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I think that's not currently possible. It does sound useful and you might wish to submit a feature request (e.g. perhaps "when setting per-folder duplication, can we please also be able to set whether duplication for a folder is real-time or scheduled") to see if it's feasible?

I'm sure you figured it out already... From the images you posted, it just looks like a simple change is needed. The pool called ORICO BOX is fine as is. The one in the first image is not correct. You should have: A pool that has 12TB1 & 12TB2 with NO duplication set. (lets give it drive letter W:) A pool called ORICO BOX with NO duplication set. (with the assorted drives) (Lets call it drive letter X:) Now, drive W: essentially has 24TB of storage since anything written to W: will only be saved to ONE of the two drives. You can set the balancing plugin to make them fill up equally with new data. Drive X: essentially has 28TB of storage since anything written to X: will only be saved to ONE of the five drives. At this point, you make ANOTHER new pool, Lets call it Z: In it, put Drivepool W: and Drivepool X:. Set the duplication settings to 2X for the entire pool. Remember, you are only setting Drivepool Z: to 2X duplication, no other drivepools need changed. What this should do (if I didn't make a dumb typo): Any file written to drive Z: will have one copy stored on either 12TB1 OR 12TB2, AND a duplicate copy will be stored on ONE of the five Orico Box drives. You must read & write your files on drive Z: to make this magic happen. Draw it out as a flowchart on paper and it is much easier to visualise.