TY - JOUR
T1 - One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler?Volmer and Symmetric Marcus?Hush Theories Using Microdisk Electrodes
AU - Tanner, Eden E. L.
AU - Barnes, Edward O.
AU - Goodrich, Peter
AU - Hardacre, Christopher
AU - Compton, Richard G.
PY - 2015/2/19
Y1 - 2015/2/19
N2 - The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.
AB - The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.
KW - POTENTIAL-STEP CHRONOAMPEROMETRY
KW - EXPONENTIALLY EXPANDING MESH
KW - DIFFUSION-COEFFICIENTS
KW - EFFICIENT SIMULATION
KW - OXYGEN REDUCTION
KW - EUROPIUM III
KW - STEADY-STATE
KW - VOLTAMMETRY
KW - SOLVENTS
KW - KINETICS
U2 - 10.1021/jp512419d
DO - 10.1021/jp512419d
M3 - Article
SN - 1932-7447
VL - 119
SP - 3634
EP - 3647
JO - The Journal of Physical Chemistry Part C: Nanomaterials, Interfaces and Hard Matter
JF - The Journal of Physical Chemistry Part C: Nanomaterials, Interfaces and Hard Matter
IS - 7
ER -