Carbon neutral electrochemical conversion of carbon dioxide mediated by [Mn+(cyclam)Cln] (M = Ni2+ and Co3+) on mercury free electrodes and ionic liquids as reaction media
Date Issued
2017
Author(s)
Honores, J.
Quezada, D.
Garcia, M.
Calfuman, K.
Muena, J. P.
Aguirre, M. J.
Arevalo, M. C.
Isaacs, M.
DOI
http://dx.doi.org/10.1039/c6gc02599d
Abstract
In this work, the electrochemical reduction of carbon dioxide using [Mn+(cyclam) Cl-n] (M= Ni2+ and Co3+) as electrocatalysts has been studied in 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (BMImBF(4) and BMImNTf(2) respectively) ionic liquids as reaction media. Complexes were characterized electrochemically in these salts and relevant parameters, such as a heterogeneous electron transfer rate was calculated. Results indicate a faster M(II)/M(I) redox process in BMImBF(4) despite its higher viscosity compared to BMImNTF(2). Cyclic voltammetry experiments demonstrated that [Ni(cyclam) Cl-2] is the most active macrocycle, towards the reaction under survey. For this compound, potential controlled electrolysis was carried out at-1.4 V vs. Ag/ AgCl in BMImBF4 as a solvent, yielding only CO as a reaction product, with a turnover frequency (TOF) of 0.73 h(-1). NMR spectra for the ionic liquids, after electrolysis, show that the applied potential does not affect the chemical structure of the salts. FT-IR thin layer spectroelectrochemical experiments in CO2 saturated solution in BMImBF(4) at -1.4 V vs. Ag/AgCl show the formation of [Ni(cyclam)CO](+) as precursor species, and also the most stable [Ni(CO)(4)].


