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C 2020, 6, 34 10 of 21 Table 2. Catalytic parameters in homogeneous catalysis of CO2. E0catalyst (V vs. SHE) η (V) DMF/0.1M EMIM TBABF4 TFSI 0.90 0.92 0.88 0.92 0.90 0.91 1.00 0.98 1.00 0.97 1.00 0.98 1.09 1.01 1.09 1.01 1.09 1.01 1.05 0.98 1.00 0.95 1.06 0.94 TOF (s−1) DMF/0.1M EMIM TBA BF4 TFSI [C2O42-] (mM) DMF/0.1M EMIM TBA BF4 TFSI Entry 1 2 3 4 5 6 7 8 9 Cat. WE DMF/0.1M TBA BF4 EMIM TFSI −0.919 −0.919 −0.919 −0.859 −0.859 −0.859 −0.829 −0.819 −0.829 −0.829 −0.839 −0.869 1 2 3 11 - - 6 18.2 3.41 Ag −0.919 Cu −0.889 C −0.899 Ag −0.839 Cu −0.80 C −0.839 Ag −0.699 Cu −0.689 C −0.689 Ag −0.719 Cu −0.699 −0.769 7 6 - - 24 9 10 8 13 - - 10 11 4 12 C 10 5 29 7 22 5 17 6 8 7 14 6 17 5 33.4 6.57 -- - - 38.1 9.37 -- - - 3.56 1.12 7-- Knowing that with carbon cathode it is possible to determine oxalate’s peak with CV, with a calibration curve is determined the amount of oxalate obtained with each p-nitro compound. Also, it is possible to obtain TOF values through Fowa’s method [92–96]. All the values were summarized in Table 2. Note that changing a methyl group by halides, the standard potential is lowered between 80–200 mV depending on electrode and halide. TOF values and oxalate amount obtained in DMF were higher than in EMIM TFSI. Faraday efficiencies were slightly higher in DMF solutions (from 30% to 88%) than in EMIM TFSI (from 10 to 51%) depending on the organic mediator used. These results can be explained due to low viscosity of the ionic liquid and coefficient diffusion value of CO2 (Table 3). Table 3. Viscosities and coefficient diffusion values of DMF and EMIM TFSI. Entry 1 Solvent Viscosity (mPa) a 0.92 Coefficient Diffusion (m2/s) b 3.6 · 10−9 9.7 · 10−11 Note, that it is possible to see an improvement in overpotential values with the use of ionic liquid instead DMF when p-nitrocompound has a halide group in its structure. Finally, note that it is possible to use small organic compound and ionic liquids to obtaining similar TOF values (in the order of s−1) to previously published one for organometallic and more sophisticated organic compounds [89,138,149,150]. On the other hand, we observed that for compound 4 the anion radical generated after electron transfer evolves to nitrobenzene radical at the same time that the CO2 reduction is electrocatalyzed. To check if it is possible to obtain electrocarboxylation product of 5 upon reaction of its radical with CO2, a control potential electrolysis at −0.96 V (vs. SHE) was performed. After the passage of 1F, no electrocarboxylated aromatic compounds were formed, being oxalate the only electroreduced product of CO2 formed. These results seem to indicate that the nitrobenzene radical formed upon reduction of 4 (Scheme 4) show a low nucleophility, being not able to attack and capture CO2. 3.3. Electrocarboxylation of Cyano-Compounds 6 and 7 under CO2 Atmposphere According to previous results obtained in our research group [151], 4-iodobenzonitrile follows an ECE reduction mechanism in ionic liquids (Scheme 6). In the presence of CO2 the electrogenerated anion intermediate leads to the corresponding carboxylation process. Hence, with the aim to obtain a stronger electrogenerated nucleophile, R− (Scheme 6), we decided to move from nitro to cyano DMF EMIM TFSI 37.3 from our laboratory research group [131]. 2 a Data obtained from Sigma Aldrich/Solvionic Safety Data Sheet (MSDS). b Data obtainedPDF Image | Electrochemical Tuning of CO2 Reactivity in Ionic Liquids
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