A couple of wires of dissimilar metals forming a loop and producing thermoelectricity is called thermocouple. The magnitude of emf produced and the direction of current depends on the pair of metals selected from the thermoelectric series and temperature of the junction. In iron – copper thermocouple, current flows from iron to copper at the cold junction. The direction of current flow changes if heating and cooling of the junction are reversed.
It is not about the metal we are placing. Its about the temperature difference in both dissimilar metals occurs. One metal must have a higher or lower temperature than the other.
If we change the metal the temperature difference may changed according to the property of the metal used.