Turning Carbon Dioxide into Sustainable Food and Chemicals: How Electrosynthesized Acetate Is Paving the Way for Fermentation Innovation.

The 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.

Electrochemical Approaches for CO2 Conversion to Chemicals: A Journey toward Practical Applications.

Carbon capture, utilization, and sequestration play an essential role to address CO2 emissions. Among all carbon utilization technologies, CO2 electroreduction has gained immense interest due to its potential for directly converting CO2 to a variety of valuable commodity chemicals using clean, renewable electricity as the sole energy source. The research community has witnessed rapid advances in CO2 electrolysis technology in recent years, including highly selective catalysts, larger-scale reactors, specific process modeling, as well as a mechanistic understanding of the CO2 reduction reaction. The rapid advances in the field brings promise to the commercial application of the technology and the rapid rollout of the CO2 electroreduction for chemical manufacturing.This Account focuses on our contributions in both fundamental and applied research in the field of electrocatalytic CO2 and CO reduction reactions. We first discuss (1) the development of novel electrocatalysts for CO2/CO electroreduction to enhance the product selectivity and lower the energy consumption. Specifically, we synthesized nanoporous Ag and homogeneously mixed Cu-based bimetallic catalysts for the enhanced production of CO from CO2 and multicarbon products from CO, respectively. Then, we review our efforts in (2) the field of reactor engineering, including a dissolved CO2 H-type cell, vapor-fed CO2 three-compartment flow cell, and vapor-fed CO2 membrane electrode assembly, for enhancing reaction rates and scalability. Next, we describe (3) the investigation of reaction mechanisms using in situ and operando techniques, such as surface-enhanced vibrational spectroscopies and electrochemical mass spectroscopy. We revealed the participation of bicarbonate in CO2 electroreduction on Au using attenuated total-reflectance surface-enhanced infrared absorption spectroscopy, the presence of an "oxygenated" surface of Cu under CO electroreduction conditions using surface-enhanced Raman spectroscopy, and the origin of oxygen in acetaldehyde and other CO electroreduction products on Cu using flow electrolyzer mass spectrometry. Lastly, we examine (4) the commercial potential of the CO2 electrolysis technology, such as understanding pollutant effects in CO2 electroreduction and developing techno-economic analysis. Specifically, we discuss the effects of SO2 and NOx in CO2 electroreduction using Cu, Ag, and Sn catalysts. We also identify technical barriers that need to be overcome and offer our perspective on accelerating the commercial deployment of the CO2 electrolysis technology.

Emerging Electrochemical Processes to Decarbonize the Chemical Industry.

Electrification is a potential approach to decarbonizing the chemical industry. Electrochemical processes, when they are powered by renewable electricity, have lower carbon footprints in comparison to conventional thermochemical routes. In this Perspective, we discuss the potential electrochemical routes for chemical production and provide our views on how electrochemical processes can be matured in academic research laboratories for future industrial applications. We first analyze the CO2 emission in the manufacturing industry and conduct a survey of state of the art electrosynthesis methods in the three most emission-intensive areas: petrochemical production, nitrogen compound production, and metal smelting. Then, we identify the technical bottlenecks in electrifying chemical productions from both chemistry and engineering perspectives and propose potential strategies to tackle these issues. Finally, we provide our views on how electrochemical manufacturing can reduce carbon emissions in the chemical industry with the hope to inspire more research efforts in electrifying chemical manufacturing.

A hybrid inorganic-biological artificial photosynthesis system for energy-efficient food production.

Artificial photosynthesis systems are proposed as an efficient alternative route to capture CO2 to produce additional food for growing global demand. Here a two-step CO2 electrolyser system was developed to produce a highly concentrated acetate stream with a 57% carbon selectivity (CO2 to acetate), allowing its direct use for the heterotrophic cultivation of yeast, mushroom-producing fungus and a photosynthetic green alga, in the dark without inputs from biological photosynthesis. An evaluation of nine crop plants found that carbon from exogenously supplied acetate incorporates into biomass through major metabolic pathways. Coupling this approach to existing photovoltaic systems could increase solar-to-food energy conversion efficiency by about fourfold over biological photosynthesis, reducing the solar footprint required. This technology allows for a reimagination of how food can be produced in controlled environments.

Multi-principal elemental intermetallic nanoparticles synthesized via a disorder-to-order transition.

Nanoscale multi-principal element intermetallics (MPEIs) may provide a broad and tunable compositional space of active, high-surface area materials with potential applications such as catalysis and magnetics. However, MPEI nanoparticles are challenging to fabricate because of the tendency of the particles to grow/agglomerate or phase-separated during annealing. Here, we demonstrate a disorder-to-order phase transition approach that enables the synthesis of ultrasmall (4 to 5 nm) and stable MPEI nanoparticles (up to eight elements). We apply just 5 min of Joule heating to promote the phase transition of the nanoparticles into L10 intermetallic structure, which is then preserved by rapidly cooling. This disorder-to-order transition results in phase-stable nanoscale MPEIs with compositions (e.g., PtPdAuFeCoNiCuSn), which have not been previously attained by traditional synthetic methods. This synthesis strategy offers a new paradigm for developing previously unexplored MPEI nanoparticles by accessing a nanoscale-size regime and novel compositions with potentially broad applications.

The impact of nitrogen oxides on electrochemical carbon dioxide reduction.

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.

Central composite design parameterization of microalgae/cyanobacteria co-culture pretreatment for enhanced lipid extraction using an external clamp-on ultrasonic transducer.

Lipids extracted from algal biomass could provide an abundant, rapidly growing, high yield feedstock for bio-diesel and other green fuels to supplement current fossil-based sources. Ultrasound pretreatment is a mechanical cell disruption method that has been shown to enhance lipid recovery from algae due to cavitation effects that disrupt algae cell walls. In this study, a locally grown mixture of Chlorella vulgaris/Cyanobacteria leptolyngbya was sonicated in an ultrasonic reactor with a clamp-on transducer prior to solvent lipid extraction. This configuration allows for a non-contact delivery method of ultrasonic energy with improved operational advantages (no fouling of transducer, continuous operation, and fully scalable design). A central composite design (CCD) was implemented to statistically analyze and evaluate the effect of ultrasonic power (350-750 W) and treatment time (5-30 min) on lipid yield. Lipid recovery was found to increase with both ultrasonic power and treatment time. Total lipid yields (on dry biomass basis) extracted via the Bligh and Dyer method from Chlorella vulgaris/cyanobacteria co-culture ranged from 8.3% for untreated algae to 16.9% for algae sonicated with 750 W power for 30 min, which corresponds to more than a doubling of lipid recovery due to ultrasound pretreatment. Increased power and treatment times were found to increase the degree of cell disruption as observed in the SEM and TEM images after ultrasonic pretreatment. Additionally, hexane (1:1 v/v) was evaluated as an alternative to the standard Bligh & Dyer (2:2:1.8 v/v/v chloroform/methanol/cell suspension) lipid extraction solvent system. On average, the Bligh and Dyer method extracted on average over twice the amount of lipids compared to hexane extraction. The lipid profile of the algae extracts indicates high concentrations of lauric acid (12:0), palmitic acid (16:0), stearic acid (18:0), oleic acid (18:1), and linoleic acid (18:2). This particular configuration of an ultrasonic system proved to be a viable method for the pretreatment of algae for enhanced lipid yields. Future research should focus on identifying alternative extraction solvents and expanding the range of treatment conditions to optimize the ultrasonic power and treatment times for maximum lipid recovery.