn't designed to have other apps installed on top of it. RasPis are cheap - just run two of them :.)