If it was easier for me to get away with at work I'd prefer 24/7 no question.
I love them any time of the day and in any situation but for some times in the day there are different reasons why I like them at that time.
However if I was told I could only ever put on one nappy per day and had to choose a time to do so and it always had to be the same time, I would probably say put it on maybe 2 hours before bed.
why?
Because this would give me a little bit of time before sleeping to just enjoy being in a nappy, I could wet a little if I wanted and having it on before going to bed would help me relax, unwind and go to sleep. If I then woke in the night needing the toilet I could go in the nappy without having to get out of bed and walk through a cold house/sit on a cold toilet. In the morning I could wake up possibly in a nice wet nappy, potentially (depending on how used) I could pee a little bit more and even have a morning BM before taking it off to get ready for work and on a weekend I could still lay in bed for a bit and just enjoy it for a bit longer.