CO₂ from carbonate-based capture solutions requires a substantial energy input. Replacing this step with (bi)carbonate electrolysis has been commonly proposed as an efficient alternative that coproduces CO/syngas. Here, we assess the feasibility of directly integrating air contactors with (bi)carbonate electrolyzers by leveraging process, multiphysics, microkinetic, and technoeconomic models. We show that the copresence of CO₃^2- with HCO₃^- in the contactor effluent greatly diminishes the electrolyzer performance and eventually results in a reduced CO₂ capture fraction to ≤1%. Additionally, we estimate suitable effluents for (bi)carbonate electrolysis to require 5-14 times larger contactors than conventionally needed contactors, leading to unfavorable process economics. Notably, we show that the regeneration of the capture solvent inside (bi)carbonate electrolyzers is insufficient for CO₂ recapture. Thus, we suggest process modifications that would allow this route to be operationally feasible. Overall, this work sheds light on the practical operation of integrated direct air capture with (bi)carbonate electrolysis.

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Electrochemical CO₂ reduction aims to compete with Power-to-X alternatives but is well behind the scales of water electrolyzers and thermochemical reactors. In a recent issue of Nature Chemical Engineering, Crandall and co-workers demonstrate a 1000 cm² tandem CO₂/CO electrolyzer for acetate production. The work invites discussion on scientific and engineering scale-up challenges.

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Covalent organic frameworks (COFs) are ideal platforms to spatially control the integration of multiple molecular motifs throughout a single nanoporous framework. Despite this design flexibility, COFs are typically synthesized using only two monomers. One bears the functional motif for the envisioned application, while the other is used as an inert connecting building block. Integrating more than one functional motif extends the functionality of COFs immensely, which is particularly useful for multistep reactions such as electrochemical reduction of CO2. In this systematic study, we synthesized five Ni(II)- and Zn(II)-porphyrin-based COFs, including two pure component COFs (Ni100 and Zn100) and three mixed Ni/Zn-COFs (Ni75/Zn25, Ni50/Zn50, and Ni25/Zn75). Among these, the Ni50/Zn50-COF exhibited the highest catalytic performance for the electroreduction of CO2 to CO and formate at −0.6 V vs RHE, as was observed in an H-cell. The catalytic performance of the COF catalysts was further extended to a zero-gap membrane electrode assembly (MEA) operation where, utilizing Ni50/Zn50, CH4 was detected along with CO and formate at a high current density of 150 mA cm–2. In contrast, under these conditions predominantly H2 and CO were detected at Ni100 and Zn100 respectively, indicating a clear synergistic effect between the Ni- and Zn-porphyrin units.@en

Using copper (Cu) as an electrocatalyst uniquely produces multicarbon products (C₂₊-products) during the CO₂ reduction reaction (CO2RR). However, the CO2RR stability of Cu is presently 3 orders of magnitude shorter than required for commercial operation. One means of substantially increasing Cu catalyst lifetimes is through periodic oxidative processes, such as cathodic-anodic pulsing. Despite 100-fold improvements, these oxidative methods only delay, but do not circumvent, degradation. Here, we provide an interrogation of chemical and electrochemical Cu oxidative processes to identify the mechanistic processes leading to stable CO2RR through electrochemical and in situ Raman spectroscopy measurements. We first examine chemical oxidation using an open-circuit potential (OCP), identifying that copper oxidation is regulated by the transient behavior of the OCP curve and limited by the rate of the oxygen reduction reaction (ORR). Increasing O₂ flux to the cathode subsequently increased ORR rates, both extending lifetimes and reducing “off” times by 3-fold. In a separate approach, the formation of Cu₂O is achieved through electrochemical oxidation. Here, we establish the minimum electrode potentials required for fast Cu oxidation (−0.28 V vs Ag/AgCl, 1 M KHCO₃) by accounting for transient local pH changes and tracking oxidation charge transfer. Lastly, we performed a stability test resulting in a 20-fold increase in stable ethylene production versus the continuous case, finding that spatial copper migration is slowed but not mitigated by oxidative pulsing approaches alone.

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Carbon dioxide (CO2) electrolysis on copper (Cu) catalysts has attracted interest due to its direct production of C2+ feedstocks. Using the knowledge that CO2 reduction on copper is primarily a tandem reaction of CO2 to CO and CO to C2+ products, we show that modulating CO concentrations within the liquid catalyst layer allows for a C2+ selectivity of >80% at 200 mA cm−2 under broad conversion conditions. The importance of CO pooling is demonstrated through residence time distribution curves, varying flow fields (serpentine/parallel/interdigitated), and flow rates. While serpentine flow fields require high conversions to limit CO selectivity and maximize C2+ selectivity, the longer CO residence times of parallel flow fields achieve similar selectivity over broad flow rates. Critically, we show that parts of the catalyst area predominantly reduce CO instead of CO2 as supported by CO reduction experiments, transport modelling, and achieving a CO2 utilization efficiency greater than the theoretical limit of 25% for C2+ products.@en

CO2 electrolysis allows the sustainable production of carbon-based fuels and chemicals. However, state-of-the-art CO2 electrolysers employing anion exchange membranes (AEMs) suffer from (bi)carbonate crossover, causing low CO2 utilization and limiting anode choices to those based on precious metals. Here we argue that bipolar membranes (BPMs) could become the primary option for intrinsically stable and efficient CO2 electrolysis without the use of scarce metals. Although both reverse- and forward-bias BPMs can inhibit CO2 crossover, forward-bias BPMs fail to solve the rare-earth metals requirement at the anode. Unfortunately, reverse-bias BPM systems presently exhibit comparatively lower Faradaic efficiencies and higher cell voltages than AEM-based systems. We argue that these performance challenges can be overcome by focusing research on optimizing the catalyst, reaction microenvironment and alkali cation availability. Furthermore, BPMs can be improved by using thinner layers and a suitable water dissociation catalyst, thus alleviating core remaining challenges in CO2 electrolysis to bring this technology to the industrial scale.@en

Molecular catalysts play a significant role in chemical transformations, utilizing changes in redox states to facilitate reactions. To date molecular electrocatalysts have efficiently produced single-carbon products from CO2 but have struggled to achieve a carbon–carbon coupling step. Conversely, copper catalysts can enable carbon–carbon coupling, but lead to broad C2+ product spectra. Here we subvert the traditional redox-mediated reaction mechanisms of organometallic compounds through a heterogeneous nickel-supported iron tetraphenylporphyrin electrocatalyst, facilitating electrochemical carbon–carbon coupling to produce ethanol. This represents a marked behavioural shift compared with carbon-supported metalloporphyrins. Extending the approach to a three-dimensional porous nickel support with adsorbed iron tetraphenylporphyrin, we attain ethanol Faradaic efficiencies of 68% ± 3.2% at −0.3 V versus a reversible hydrogen electrode (pH 7.7) with partial ethanol current densities of −21 mA cm−2. Separately we demonstrate maintained ethanol production over 60 h of operation. Further consideration of the wide parameter space of molecular catalyst and metal electrodes shows promise for additional chemistries and achievable metrics.@en

Bipolar membranes in electrochemical CO2 conversion cells enable different reaction environments in the CO2-reduction and O2-evolution compartments. Under ideal conditions, water-splitting in the bipolar membrane allows for platinum-group-metal-free anode materials and high CO2 utilizations. In practice, however, even minor unwanted ion crossover limits stability to short time periods. Here we report the vital role of managing ionic species to improve CO2 conversion efficiency while preventing acidification of the anodic compartment. Through transport modelling, we identify that an anion-exchange ionomer in the catalyst layer improves local bicarbonate availability and increasing the proton transference number in the bipolar membranes increases CO2 regeneration and limits K+ concentration in the cathode region. Through experiments, we show that a uniform local distribution of bicarbonate ions increases the accessibility of reverted CO2 to the catalyst surface, improving Faradaic efficiency and limiting current densities by twofold. Using these insights, we demonstrate a fully platinum-group-metal-free bipolar membrane electrode assembly CO2 conversion system exhibiting <1% CO2/cation crossover rates and 80-90% CO2-to-CO utilization efficiency over 150 h operation at 100 mA cm−2 without anolyte replenishment.@en

Electrolyte flooding in porous catalyst layers on gas diffusion electrodes (GDE) limits the stability and high-current performance of CO2 and CO electrolyzers. Here, we demonstrate the in situ electroreduction of graphene oxide (GO) to reduced graphene oxide (r-GO) within a silver catalyst layer on a carbon GDE. The r-GO introduces hydrophobicity regions in the catalyst layer that help mitigate electrolyte flooding during high current density CO2 electrolysis to CO. The flooding-resistant r-GO/Ag-coated GDE achieves a sustained Faradaic efficiency of CO at 94% for more than 8 h, compared to a rapid drop from 95% to 66% in an Ag-coated GDE without r-GO at 100 mA·cm–2. We found that GO enhances the electrochemically active surface area of the catalyst layer during CO2 electrolysis tests because the incorporation of GO increases the roughness of the catalyst layer. The in situ method of electrochemically reducing GO to r-GO provides a low-cost, practical approach that can be applied during standard spray-deposition procedures to develop flooding-resistant GDEs.@en

Electrochemical ammonia (NH₃) synthesis from nitrate (NO₃⁻) offers a promising greener alternative to the fossil-fuel-based Haber-Bosch process to support the increasing demand for nitrogen fertilizers while removing environmental waste. Previous studies have mainly focused on designing catalysts to promote the direct conversion (NO₃⁻ → NH₃) while suppressing the two-step pathway (NO₃⁻ → NO₂⁻ → NH₃). We hypothesize that efficient nitrate reduction is possible on simple catalysts by instead promoting the two-step reaction and using chemical reactor principles in a membrane electrode assembly, despite NO₂⁻ intermediates. Here, we use an unmodified copper catalyst and control reactivity through current density, flow rate, and electrolyte recycling. Balancing the electrolyte flow rate with current density results in ideal residence times for NO₂⁻, allowing for 91% FE_NH3 in a 5 cm² electrolyzer with a NO₃⁻ to NH₃ partial current of 1.8 A. This work shows that traditional engineering principles can substantially boost the NO₃ reduction reaction, even for simple catalysts.

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To explore the effects of solvent-ionomer interactions in catalyst inks on the structure and performance of Cu catalyst layers (CLs) for CO₂ electrolysis, we used a “like for like” rationale to select acetone and methanol as dispersion solvents with a distinct affinity for the ionomer backbone or sulfonated ionic heads, respectively, of the perfluorinated sulfonic acid (PFSA) ionomer Aquivion. First, we characterized the morphology and wettability of Aquivion films drop-cast from acetone- and methanol-based inks on flat Cu foils and glassy carbons. On a flat surface, the ionomer films cast from the Aquivion and acetone mixture were more continuous and hydrophobic than films cast from methanol-based inks. Our study’s second stage compared the performance of Cu nanoparticle CLs prepared with acetone and methanol on gas diffusion electrodes (GDEs) in a flow cell electrolyzer. The effects of the ionomer-solvent interaction led to a more uniform and flooding-tolerant GDE when acetone was the dispersion solvent (acetone-CL) than when we used methanol (methanol-CL). As a result, acetone-CL yielded a higher selectivity for CO₂ electrolysis to C₂₊ products at high current density, up to 25% greater than methanol-CL at 500 mA cm^-2. Ethylene was the primary product for both CLs, with a Faradaic efficiency for ethylene of 47.4 ± 4.0% on the acetone-CL and that of 37.6 ± 5.5% on the methanol-CL at a current density of 300 mA cm^-2. We attribute the enhanced C₂₊ selectivity of the acetone-CL to this electrode’s better resistance to electrolyte flooding, with zero seepage observed at tested current densities. Our findings reveal the critical role of solvent-ionomer interaction in determining the film structure and hydrophobicity, providing new insights into the CL design for enhanced multicarbon production in high current densities in CO₂ electrolysis processes.

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Immobilizing molecular catalysts on electrodes is vital for electrochemical applications. However, creating robust electrode-catalyst interactions while maintaining good catalytic performance and rapid electron transfer is challenging. Here, without introducing any foreign elements, we show a bottom-up synthetic approach of constructing the conjugated C−C bond between the commercial Vulcan carbon electrode and an organometallic catalyst. Characterization results from FTIR, XPS, aberration-corrected TEM and EPR confirmed the successful and uniform heterogenization of the complex. The synthesized Vulcan-LN₄−Co catalyst is highly active and selective in the oxygen reduction reaction in neutral media, showing an 80 % hydrogen peroxide selectivity and a 0.72 V (vs. RHE) onset potential which significantly outperformed the homogenous counterpart. Based on single-crystal XRD and NMR data, we built a model for density functional theory calculations which showed a nearly optimal binding energy for the *OOH intermediate. Our results show that the direct conjugated C−C bonding is an effective approach for heterogenizing molecular catalysts on carbon, opening new opportunities for employing molecular catalysts in electrochemical applications.

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