Within the frontier orbital picture for metal chemistry, the local density of states at the Fermi energy (E-f-LDOS) plays the equivalencies of the highest-occupied molecular orbitals (HOMO) and the lowest-unoccupied molecular orbitals (LUMO) in the molecular cases. We show here that one can effectively engineer the clean surface E-f-LDOS, i.e., the frontier orbitals, of a platinum catalyst already formed within a zeolite-NaY matrix, by simply exchanging the counterion in the matrix. The potassium (K) increases while the proton (H) decreases the clean surface E-f-LDOS. The degree of enhancement or reduction depends on the degree of ion-exchange. When the intramolecular stretching frequencies of chemisorbed carbon monoxide (GO) on these E-f-LDOS enhanced and decreased samples were measured, the values extrapolated to zero coverage show an almost linear relationship with their corresponding clean surface E-f-LDOS before chemisorption.