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Preheat oven to 440 degrees F (227 degrees C). Whisk onion, ketchup, vinegar, honey, brown sugar, Worcestershire sauce, mustard, and cayenne pepper together in a bowl until barbeque sauce is smooth. Place pork chops on a baking sheet and season with salt and pepper. Top each pork chop with 2 tablespoons barbeque sauce. Bake in the preheated oven until pork chops are cooked through, about 30 minutes. An instant-read thermometer inserted into the center should read at least 145 degrees F (63 degrees C).
Sprinkle both sides of the pork chops with salt and pepper and place in a re-sealable plastic bag with the marinade. Let rest on the counter for 1 hour. That's easy. Heat a grill or grill pan over medium heat. Remove the pork chops from the bag and lightly sprinkle with salt and pepper. Place on the grill and cook until the pork chop releases from the grill, about 4 minutes. Flip and cook on the other side for another 3 minutes. If using a grill pan, be sure to do in batches so you don't steam the chops. And don't worry if you have neither; you can do this in a pan.