In-Site Polarization Modulated FTIR and Differential Electrochemical Mass Spectroscopy

We recently report the electrochemical promotion of the heterogeneously catalyzed isomerization of 1-butene to cis- and trans-butene with p values of 38 and 46, respectively. at the remarkably low temperature of 70 Deg C using Nafion as the electrolyte in a fuel cell configuration. This was the first reported case of a NEMCA promoted unimolecular and non-redox reaction concomitant with the reduction of butene to butane. We now present isotopic mass spectral and FTIR data confirming the mechanism involves abstraction of a proton from the catalytic surface for Markovnikov addition to the C-I carbon concomitant with removal of a proton from C-3 to yield the isomer. This striking example of an acid catalyzed reaction at a metal surface is facilitated by the use of the super acidic Nafion electrolyte. Material: 1-butene: cis-2-butene; trans-2-butene; Nafion; Pd; Deuterium; D2O.