Synching your
CO2 with your lights is the safe way to go. Plants do not uptake
CO2 during lights-out so it is not necessary to supplement it at that time.
On the other hand, you will experience larger pH swings with the
CO2 off at night. When the lights come on in the morning the
CO2 will have to catch up with the amount that out-gassed during the night. This shouldn't be too much of a concern though.
If you have a pH controller you can leave your
CO2 on 24-hours-a-day without any concern because it won't let the
CO2 reach dangerous levels.