Electrochemical CO2 reduction is an attractive option for storing renewable electricity and for the sustainable production of valuable chemicals and fuels. In this roadmap, we review recent progress in fundamental understanding, catalyst development, and in engineering and scale-up. We discuss the outstanding challenges towards commercialization of electrochemical CO2 reduction technology: energy efficiencies, selectivities, low current densities, and stability. We highlight the opportunities in establishing rigorous standards for benchmarking performance, advances in in operando characterization, the discovery of new materials towards high value products, the investigation of phenomena across multiple-length scales and the application of data science towards doing so. We hope that this collective perspective sparks new research activities that ultimately bring us a step closer towards establishing a low- or zero-emission carbon cycle.

The all-iron redox flow battery is an attractive solution for large-scale energy storage because of the low cost and eco-friendliness of iron-based materials. A major challenge to realizing a continuously operable battery is the parasitic evolution of hydrogen at the iron electrode during battery charging. We found that the adsorption of ascorbic acid added to the electrolyte inhibited hydrogen evolution at pH = 0. Elevation of pH near the surface of the electrode during electrodeposition also raised the coulombic efficiency. Thus, electrolyte flow rates significantly influence the coulombic efficiency. Ascorbic acid also served to regulate the pH near the surface of the negative electrode by buffering action. We found that increasing the operating temperature enhanced the kinetics of iron deposition relative to the kinetics of hydrogen evolution, leading to a net rise of coulombic efficiency. Thus, by operating at 60 • C and a pH of 3 with ascorbic acid and ammonium chloride, we achieved a coulombic efficiency of 97.9%. While this value of coulombic efficiency is among the highest values reported for the iron electrode in the context of the all-iron flow battery, further improvement in efficiency is needed for supporting repeated cycling. The results presented here provide insights for further improvements.

A new redox flow battery system based on iron sulfate and anthraquinone disulfonic acid (AQDS) is shown here to have excellent electrical performance, capacity retention, and chemical durability. While these redox couples, iron(II)/iron(III) and AQDS are well known individually, their combination in a redox flow battery is shown here for the first time to provide unique benefits for large-scale energy storage. Based on iron sulfate, a waste product of the steel industry, the active materials cost for this battery is anticipated to be $66/kWh. Cycling studies of over 500 cycles in the symmetric cell configuration show a negligibly low capacity fade rate of 7.6 × 10−5% per cycle. This symmetric cell also shows a notably high average coulombic efficiency of 99.63%. Using a graphite felt electrode modified with multi-walled carbon nanotubes (MWCNTs), we could achieve a peak power density of 194 mW cm−2. The major voltage losses are ascribed to the ohmic resistance of the electrode and electrolyte. Despite the lower cell voltage of the system relative to the vanadium flow battery, the iron–AQDS flow battery system presents a good prospect for simultaneously meeting the demanding requirements of cost, durability and scalability for large-scale sustainable energy storage.

Conspectus Increasing levels of carbon dioxide in the atmosphere and the growing need for energy necessitate a shift toward reliance on renewable energy sources and the utilization of carbon dioxide. Thus, producing carbonaceous fuel by the electrochemical reduction of carbon dioxide has been very appealing. We have focused on addressing the principal challenges of poor selectivity and poor energy efficiency in the electrochemical reduction of carbon dioxide. We have demonstrated here a viable pathway for the efficient and continuous electrochemical reduction of CO2 to formate using the metal-independent enzyme type of formate dehydrogenase (FDH) derived from Candida boidinii yeast. This type of FDH is attractive because it is commercially produced. In natural metabolic processes, this type of metal-independent FDH oxidizes formate to carbon dioxide using NAD+ as a cofactor. We show that FDH can catalyze the reverse process to generate formate when the natural cofactor NADH is replaced with an artificial cofactor, the methyl viologen radical cation. The methyl viologen radical cation is generated in situ, electrochemically. Our approach relies on the special properties of methyl viologen as a “unidirectional” redox cofactor for the conversion of CO2 to formate. Methyl viologen (in the oxidized form) does not catalyze formate oxidation, while the methyl viologen radical cation is an effective cofactor for the reduction of carbon dioxide. Thus, although the thermodynamic driving force is favorable for the oxidized form of methyl viologen to oxidize formate to carbon dioxide, the kinetic factors are not favorable. Only the reverse reaction of carbon dioxide reduction to formate is kinetically viable with the cofactor, methyl viologen radical cation. Binding free energy calculated from atomistic molecular dynamics (MD) simulations consolidate our understanding of these special binding properties of the methyl viologen radical cation and its ability to facilitate the two-electron reduction of carbon dioxide to formate in metal-independent FDH. By carrying out the reactions in a novel three-compartment cell, we have demonstrated the continuous production of formate at high energy efficiency and yield. This cell configuration uses judiciously selected ion-exchange membranes to separate the reaction compartments to preserve the yields of the methyl viologen radical cation and formate. By the electroregeneration of the methyl viologen radical cation at −0.44 V versus the normal hydrogen electrode, we could produce formate at 20 mV negative to the reversible electrode potential for carbon dioxide reduction to formate. Our results are in sharp contrast to the large overpotentials of −800 to −1000 mV required on metal catalysts, vindicating the selectivity and kinetic facility provided by FDH. Formate yields as high as 97% ± 1% could be realized by avoiding the adventitious reoxidation of the methyl viologen radical cation by molecular oxygen. We anticipate that the insights from the electrochemical studies and the MD simula...

The efficient delivery of electrochemically in situ produced H2 can be a key advantage of microbial electrosynthesis over traditional gas fermentation. However, the technical details of how to supply large amounts of electric current per volume in a biocompatible manner remain unresolved. Here, we explored for the first time the flexibility of complex 3D-printed custom electrodes to fine tune H2 delivery during microbial electrosynthesis. Using a model system for H2-mediated electromethanogenesis comprised of 3D fabricated carbon aerogel cathodes plated with nickel-molybdenum and Methanococcus maripaludis, we showed that novel 3D-printed cathodes facilitated sustained and efficient electromethanogenesis from electricity and CO2 at an unprecedented volumetric production rate of 2.2 LCH4 /Lcatholyte/day and at a coulombic efficiency of 99%. Importantly, our experiments revealed that the efficiency of this process strongly depends on the current density. At identical total current supplied, larger surface area cathodes enabled higher methane production and minimized escape of H2. Specifically, low current density (<1 mA/cm2) enabled by high surface area cathodes was found to be critical for fast start-up times of the microbial culture, stable steady state performance, and high coulombic efficiencies. Our data demonstrate that 3D-printing of electrodes presents a promising design tool to mitigate effects of bubble formation and local pH gradients within the boundary layer and, thus, resolve key critical limitations for in situ electron delivery in microbial electrosynthesis.