Electrochemical reduction of CO2 in the presence of 1,3-butadiene using a hydrogen anode in a nonaqueous medium

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

“…CO 2 bubbling through a catholyte solution of 1 wt % water in DMF, saturated with butadiene, yielded up to 50% of 3-hexenedioic acid [45], a result which unfortunately was difficult to reproduce [42,46]. At that time, various substrates, like olefins, alkynes and aromatic ketones, have been electrocarboxylated in these divided cells [47].…”

“…The direct formation of free carboxylic acids is a very interesting approach in this respect, minimizing the amount of process steps and waste ( Scheme 6 ). Protons produced at the anode, however, can have a detrimental effect on the electrocarboxylation efficiency, through cathodic formation of hydrogen, formic acid and other side products [ 41 – 42 ]. Hydrogen formation can be limited by usage of cathode materials with high hydrogen overvoltage like lead and mercury, or more environmentally friendly tantalum and zinc [ 43 ].…”

“…The first reports on electrocarboxylation date back to the early 1960s with a patent of Loveland, demonstrating the dicarboxylation of 1,3-butadiene in a two-compartment cell with a mercury cathode and a platinum anode, giving a mixture of mono- and dicarboxylic acids. CO 2 bubbling through a catholyte solution of 1 wt % water in DMF, saturated with butadiene, yielded up to 50% of 3-hexenedioic acid [ 45 ], a result which unfortunately was difficult to reproduce [ 42 , 46 ]. At that time, various substrates, like olefins, alkynes and aromatic ketones, have been electrocarboxylated in these divided cells [ 47 ].…”

Paired Electrosynthesis of Diacid and Diol Precursors Using Dienes and CO2 as the Carbon Source

“…[10,11] Protons favor the cathodic formation of hydrogen, formic acid, monocarboxylic acids and dimerization products. [10,11] Protons favor the cathodic formation of hydrogen, formic acid, monocarboxylic acids and dimerization products.…”

“…The anodic generation of protons from water, hydrogen or ammonia, aiming at a direct formation of carboxylic acids, gives rather low current efficiencies, even when the proton supply to the cathode is controlled by a cation exchange membrane (CEM) (Scheme 1 b). [10,11] Protons favor the cathodic formation of hydrogen, formic acid, monocarboxylic acids and dimerization products.…”