Abstract
The exchange reaction of adsorbed formate on Ni(110) with formic acid in gas phase was studied by the time-resolved infrared reflection absorption spectroscopy (TR-IRAS). It was found that the pre-adsorbed deuterated formate (DCOO(a)) was changed to HCOO(a) in the presence of HCOOD(g) at the temperature region from 240 to 300 K. In such a temperature region, the formate was stable on the surface in vacuum and the decomposition of formate was not observed. It was suggested that the pre-adsorbed DCOO(a) was desorbed as DCOOD accepting deuterium atom from HCOOD. The activation energy of the exchange reaction was estimated to be 23±2 kJ mol −1. The reaction order with respect to formic acid pressure was 0.3±0.1, while that as to the coverage of DCOO(a), was unity. Taking into account all the experimental results, the exchange of pre-adsorbed formate with post-exposed formic acid is suggested to proceed via forming a hydrogen-bonded intermediate complex on the formate's site, because all the sites were already occupied by formate. The small activation energy of the exchange reaction is discussed on the basis of `adsorption–assisted desorption'. We propose that when desorption and adsorption are coupled, the activation energy of the exchange reaction should be described as a sum of the potential energy profiles of a desorbing and an adsorbing molecule.
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