at speed your fan shouldn't be locked/on the speed of the air going through the radiator should be enough to cool it.
Do you have a shroud on your radiator?
Could be a suction problem, a bad lower radiator hose can collapse, since you are holding your rig at a higher RPM it will be more evident then when you wheel and the RPM varies.
it could be a cat, but unlikely, have you noticed a drop in power/acceleration? (more then the ordinary 4.0)
It could be a combination of problems, and I think you're on the right track. After it's fixed I'd drop another 210 thermostat in though. Those 4.0s are made to run at that temp and will not close the loop until it's close to 210.
My brothers CAT started to clogg and over time took longer and longer to start untill finally it wouldn't even turn over. His also started to run hotter but not that hot. Bang on your CAT and listen for stuff rattling around in there.
As dumb as it sounds, try a new radiator cap too. My family's van was having the same problems and dealership tried everything to get it to stop overheating. Hundreds of dollars later, someone figured out it was a cap that wasn't sealing properly.