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The enhancement of catalytic activity is always limited by the dilemma in activation and desorption due to Sabatier principle. Locating the Sabatier optimum by manipulating catalyst electronic structure has been a long‐standing challenge in heterogeneous catalysis. Herein, we presented a generic strategy to continuously tailor the Pt 5d state occupancy via tuning the PtOMn electronic linkage over Al2O3‐confined MnOx islands, aiming at accommodating the CH cleavage and product desorption capabilities in dehydrogenation of liquid organic hydrogen carriers (monocyclic/bicyclic hydrides). Rising Mn valence can decrease the Pt 5d state occupancy through more electron transfer from Pt 5d to O 2p due to the strong π‐donation of O 2p to Mn 3d. This will lead to the lower initial CH activation energy barrier while higher product desorption energy barrier. An intermediate Pt 5d filling of ~8.4 in PtMn2O3/Al2O3 enables the balanced level of product desorption and CH activation, thus ensuring a superior dehydrogenation activity. The electron structure‐adsorption‐performance modulation mechanism described herein provides a benchmark to locate the Sabatier optimum for the metal catalyst design. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: The catalytic properties of the CeO2 catalyst for propane dehydrogenation (PDH) are examined by employing the density functional theory calculations. Surface modifications and their effects on the surface reactivity are explored by creating the oxygen vacancy and single Pt atom doping. A comparative study between the binding energies of the different PDH reaction species reveals a considerable Lewis acid‐base interaction over the pristine and defective surfaces, which dominantly strengthens the bond formation between the adsorbates and the catalyst surface, resulting in the enhancement of surface reactivity. The creation of oxygen vacancy and doping the CeO2(111) surface with single Pt atoms changes the charge distribution over the surface on account of excess 4f electrons. This electronic change increases the bond formation abilities of the inactive Ce atom and hence increases the adsorption strength. Oxygen vacancy in the defective CeO2(111) surface migrates over the surface with the addition of an appropriate adsorbate. Moreover, it is revealed that the propylene is more strongly adsorbed on the single‐Pt‐atom‐doped CeO2(111) surface than the pristine and defective surfaces, which decreases the deep dehydrogenation energy barrier and ultimately results in the lowering of the selectivity. [ABSTRACT FROM AUTHOR]