Oxygenated fluorocarbons adsorbed at metal surfaces: chemisorption bond strengths and decomposition

Journal Article · Wed Sep 16 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00253a010· OSTI ID:5954641

Walczak, M M; Leavitt, P K; Thiel, P A

The authors report studies of the adsorption bond strengths and decomposition of perfluorodiethyl ether and hexafluoroacetone on clean and oxygen-dosed Ru(001). Perfluorodiethyl ether bonds weakly to Ru(001) (39 kJ/mol) without decomposing. This binding energy is typical for a metal-adsorbate interaction in which the adsorbate donates electrons to the metal from the oxygen lone pair. Hexafluoroacetone bonds to the surface in both a weakly bonded configuration (38 kJ/mol) and a strongly bonded configuration (66-87 kJ/mol), and there is some decomposition. They compare the chemistry of these oxygenated fluorocarbons to analogous oxygenated hydrocarbons. They propose that the net effect of fluorination is to weaken those chemisorption bonds which rely upon electron donation from the oxygen lone pairs to the metal but to strengthen the chemisorption bonds which rely primarily upon electron donation from the metal into antibonding C-O orbitals. Both phenomena can be explained by electronic effects resulting from fluorination.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5954641
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ADSORPTION
BINDING ENERGY
CHEMICAL BONDS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
ENERGY
ETHERS
EXPERIMENTAL DATA
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
INFORMATION
METALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PLATINUM METALS
RUTHENIUM
SORPTION
SORPTIVE PROPERTIES
SURFACE PROPERTIES
TRANSITION ELEMENTS