In terms of commercial electrocatalytic reactions, there are actually very few.  There are electrowinning reactions, (i.e. electrochemical reduction of metals salts), mostly notably the Hall-Heroult process for aluminum, and the electrosynthesis of halides, but beyond that there is very little.  Though water electrolysis to hydrogen is often hyped, most electrocatalytic hydrogen comes as a byproduct of chlorine evolution.  In terms of organic chemistry, there is really only one notable process and that is the adiponitriled process as shown on the right.  Thus it is possible for the economics to work, but we have just not been able to find other reactions.  One of my research thrusts is to look in this direction.

Valuable products One of the main reasons we have not been able to find economically viable electrosynthesis processes is simply because we have not cared to  focus on it. A large amount of electrosynthesis research and development funding has been on fuels and bulk chemicals due to their large market value. However the lack of an emerging H2 economy after decades of effort has shown that another approach is needed. CO2 electrolysis does provide the potential for niche products such as isotopically labelled ethanol and ethylene synthesis (which I am involved in a start-up with), and I believe this can be a starting point for other products as well.  While bulk chemicals such as ethanol and ethylene are 2.5 times more valuable than hydrogen on a $/MWh basis, other organics have the potential to be even higher.  Aqueous based electrolytes are almost exclusively used in electrochemistry, however organics are not soluble in aquoeous solutions, thus we need to operate in non-aqueous studies.  We have had a project recently analyzing CO2 electrolysis is non-aqueous solutions and our biggest finding was that while aqueous reactions allow for catalytic based inner-sphere reactions (i.e. sharing electron density with a catalysts), switching to non-aqueous reactions tend to favor outer-sphere reactions (i.e. non-catalytic), and thus much lower energy efficiencies.  Thus one of our major goals is to figure out how to resolve this. Integrating electrochemistry into Nylon synthesis About 6-7M tons of Nylon is produced every year, and this is derived from reacting hexamethylenediamine and adipic acid.  Adipic acid is a 6-carbon chain molecule that is typically produced via KA Oil (fossil fuel derived) and nitric acid (environmentally unfriendly) .  Interestingly, a few research works have shown that CO2 can be electrochemically reduced onto butadiene to form adipic acid.  While butadiene is normally produced via fossil fuels, there is a non-negligible market share that is produced via dehyrogenation of ethanol, thus providing a sustainable approach to butadiene. This approach has substantial potential for economic viability, however the CO2 is currently reduced onto the butadiene via a high overpotential outer-sphere radical reaction rather than a more efficient catalytically driven inner-sphere reaction.  Thus our goal is to work to achieve a catalytically active coupling of the CO2 and the butadiene.  From a more fundamental aspect, this work will analyze how alkene behaves on an electrocatalyst at an applied potential, especially when compared to competing adsorbates such as hydrogen and CO.  Given that alkenes is a pretty large class of molecules the overall scientific understanding could be quite broadly applicable.

CO₂ electrolysis coupled with amines
In 2019 a colleague of mine, Professor Feng Jiao, was trying to analyze the mechanism of CO₂ electrolysis and inserted amines into the electrolyte to help see if any of the intermediates would react with the amine to form an amide.   Fortunately it did and this study, along with some of our studies, and further studies by Professor Jiao & DTU computational chemists all led to a pretty clear indication that CO₂ electrolysis proceeds through ethenone, which then would either desorb and hydrolyze to acetate or get further reduced on the electrode to ethanol. This also demonstrated that the step before the ethenone intermediate was the branching point between ethanol and ethylene, the 2 major products from Cu based CO₂ electrolysis.  This concept is shown on the figure to the right, which is a mesh of Jouny et al. Nat Chem. 2019. and Kastlunger et al. ACS Cat 2023.

However what was forgotten in all this mechanistic understanding was that CO₂ electrolysis could take amines and produce amides. Furthermore we repeated some of the experiments and could reproduce their results.  Amines is a very broad class of chemicals, and the thought is that we can find an amine that can interact with the ethenone to form a high value product.  Thus the goal of this direction is to both understand how the amide is formed and to produce a proudct of value.