The effect of fluorination on the surface chemistry of alkyl ethers on Cu(111)

Abstract

By using small fluorinated ethers as models for perfluoropolyalkylether (PFPAE) lubricants, we have been able to determine the effect of fluorination on the bonding of the alkyl ethers adsorbed on the Cu(111) surface. The desorption energies have been determined by using temperature programmed desorption (TPD). The model compounds studied were dioxolane , \(({\text{H}}_{\text{2}} )\)diethyl ether ((CH3CH2)2O), dimethoxymethane ((CH3O)2CH2), dimethyl ether ((CH3)2O) and their perfluorinated analogues. All of the molecules studied adsorb molecularly and reversibly on the Cu(111) surface exhibiting first-order desorption kinetics. Upon fluorination of the alkyl ethers, the adsorbate-metal bond was weakened by ∽14 to ∽8 kcal/mol. The intermolecular interaction parameters for the hydrogenated ethers indicated repulsive adsorbate-adsorbate interactions, while the fluorinated ethers have attractive adsorbate-adsorbate interactions.