Energetics of adsorbed methanol and methoxy on Pt(111) by microcalorimetry

The heat of adsorption and sticking probability of methanol were measured on clean Pt(111) at 100, 150, and 210 K and on oxygen-precovered Pt(111) at 150 K by single-crystal adsorption calorimetry (SCAC). On clean Pt(111) at 100 K, the heat of methanol adsorption was found to be 60.5 ± 0.8 kJ/mol in the limit of low coverage, resulting in a standard enthalpy of formation (ΔH(f)°) of CH(3)OH(ad) of -263 ± 0.8 kJ/mol. The results at 150 and 210 K on clean Pt(111) were indistinguishable from the energetics measured at 100 K in the same coverage range. Calorimetry of methanol on oxygen-precovered Pt(111) at 150 K yielded the energetics of adsorbed methoxy, giving ΔH(f)°[CH(3)O(ad)] = -170 ± 10 kJ/mol and a CH(3)O-Pt(111) bond enthalpy of 187 ± 11 kJ/mol. By use of these enthalpies, the dissociation of adsorbed methanol on Pt(111) to form methoxy and a hydrogen adatom is found to be uphill by +57 kJ/mol. At coverages below 0.2 monolayer (ML), the sticking probability for methanol on both surfaces at or below 150 K was >0.95. At 210 K, ∼80% of the methanol beam pulse transiently adsorbs to clean Pt(111) with a surface residence time of 238 ms and heat of adsorption of 61.2 ± 2.0 kJ/mol, giving a prefactor for methanol desorption of 4 × 10(15±0.5) s(-1). These measured energetics for methoxy and methanol were compared to density functional theory (DFT) calculations from previous literature, showing DFT to routinely underestimate the bond energy of both adsorbed methanol and methoxy by 15-52 kJ/mol.