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Sustainable Electrocoupling of the Biogenic Valeric Acid under in Situ Low-Field Nuclear Magnetic Resonance Conditions

2019; American Chemical Society; Volume: 7; Issue: 22 Linguagem: Inglês

10.1021/acssuschemeng.9b02768

2168-0485

Bruna Ferreira Gomes, F. Joschka Holzhäuser, Carlos Manuel Silva Lobo, Pollyana Ferreira da Silva, Ernesto Danieli, Marcelo Carmo, Luiz Alberto Colnago, Stefan Palkovits, Regina Palkovits, Bernhard Blümich,

Catalysis for Biomass Conversion

In situ nuclear magnetic resonance (NMR) investigations of a Kolbe electrolysis reaction using a 43 MHz 1H NMR spectrometer were performed in this work. The electrochemical oxidative decarboxylation of biomass-derived valeric acid into the value-added product n-octane has been monitored. All reactions were conducted in nondeuterated methanolic solution, using KOH as the supporting electrolyte. The working and counter electrodes consisted of Pt wire, and Ag wire was used as a pseudo-reference electrode. The influence of the magnetic field on the reaction kinetics, as well as on mass transfer, has been studied in detail. The findings show that the resulting mass transfer is highly dependent on the magnetic field. The significantly higher reaction velocity for in situ experiments is partly due to the strong Lorentz force, which agitates the solution and reduces the thickness of the electric double layer. The obtained results also suggest a strong influence of the magnetic field on the charge transfer from the electrode to the solution. The total resistance for the electrochemical reaction was significantly reduced by the presence of the magnetic field for all in situ experiments, at all points of the reaction. According to the reaction products, it was found that, at high applied potentials (>5 V) or currents (>15 mA), the reaction velocity can be increased but evaporation and overoxidation phenomena become more apparent. The results presented here show how NMR in situ electrochemistry can help to determine the optimal reaction conditions and improve quantitative analyses by example of a prominent green chemistry application.