Haeun Shin

ConspectusThe agricultural and chemical industries are major contributors to climate change. To address this issue, hybrid electrocatalytic-biocatalytic systems have emerged as a promising solution for reducing the environmental impact of these key sectors while providing economic onboarding for carbon capture technology. Recent advancements in the production of acetate via CO₂/CO electrolysis as well as advances in precision fermentation technology have prompted electrochemical acetate to be explored as an alternative carbon source for synthetic biology. Tandem CO₂ electrolysis coupled with improved reactor design has accelerated the commercial viability of electrosynthesized acetate in recent years. Simultaneously, innovations in metabolic engineering have helped leverage pathways that facilitate acetate upgrading to higher carbons for sustainable food and chemical production via precision fermentation. Current precision fermentation technology has received much criticism for reliance upon food crop-derived sugars and starches as feedstock which compete with the human food chain. A shift toward electrosynthesized acetate feedstocks could help preserve arable land for a rapidly growing population.Technoeconomic analysis shows that using electrochemical acetate instead of glucose as a fermentation feedstock reduces the production costs of food and chemicals by 16% and offers improved market price stability. Moreover, given the rapid decline in utility-scale renewable electricity prices, electro-synthesized acetate may become more affordable than conventional production methods at scale. This work provides an outlook on strategies to further advance and scale-up electrochemical acetate production. Additional perspective is offered to help ensure the successful integration of electrosynthesized acetate and precision fermentation technologies. In the electrocatalytic step, it is critical that relatively high purity acetate can be produced in low-concentration electrolyte to help ensure that minimal treatment of the electrosynthesized acetate stream is needed prior to fermentation. In the biocatalytic step, it is critical that microbes with increased tolerances to elevated acetate concentrations are engineered to help promote acetate uptake and accelerate product formation. Additionally, tighter regulation of acetate metabolism via strain engineering is essential to improving cellular efficiency. The implementation of these strategies would allow the coupling of electrosynthesized acetate with precision fermentation to offer a promising approach to sustainably produce chemicals and food. Reducing the environmental impact of the chemical and agricultural sectors is necessary to avoid climate catastrophe and preserve the habitability of the planet for future generations.

The selectivity between high value C–C coupled (C₂) products (ethylene and ethanol against acetate) in the electrochemical CO₍₂₎reduction reaction on Cu catalysts is governed by potential, local pH, and roughness.

Electrifying chemical manufacturing using renewable energy is an attractive approach to reduce the dependence on fossil energy sources in chemical industries. Primary amines are important organic building blocks; however, the synthesis is often hindered by the poor selectivity because of the formation of secondary and tertiary amine byproducts. Herein, we report an electrocatalytic route to produce ethylamine selectively through an electroreduction of acetonitrile at ambient temperature and pressure. Among all the electrocatalysts, Cu nanoparticles exhibit the highest ethylamine Faradaic efficiency (~96%) at −0.29 V versus reversible hydrogen electrode. Under optimal conditions, we achieve an ethylamine partial current density of 846 mA cm⁻². A 20-hour stable performance is demonstrated on Cu at 100 mA cm⁻² with an 86% ethylamine Faradaic efficiency. Moreover, the reaction mechanism is investigated by computational study, which suggests the high ethylamine selectivity on Cu is due to the moderate binding affinity for the reaction intermediates.

The electroreduction of carbon dioxide offers a promising avenue to produce valuable fuels and chemicals using greenhouse gas carbon dioxide as the carbon feedstock. Because industrial carbon dioxide point sources often contain numerous contaminants, such as nitrogen oxides, understanding the potential impact of contaminants on carbon dioxide electrolysis is crucial for practical applications. Herein, we investigate the impact of various nitrogen oxides, including nitric oxide, nitrogen dioxide, and nitrous oxide, on carbon dioxide electroreduction on three model electrocatalysts (i.e., copper, silver, and tin). We demonstrate that the presence of nitrogen oxides (up to 0.83%) in the carbon dioxide feed leads to a considerable Faradaic efficiency loss in carbon dioxide electroreduction, which is caused by the preferential electroreduction of nitrogen oxides over carbon dioxide. The primary products of nitrogen oxides electroreduction include nitrous oxide, nitrogen, hydroxylamine, and ammonia. Despite the loss in Faradaic efficiency, the electrocatalysts exhibit similar carbon dioxide reduction performances once a pure carbon dioxide feed is restored, indicating a negligible long-term impact of nitrogen oxides on the catalytic properties of the model catalysts.