IR studies show that Cu+ ions in zeolites CuX, CuY, and CuZSM-5 are able to activate CC bond in alknenes
(ethene, propene, but-1-ene, and cis-but-2-ene). The stretching frequency of the CC− band decreased by
78−115 cm-1, indicating a significant weakening of the double bond. In ethene, the IR inactive CC stretching
became IR active when interacting with Cu+ as the result of the loss of symmetry. The band of CC interacting
with alkenes was split into two submaxima suggesting that Cu+ ions activate alkenes to a different extent.
The IR bands corresponding to C−H stretching, deformation, and bending of the CH2 and C−H groups
near the double bond also shifted to lower frequencies. At high loadings, some of the Cu+ ions were able to
bond two alkene molecules. The interaction of alkenes with Cu+ was so strong that alkenes replaced CO and
NO in relatively stable Cu+CO and Cu+(NO)2. Very strong interaction of alkenes with Cu+ was also evidenced
by a large shift of IR band of oxygen ring which was deformed by the interaction with Cu+ and relaxed when
Cu+ was withdrawn from the ring by alkene. Most probably the mechanism of the activation of alkenes by
Cu+ is similar to the mechanism of activation of NO, that is, involves the π-back-donation of d electrons of
Cu+ to π* antibonding orbitals of the alkenes.
The activation of CdO bond in formaldehyde molecule was followed by IR spectroscopy. IR studies showed that the interaction of formaldehyde with Cu + weakens of the CdO bond and results in a red shift of the CdO IR band (∆ν ) 56 cm -1 ). The activation of the CdO bond is the result of π back-donation of d electrons of Cu + to π * antibonding orbitals of the molecule. Experiments on coadsorption of formaldehyde and CO on the same Cu* showed that formaldehyde acts as electron donor to the Cu + -CO system, resulting in stronger π back-donation to antibonding orbitals of CO. IR studies showed that formaldehyde molecules sorbed in zeolite Cu-ZSM-5 are oxidized to formate ions. Cu 2+ ions, which survived the self-reduction to Cu + during the pretreatment of zeolite under vacuum, were oxidant. Such Cu 2+ ions are reduced to Cu + during the reaction with formaldehyde molecules.
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