Low temperature adsorption and site-conversion process of CO on the Ni(111) surface

Low-temperature (25 K) adsorption states and the site conversion of adsorbed CO between the ontop and the hollow sites on Ni(111) were studied by means of temperature programmed desorption and infrared reflection absorption spectroscopy. The activation energy and pre-exponential factor of desorption were estimated to be 1.2 eV and 2.6 × 1013 s− 1, respectively, in the limit of zero coverage. At low coverage, CO molecules preferentially adsorbed at the hollow sites below 100 K. With increasing temperature, the ontop sites were also occupied. Using a van't Hoff plot, the enthalpy and the entropy differences between the hollow and ontop CO were estimated to be 36 meV and 0.043 meV K− 1, respectively, and the vibrational entropy difference was estimated to be 0.085 meV K− 1. The positive entropy difference was the result of the low-energy frustrated translational mode of the ontop CO, which was estimated to be 4.6 ± 0.3 meV. With the harmonic approximation, the upper limit of the activation energy of site hopping from ontop sites to hollow sites was estimated to be 61 meV. In addition, it was suggested that the activation energy of hollow-to-hollow site hopping via a bridge site was less than 37 meV.

► CO adsorption on the Ni(111) surface was investigated with IRAS and TPD. ► The enthalpy and vibrational entropy differences between hollow and ontop CO were estimated. ► The energy of frustrated translational mode of ontop CO was estimated. ► Energy barrier of site hopping from the ontop sites to hollow sites is larger than that of hollow-to-hollow site hopping.