Oxygen Affinity of Transition Metal Cations: A Coherent Descriptor in
Catalytic Oxygenate Transformations
Abstract
This work reports a complementary descriptor to acidity for metal
cations, oxygen affinity, to scale the interaction strength of metal
cations with oxygenate groups. A method for measuring oxygen affinity is
developed in alkyl methylimidazolium chloride solvents using in-situ far
infrared (FIR) spectroscopy. The relative oxygen affinity values of
metal cations in metal chlorides with model compounds including
cyclopentanol (for alcohols), cyclohexanone (for ketones), ethylene
glycol diethyl ether (for ethers), and H2O are measured from the
dissociation kinetics of the metal-oxygenate complexes. The
concentrations of metal-chloride and metal-oxygenate complexes are
determined during evaporative removal of oxygenate molecules according
to the FIR absorbance of metal-Cl bonds. The oxygen affinity values are
shown to reasonably account for the catalytic performances of metal
cations in furfural-acetone condensation and glucose isomerization
reactions. The oxygen affinity descriptor could be potentially exploited
as an intrinsic property of metal cations broadly in metal chlorides and
metal oxides.