A couple of things come to mind???
(1.) Super heated steam is an attempt at eliminating any saturation or existing liquid in the steam (already a gas). The more energy present the more that energy becomes mechanical energy via the controlled explosion(expansion) in the cylender/piston.
(2.) Can you get it hot enough to seperate Water (steam) into Hydrogen and Oxygen? I would say no not in the confines of the pressure vessel discussed here. I could be wrong on this.
Superheated steam is a "hotter" steam (sometimes called "dry" steam) which contains more thermal energy than saturated steam. It becomes mechanical energy through expansion, not a "...controlled explosion..." Steam is not a combustible..it cannot "explode." Because the steam is heated far above its condensation temperature, it can do a lot of work before its heat energy is exhausted and it condenses back to water.
You cannot heat water in a steam locomotive anywhere close to 4,500 degrees F. At its hottest, the firebox will approach 2,500 degrees in the fire. The highest super heat steam temperature I have ever seen in a steam locomotive was just under 700 degrees F. And that was on a locomotive working HARD at maximum operating pressure (temperature) with an almost perfect fire and good coal.