Preheat the oven to 450 degrees F.
Spray a baking sheet slightly with oil and set aside. Place potato chips in the bowl of a food processor and process into crumbs, about 20 seconds. Transfer to a shallow bowl, add cayenne, and set aside. In another bowl, combine buttermilk, 2 tablespoons of flour, salt and pepper and set aside. Slice onions into 1/2-inch circles and separate into rings, keeping only large, whole rings (reserve rest of onions for other uses). You should come out with about 12 to 14 rings.
Place the remaining flour in a sealable plastic bag, then add onions, and shake to coat. Dip onions 1 at a time into the buttermilk mixture, then dip into potato chip crumbs and place on baking sheet. Spray canola oil evenly over rings and bake for 20 minutes, or until coating is crisp. Season with salt, to taste, and serve immediately.