Hi there, @andy11… like pretty much all things Bubble, there are a number of ways to do what you described. One of those ways would be to put a condition on the workflow event to create a thing in the data type only when a count of a search for a thing created by the current user for the selected day is 0. As you can imagine, though, such a search might not be the most performant way to go if you have lots of sellers creating lots of things in the data type.
Another way to go (which might be viewed as a bit “unconventional”) would be to remove the possibility of the user creating a duplicate thing for the same day by removing days from the dropdown as a user creates things for them. You could make that happen by having a list field on the User data type that stores a list of the days that have already been selected. With that field in place, you would configure the choices source for the dropdown as all of the days minus the list of days stored for the current user, and then you wouldn’t have to worry about checking for duplicate things.
Anyway, those are a couple of ways you could go, and I hope this helps.
In the first screenshot, do you have any constraints on the Search for OpeningTimess? If you don’t, try adding a constraint on that search where Created by = Current User and see if that does the trick.