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C 2020, 6, 34 14 of 21 concentration of CO2 is rising. These results can be explained taking into account that under these experimental conditions two electrochemical processes are happening at the electrode surface at same potential; the reduction of the cyanoaromatic halide and the direct reduction of CO2 (Figure 6b,d). The same trend is observed with the use of copper cathode and a ionic liquid with wide electrochemical window, such as 1-methyl-1-propylpiperidinium bis(trifluoromethylsulphonyl)-imide ([PP13] TFSI). Note that in this cases EMIM TFSI cannot be used as a IL, since the reduction of the EMIM cation takes place c.a. −2.06 V vs. SHE. [151]. 4. Conclusions In conclusion, we describe an efficient approach for producing high value products using CO2 as building blocks. The methodology employed is based on electrochemical techniques and ILs, which provide eco-friendly chemistry solutions. These can be employed to offer a potential long-term strategy for using CO2 feedstocks. There are two different strategies to obtain a CO2 valorization product depending on the functional group, nitro or cyano, of the aromatic halide. An electrocatalytic process using a homogeneous catalysis, which provides an easy way of obtaining oxalate is seen when nitro derivatives are used, removing metal complexes as a catalyst. The use of cyano derivatives allows to tune the reactivity in function of the reduction potential value applied from electrocarboxylated products (via a nucleophile-electrophile reaction) to oxalate. These electrochemical reactions were performed with three different electrodes and in aprotic solvents and ionic liquids, which all showed the same trend. This opens the possibility of using a cooper electrode and ionic liquids to valorize CO2, which would be a cheaper and greener alternative. Author Contributions: G.G. conceptualized the research topic, conceived and designed the experiments; S.M. perform the experiments, G.G and S.M. analyzed and interpreted the results. S.M. and G.G. prepared the manuscript. All authors corrected the draft. G.G. obt ained the funds for the research. All authors have read and agreed to the published version of the manuscript. Funding: This research was funded by MINECO/FEDER (project CTQ2015-65439-R). Acknowledgments: This work was supported by project CTQ2015-65439-R from the MINECO/FEDER. S.M. thanks the Universitat Autònoma de Barcelona for a predoctoral PIF fellowship. Conflicts of Interest: The authors declare no conflict of interest. References 1. Holtsmark, B. Quantifying the global warming potential of CO2 emissions from wood fuels. GCB Bioenergy 2015, 7, 195–206. [CrossRef] 2. Hu, L.; Song, Y.; Jiao, S.; Liu, Y.; Ge, J.; Jiao, H.; Zhu, J.; Wang, J.; Zhu, H.; Fray, D.J. Direct Conversion of Greenhouse Gas CO2 into Graphene via Molten Salts Electrolysis. ChemSusChem 2016, 9, 588–594. [CrossRef] [PubMed] 3. Kramm, G.; Dlugi, R. Scrutinizing the atmospheric greenhouse effect and its climatic impact. Nat. Sci. 2011, 3, 971–998. [CrossRef] 4. Mohan, S.V.; Modestra, J.A.; Amulya, K.; Butti, S.K.; Velvizhi, G. A circular bioeconomy with biobased products from co2 sequestration. Trends Biotechnol. 2016, 34, 506–519. [CrossRef] [PubMed] 5. Schleussner, C.F.; Lissner, T.K.; Fischer, E.M.; Wohland, J.; Perrette, M.; Golly, A.; Rogelj, J.; Childers, K.; Schewe, J.; Frieler, K.; et al. Differential climate impacts for policy-relevant limits to global warming: The case of 1.5 ◦C and 2 ◦C. Earth Syst. Dyn. 2016, 7, 327–351. [CrossRef] 6. Szulejko, J.E.; Kumar, P.; Deep, A.; Kim, K.H. Global warming projections to 2100 using simple CO2 greenhouse gas modeling and comments on CO2 climate sensitivity factor. Atmos. Pollut. Res. 2017, 8, 136–140. [CrossRef] 7. Song, C. Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing. Catal. Today 2006, 115, 2–32. [CrossRef]PDF Image | Electrochemical Tuning of CO2 Reactivity in Ionic Liquids
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