The decoupled power and energy output of a redox flow battery (RFB) offers a key advantage in long-duration energy storage, crucial for a successful energy transition. Iodide/iodine and hydrogen/water, owing to their fast reaction kinetics, benign nature, and high solubility, provide promising battery chemistry. However, H₂-I₂ RFBs suffer from low open circuit potentials, iodine crossover, and their multiphase nature. We demonstrate a H₂-I₂ operation with a combined neutral-pH catholyte (I₃^-/I^-) and an alkaline anolyte (KOH), producing an open circuit cell voltage of 1.28 V. Additionally, we incorporate a pressure-balanced gas diffusion electrode (GDE) to mitigate mass transport limitations at the anode. These improvements result in a maximum power density of 230 W/m² when allowing a mild breakthrough of H₂ through the GDE. While minimal crossover occurs, side reactions of permeating active species were found reversible, enabling long-term operation. Future work should address the stability of the GDE and optimization of the electrolyte thickness and concentration to fully leverage the potential unlocked by balancing the pressure and pH in the H₂-I₂ RFB.

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Dense polymer membranes enable a diverse range of separations and clean energy technologies, including gas separation, water treatment, and renewable fuel production or conversion. The transport of small molecular and ionic solutes in the majority of these membranes is described by the same solution-diffusion mechanism, yet a comparison of membrane separation performance across applications is rare. A better understanding of how structure-property relationships and driving forces compare among applications would drive innovation in membrane development by identifying opportunities for cross-disciplinary knowledge transfer. Here, we aim to inspire such cross-pollination by evaluating the selectivity and electrochemical driving forces for 29 separations across nine different applications using a common framework grounded in the physicochemical characteristics of the permeating and rejected solutes. Our analysis shows that highly selective membranes usually exhibit high solute rejection, rather than fast solute permeation, and often exploit contrasts in the size and charge of solutes rather than a nonelectrostatic chemical property, polarizability. We also highlight the power of selective driving forces (e.g., the fact that applied electric potential acts on charged solutes but not on neutral ones) to enable effective separation processes, even when the membrane itself has poor selectivity. We conclude by proposing several research opportunities that are likely to impact multiple areas of membrane science. The high-level perspective of membrane separation across fields presented herein aims to promote cross-pollination and innovation by enabling comparisons of solute transport and driving forces among membrane separation applications.

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Membrane technology has attracted great industrial interest in carbon capture and separation owing to the merits of energy-efficiency, environmental friendliness and low capital investment. Conventional polymeric membranes for CO₂ separation suffer from the trade-off between permeability and selectivity. Introducing porous fillers in polymers is one approach to enhance membrane separation performance. Metal-organic frameworks (MOFs), with ordered porous structure and diverse chemical functionalities, are promising fillers to prepare mixed matrix membranes (MMMs) for CO₂ separation. However, the main issue of MOF based MMMs in industry is their stability and processability. This review analyses recent work on stable and scalable MOF based MMMs for CO₂ separation. The typical stable MOFs, MOF-based MMMs and the scalable MOF synthesis are summarized. A large number of MOF-based MMM suffer from instability upon exposure to contaminants. For that reason, we also discuss the use of covalent organic frameworks (COFs) as an alternative to prepare MMMs for CO₂ separation, considering their excellent stability and good compatibility with polymers. Finally, a brief conclusion and current challenges on obtaining scalable and stable MMMs are outlined. This review may provide some guidance for designing high performance MMMs for industrial CO₂ capture and separation to help achieving carbon neutrality.

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CO2 conversion is an important part of the transition towards clean fuels and chemicals. However, low solubility of CO2 in water and its slow diffusion cause mass transfer limitations in aqueous electrochemical CO2 reduction. This significantly limits the partial current densities towards any desired CO2-reduction product. We propose using flowable suspension electrodes to spread the current over a larger volume and alleviate mass transfer limitations, which could allow high partial current densities for CO2 conversion even in aqueous environments. To identify the requirements for a well-performing suspension electrode, we use a transmission line model to simulate the local electric and ionic current distributions throughout a channel and show that the electrocatalysis is best distributed over the catholyte volume when the electric, ionic and charge transfer resistances are balanced. In addition, we used electrochemical impedance spectroscopy to measure the different resistance contributions and correlated the results with rheology measurements to show that particle size and shape impact the ever-present trade-off between conductivity and flowability. We combine the modelling and experimental results to evaluate which carbon type is most suitable for use in a suspension electrode for CO2 reduction, and predict a good reaction distribution throughout activated carbon and carbon black suspensions. Finally, we tested several suspension electrodes in a CO2 electrolyzer. Even though mass transport limitations should be reduced, the CO partial current densities are capped at 2.8 mA cm−2, which may be due to engineering limitations. We conclude that using suspension electrodes is challenging for sensitive reactions like CO2 reduction, and may be more suitable for use in other electrochemical conversion reactions suffering from mass transfer limitations that are less affected by competing reactions and contaminations.@en

Electrochemical oxygen reduction is a promising and sustainable alternative to the current industrial production method for hydrogen peroxide (H₂O₂), which is a green oxidant in many (emerging) applications in the chemical industry, water treatment, and fuel cells. Low solubility of O₂ in water causes severe mass transfer limitations and loss of H₂O₂ selectivity at industrially relevant current densities, complicating the development of practical-scale electrochemical H₂O₂ synthesis systems. We tested a flow-by and flow-through configuration and suspension electrodes in an electrochemical flow cell to investigate the influence of electrode configuration and flow conditions on mass transfer and H₂O₂ production. We monitored the H₂O₂ production using Cu-tmpa (tmpa = tris(2-pyridylmethyl)amine) as a homogeneous copper-based catalyst in a pH-neutral phosphate buffer during 1 h of catalysis and estimated the limiting current density from CV scans. We achieve the highest H₂O₂ production and a 15-20 times higher geometrical limiting current density in the flow-through configuration compared to the flow-by configuration due to the increased surface area and foam structure that improved mass transfer. The activated carbon (AC) material in suspension electrodes, which have an even larger surface area, decomposes all produced H₂O₂ and proves unsuitable for H₂O₂ synthesis. Although the mass transfer limitations seem to be alleviated on the microscale in the flow-through system, the high O₂ consumption and H₂O₂ production cause challenges in maintaining the initially reached current density and Faradaic efficiency (FE). The decreasing ratio between the concentrations of the O₂ and H₂O₂ in the bulk electrolyte will likely pose a challenge when proceeding to larger systems with longer electrodes. Tuning the reactor design and operating conditions will be essential in maximizing the FE and current density.

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Nanofluidic membranes (NFMs) are gaining prominence as alternative ion-exchange membranes, because of their distinct selectivity mechanism, which does not rely on functional groups on a polymeric backbone but rather on charged nanopores that allow straight ion-conductive pathways for efficient ion transport. We measured the conductivity of commercial anodized aluminum oxide membranes with different pore sizes under different current densities and electrolyte concentrations. We also simulated a nanopore channel with charged walls between two electrolyte reservoirs. Our findings indicate that electrolyte concentration is the main parameter that determines NFM conductivity, with a linear dependence at least up to 1 M. Our study shows that the optimal pore length is between 0.5 and 5 μm considering the trade-off between selectivity and conductance. On the other hand, the conductance is not sensitive to the pore diameter. Conical nanopores are a way to increase conductance, but according to our results, this increase comes at the expense of selectivity. Our findings suggest that NFMs can outperform polymeric ion-exchange membranes in certain electrochemical applications, such as reverse electrodialysis, but not in applications that use low electrolyte concentrations on both sides of the membrane.

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To make green hydrogen more economically attractive, the energy losses in alkaline electrolysis need to be minimized while operating at high current densities (1 A cm⁻²). At these current densities the ohmic resistance and gas bubbles effects contribute largely to the energy losses. To mitigate the gas bubbles losses, we demonstrate, for the first time, a pressure swing to remove gas bubbles in a zero-gap alkaline water electrolyzer. The pressure swing leverages the ideal gas law to increase the volume of gas in the system periodically, for a short duration (<2 s). This temporal volume increase effectively removes bubbles from the electrolyzer. We show that pressure swing can be used to measure the effect of bubbles on the ohmic resistance (R_Bubbles). Our results reveal that foam electrodes have a significantly larger R_Bubbles than perforated plate electrodes (1.8 Ω cm² vs 0.3 Ω cm²). The time-averaged cell voltage reduces by 170 mV when applying pressure swings to an electrolyzer operating at 200 mA cm⁻² in 1 M KOH with foam electrodes. The bubble resistance further depends on the electrolyte conductivity (inversely proportional) and is only moderately affected by operating pressure (25 % lower when increasing pressure amplitude from 1–2 to 1–5 bar). By implementing these findings in a model, we estimate that the pressure swing could reduce the cell voltage by ∼0.1 V for an electrolyzer operating at industrial conditions (6 M KOH, 80 °C, 1 A cm⁻²) for foam electrodes. For perforated plate electrodes, however, the reduced cell voltage is lower and does not outweigh the additional compression energy.

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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

To assist reaching net-zero emissions, the dissolved carbon in the ocean can be extracted to enable an indirect air capture. An electrochemical bipolar membrane electrodialysis (BPMED) is a sustainable method for such capture. The BPMED enables a pH-swing that manipulates the oceanic carbonate-equilibrium using electricity. However, at alkaline-pH, an in-situ process suffers from inorganic fouling within the stack, increasing the cost of capture. In the current work, we investigate fouling management strategies including fouling control (i.e., membrane- configuration and current-flow rate optimization) and fouling removal methods. Fouling removal methods including air and CO₂(g) sparging, dissolved CO₂ (aq) cleaning, back-pressure, flow rate increase, and acid-wash are investigated under accelerated fouling conditions. The stack configuration containing the BPM-AEM pairs shows 4 × lower fouling than the BPM-CEM stack, while the carbonate-extraction and faradaic efficiency are similar for both configurations. From the scaling removal methods, only the acid wash combined with the back-pressure removed all the inorganic fouling, recovering both the cell voltage and pressure drop to their initial values. Upon the air sparging, the total cell voltage and pressure drop increased even more due to the trapped gas inside the netted spacers. Cleaning via dissolved and gaseous CO₂ decreases the cell pH, dissolving hydroxide/carbonate-based fouling, but decreases the carbonate-removal significantly which is not preferred. Applying the back-pressure and higher flow rates decelerated the scaling buildup but was not enough to remove the fouling. Using BPM-AEM stacks in combination with periodic acid cleaning has potential as resilient oceanic carbon removal via BPMED.

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Polymeric ion-exchange membranes (IEMs) are key to many electrochemical processes, but their intrinsic selectivity limitations restrict scale-up possibilities. Nanofluidic IEMs, based on inorganic rigid materials and charged nanopores, offer a promising alternative. We present design criteria for selective nanofluidic membranes. We used commercial anodized aluminium oxide (AAO) membranes with varying pore sizes to measure permselectivity between different KCl concentrations. Our experiments reveal that membranes with 10-nm pores have permselectivities above 90%, comparable to those of polymeric IEMs, up to electrolyte concentrations of 0.15 vs. 0.75 M. To our knowledge, this is the highest reported ion selectivity for nanofluidic IEMs. Conversely, asymmetric AAO membranes featuring a thin selective layer, exhibited low permselectivity. We explored the influence of other parameters through simulations using the space-charge model. Our numerical results indicate that pore size and surface potential are the most sensitive parameters for increasing selectivity. Additionally, pore length has a minimum requirement for good performance although increasing it beyond the μm scale yields no significant result. This study highlights nanofluidic IEMs as a promising alternative to polymeric IEMs and their capability to improve performance of many electrochemical processes, especially those involving low electrolyte concentrations on at least one membrane side.

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CO2 electrolysis might be a key process to utilize intermittent renewable electricity for the sustainable production of hydrocarbon chemicals without relying on fossil fuels. Commonly used carbon-based gas diffusion electrodes (GDEs) enable high Faradaic efficiencies for the desired carbon products at high current densities, but have limited stability. In this study, we explore the adaption of a carbon-free GDE from a Chlor-alkali electrolysis process as a cathode for gas-fed CO2 electrolysis. We determine the impact of electrowetting on the electrochemical performance by analyzing the Faradaic efficiency for CO at industrially relevant current density. The characterization of used GDEs with X-ray photoelectron spectroscopy (XPS) and X-Ray diffraction (XRD) reveals a potential-dependent degradation, which can be explained through chemical polytetrafluorethylene (PTFE) degradation and/or physical erosion of PTFE through the restructuring of the silver surface. Our results further suggest that electrowetting-induced flooding lets the Faradaic efficiency for CO drop below 40% after only 30 min of electrolysis. We conclude that the effect of electrowetting has to be managed more carefully before the investigated carbon-free GDEs can compete with carbon-based GDEs as cathodes for CO2 electrolysis. Further, not only the conductive phase (such as carbon), but also the binder (such as PTFE), should be carefully selected for stable CO2 reduction.@en

Spatiotemporal pH imaging using fluorescence lifetime imaging microscopy (FLIM) is an excellent technique for investigating dynamic (electro)chemical processes. However, probes that are responsive at high pH values are not available. Here, we describe the development and application of dedicated pH probes based on the 1-methyl-7-amino-quinolinium fluorophore. The high fluorescence lifetime and quantum yield, the high (photo)stability, and the inherent water solubility make the quinolinium fluorophore well suited for the development of FLIM probes. Due to the flexible fluorophore-spacer-receptor architecture, probe lifetimes are tunable in the pH range between 5.5 and 11. An additional fluorescence lifetime response, at tunable pH values between 11 and 13, is achieved by deprotonation of the aromatic amine at the quinolinium core. Probe lifetimes are hardly affected by temperature and the presence of most inorganic ions, thus making FLIM imaging highly reliable and convenient. At 0.1 mM probe concentrations, imaging at rates of 3 images per second, at a resolution of 4 μm, while measuring pH values up to 12 is achieved. This enables the pH imaging of dynamic electrochemical processes involving chemical reactions and mass transport.

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Electrochemical CO₂ capture is promising for closing the carbon cycle but needs technological advances. In a recent issue of Nature Energy, a novel chemistry for electrochemical CO₂ capture is presented, demonstrating low energy consumption and high purity with virtually no degradation. This finally allows competition with amine-based capture technology.

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The use of gas diffusion electrodes that supply gaseous CO₂ directly to the catalyst layer has greatly improved the performance of electrochemical CO₂ conversion. However, reports of high current densities and Faradaic efficiencies primarily come from small lab scale electrolysers. Such electrolysers typically have a geometric area of 5 cm², while an industrial electrolyser would require an area closer to 1 m². The difference in scales means that many limitations that manifest only for larger electrolysers are not captured in lab scale setups. We develop a 2D computational model of both a lab scale and upscaled CO₂ electrolyser to determine performance limitations at larger scales and how they compare to the performance limitations observed at the lab scale. We find that for the same current density larger electrolysers exhibit much greater reaction and local environment inhomogeneity. Increasing catalyst layer pH and widening concentration boundary layers of the KHCO₃ buffer in the electrolyte channel lead to higher activation overpotential and increased parasitic loss of reactant CO₂ to the electrolyte solution. We show that a variable catalyst loading along the direction of the flow channel may improve the economics of a large scale CO₂ electrolyser.

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