Maybe you are thinking of the cover shown here:
http://www.rfrajola.com/2k16/papal.jpgI sold this cover, ex Salzer, in a 1986 auction of the Tom Alexander collection (the whole collection is available in PDF format online). The image and description I show is from the book "Etats Pontificaux, 1852-1870" published by Monte Carlo Club in 2006, page 111. I provided the image to my friend Mario Zanaria and my advertisement that also shows the cover is on facing page.
I think this is the only known example in combination with a US stamp (which served served no purpose here).
The correct amount postage due was actually 5c and could not be prepaid in a foreign country with a US stamp. Most Papal States covers to US show this 5c due rate.