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In a pourable measuring cup, combine the milk and vinegar to make buttermilk. Let the mixture sit for a few minutes while preparing the muffin batter.
Combine all-purpose flour, cocoa powder, baking powder, salt, and sugar in a large mixing bowl. Make a well in the center and add the melted butter, extra virgin olive oil, eggs, vanilla extract and buttermilk. Whisk until just combined. Fold in the chocolate chips or chunks.
Fill silicone muffin cups to the top. Add a few extra chocolate chips to the tops if desired. Air fry at 400° Fahrenheit for 3 minutes. Lower the temperature to 350° Fahrenheit and bake another 10 minutes. Insert a toothpick into the center to check for doneness, adding 1 minute at a time until cooked through if necessary.