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Issue 4, 2017
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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

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Abstract

In this work, the electrochemical reduction of carbon dioxide using [Mn+(cyclam)Cln] (M = Ni2+ and Co3+) as electrocatalysts has been studied in 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMImBF4 and BMImNTf2 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 BMImBF4 despite its higher viscosity compared to BMImNTF2. Cyclic voltammetry experiments demonstrated that [Ni(cyclam)Cl2] 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 BMImBF4 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].

Graphical abstract: 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

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Publication details

The article was received on 16 Sep 2016, accepted on 03 Jan 2017 and first published on 11 Jan 2017


Article type: Paper
DOI: 10.1039/C6GC02599D
Citation: Green Chem., 2017,19, 1155-1162
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    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

    J. Honores, D. Quezada, M. García, K. Calfumán, J. P. Muena, M. J. Aguirre, M. C. Arévalo and M. Isaacs, Green Chem., 2017, 19, 1155
    DOI: 10.1039/C6GC02599D

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