Zinc protects iron because it is more reactive than iron and therefore reacts preferentially with any reagent, for instance oxygen:2Zn + O2 --> 2ZnO
This is called sacrificial protection. If the zinc is completely covering the iron it also protects it physically as there is a coherent layer of zinc oxide on the surface which keeps the metals away from attacking reagents.
If you put clean aluminium into copper nitrate solution you get a displacement reaction:
2Al + 3Cu(NO3)2 --> 2Al(NO3)3 + 3Cu
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