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

Electrochemical ammonia synthesis via the nitrogen reduction reaction (NRR) has been poised as one of the promising technologies for the sustainable production of green ammonia. In this work, we developed extensive process models of fully integrated electrochemical NH ₃ production plants at small scale (91 tonnes per day), including their techno-economic assessments, for (Li-)mediated, direct and indirect NRR pathways at ambient and elevated temperatures, which were compared with electrified and steam-methane reforming (SMR) Haber-Bosch processes. The levelized cost of ammonia (LCOA) of aqueous NRR at ambient conditions only becomes comparable with SMR Haber-Bosch at very optimistic electrolyzer performance parameters (FE > 80% at j ≥ 0.3 A cm ⁻²) and electricity prices (<$0.024 per kW h). Both high temperature NRR and Li-mediated NRR are not economically comparable within the tested variable ranges. High temperature NRR is very capital intensive due the requirement of a heat exchanger network, more auxiliary equipment and an additional water electrolyzer (considering the indirect route). For Li-mediated NRR, the high lithium plating potentials, ohmic losses and the requirement for H ₂, limits its commercial competitiveness with SMR Haber-Bosch. This incentivises the search for materials beyond lithium.

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Increasing the electrode thickness, thereby reducing the proportion of inactive cell components, is one way to achieve higher-energy-density lithium-ion batteries. This, however, results in higher electronic and ionic overpotentials and/or mechanical failure induced by binder migration. Here, we report ethanol-induced phase inversion as an effective method for making high-mass-loading nickel-rich, layered oxide (LiNi0.8Mn0.1Co0.1O2 [NMC811]) electrodes. The ethanol-induced phase inversion electrodes significantly outperform their conventionally processed counterparts with similar loading (35 mg/cm2) and porosity (30%) in Li/NMC half-cells (131.7 mAh/g vs. 56.7 mAh/g) at 1C (7 mA/cm2) discharge. The binder structure induced by the nonsolvent improves the pore connectivity and results in lower tortuosity factors. The rapid solvent removal reduces the binder migration during drying, enabling ultrahigh active mass loadings up to 60 mg/cm2 (12 mAh/cm2). Further, the compatibility of the phase inversion process with current roll-to-roll coating setups makes this a processing technique with high industrial feasibility.@en

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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Ammonia is an indispensable commodity and a potential carbon free energy carrier. The use of H permeable electrodes to synthesize ammonia from N ₂, water and electricity, provides a promising alternative to the fossil fuel based Haber-Bosch process. Here, H permeable Ni electrodes are investigated in the operating temperature range 25–120 °C, and varying the rate of electrochemical atomic hydrogen permeation. At 120 °C, a steady reaction is achieved for over 12 h with 10 times higher cumulative NH ₃ production and almost 40-fold increase in faradaic efficiency compared to room temperature experiments. NH ₃ is formed with a cell potential of 1.4 V, corresponding to a minimum electrical energy investment of 6.6 kWh kg ⁻¹ (Figure presented.). The stable operation is attributed to a balanced control over the population of N, NH _x and H species at the catalyst surface. These findings extend the understanding on the mechanisms involved in the nitrogen reduction reaction and may facilitate the development of an efficient green ammonia synthesis process.

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The electrochemical dinitrogen reduction reaction (NRR) has recently gained much interest as it can potentially produce ammonia from renewable intermittent electricity and replace the Haber-Bosch process. Previous literature studies report Fe- and Mo-carbides as promising electrocatalysts for the NRR with activities higher than other metals. However, recent understanding of extraneous ammonia and nitrogen oxide contaminations have challenged previously published results. Here, we critically assess the NRR performance of several Fe- and Mo-carbides reported as promising by implementing a strict experimental protocol to minimize the effect of impurities. The successful synthesis of α-Mo₂C decorated carbon nanosheets, α-Mo₂C nanoparticles, θ-Fe₃C nanoparticles, and χ-Fe₅C₂ nanoparticles was confirmed by X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron and Mössbauer spectroscopy. After performing NRR chronoamperometric tests with the synthesized materials, the ammonia concentrations varied between 37 and 124 ppb and are in close proximity with the estimated ammonia background level. Notwithstanding the impracticality of these extremely low ammonia yields, the observed ammonia did not originate from the electrochemical nitrogen reduction but from unavoidable extraneous ammonia and NO_x impurities. These findings are in contradiction with earlier literature studies and show that these carbide materials are not active for the NRR under the employed conditions. This further emphasizes the importance of a strict protocol in order to distinguish between a promising NRR catalyst and a false positive.

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Nanostructured solid composite electrolyte or nano-SCE, which is composed of an ionic liquid, nanoporous silica, and residuals of immobilized precursor components, shows promising synergistic properties. The ionic conductivity of nano-SCE is in the range of 2–5 mS cm⁻¹, which exceeds the bulk ionic liquid conductivity at ambient temperature, while maintaining characteristics of a solid electrolyte such as having no leakage issues as the ionic liquid is confined, and lower flammability compared to conventional liquid electrolytes. In this study, the underlying mechanism of enhanced conductivity is investigated by using magic angle spinning NMR and NMR relaxometry analysis. Water, one of the volatile precursor molecules has shown to play a key role in the final conductivity and stability at the solid-electrolyte interface, as it enhances the temperature range in which the ionic liquid remains mobile. In line with previous studies, water with lowered mobility is found in the silicon matrix. The activation energies of lithium ion transfer probed by NMR relaxometry, however, do not change as function of water content. The increase in bulk mobility of lithium ions under ambient conditions compared to water-less nano-SCE is found to be the origin of the altered conductivity of this material.

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The electrochemical nitrogen reduction reaction (NRR) is a promising alternative to the current greenhouse gas emission intensive process to produce ammonia (NH₃) from nitrogen (N₂). However, finding an electrocatalyst that promotes NRR over the competing hydrogen evolution reaction (HER) has proven to be difficult. This difficulty could potentially be addressed by accelerating the electrocatalyst development for NRR by orders of magnitude using high-throughput (HTP) workflows. In this work, we developed a HTP gas diffusion electrode (GDE) cell to screen up to 16 electrocatalysts in parallel. The key innovation of the cell is the use of expanded Polytetrafluoroethylene (ePTFE) gas diffusion layers (GDL) which simplifies the handling of catalyst arrays compared to carbon fabrics and enables sufficient N₂ mass transport. We demonstrate the robustness of the HTP workflow by screening 528 bimetallic catalysts of composition AB (A,B = Ag, Al, Au, Co, Cu, Fe, Mn, Mo, Ni, Pd, Re, Ru, W) for NRR activity. None of the materials produced ammonia significantly over background level which emphasizes the difficulty of finding active electrocatalysts for NRR and narrows down the search space for future studies.

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Hydrogen permeable electrodes can be utilized for electrolytic ammonia synthesis from dinitrogen, water, and renewable electricity under ambient conditions, providing a promising route toward sustainable ammonia. The understanding of the interactions of adsorbing N and permeating H at the catalytic interface is a critical step toward the optimization of this NH3 synthesis process. In this study, we conducted a unique in situ near ambient pressure X-ray photoelectron spectroscopy experiment to investigate the solid-gas interface of a Ni hydrogen permeable electrode under conditions relevant for ammonia synthesis. Here, we show that the formation of a Ni oxide surface layer blocks the chemisorption of gaseous dinitrogen. However, the Ni 2p and O 1s XPS spectra reveal that electrochemically driven permeating atomic hydrogen effectively reduces the Ni surface at ambient temperature, while H2 does not. Nitrogen gas chemisorbs on the generated metallic sites, followed by hydrogenation via permeating H, as adsorbed N and NH3 are found on the Ni surface. Our findings suggest that the first hydrogenation step to NH and the NH3 desorption might be limiting under the operating conditions. The study was then extended to Fe and Ru surfaces. The formation of surface oxide and nitride species on iron blocks the H permeation and prevents the reaction to advance; while on ruthenium, the stronger Ru-N bond might favor the recombination of permeating hydrogen to H2 over the hydrogenation of adsorbed nitrogen. This work provides insightful results to aid the rational design of efficient electrolytic NH3 synthesis processes based on but not limited to hydrogen permeable electrodes.

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The nitrogen reduction reaction (NRR) is a promising pathway toward the decarbonization of ammonia (NH3) production. However, unless practical challenges related to the detection of NH3 are removed, confidence in published data and experimental throughput will remain low for experiments in aqueous electrolyte. In this perspective, we analyze these challenges from a system and instrumentation perspective. Through our analysis we show that detection challenges can be strongly reduced by switching from an Hcell to a gas diffusion electrode (GDE) cell design as a catalyst testing platform. Specifically, a GDE cell design is anticipated to allow for a reduction in the cost of crucial 15N2 control experiments from €100−2000 to less than €10. A major driver is the possibility to reduce the 15N2 flow rate to less than 1 mL/min, which is prohibited by an inevitable drop in mass-transport at low flow rates in H-cells. Higher active surface areas and improved mass transport can further circumvent losses of NRR selectivity to competing reactions. Additionally, obstacles often encountered when trying to transfer activity and selectivity data recorded at low current density in Hcells to commercial device level can be avoided by testing catalysts under conditions close to those in commercial devices from the start.@en

Rapid advances in electrocatalytic ammonia synthesis are impeded by laborious detection methods commonly used in the field and by constant risk of external contaminations, which generates misleading false positives. We developed a facile real-time GC-MS method for sensitive isotope NH3 quantification, requiring no external sample manipulations. This method ensures high detection reliability paramount to accelerate (electro-)catalyst screening.@en

The transition to renewable electricity sources and green feedstock implies the development of electricity storage and conversion systems to both stabilise the electricity grid and provide electrolytic hydrogen. We have recently introduced the concept of a hybrid Ni/Fe battery-electrolyser (battolyser) for this application1. The hydrogen produced during the Ni/Fe cell charge and continued electrolysis can serve as chemical feedstock and a fuel for long-term storage, while the hybrid battery electrodes provide short term storage. Here, we present Ni-Fe layered double hydroxides (NiFe-LDHs) for enhancing the positive electrode performance. The modified Ni(OH)2 material capacity, high rate performance and stability have been tested over a large range of charge rates (from 0.1C to 20C) over 1000 cycles. The Ni-Fe layered double hydroxides allow the capacity per nickel atom to be multiplied by 1.8 in comparison to the conventional β-Ni(OH)2 material which suggests that the nickel content can be reduced by 45% for the same capacity. This reduction of the nickel content is extremely important as this presents the most costly resource. In addition, Fe doped Ni(OH)2 shows improved ionic and electronic conductivity, OER catalytic activity outperforming the benchmark (Ir/C) catalyst, and long term cycling stability. The implementation of this Fe doped Ni(OH)2 material in the Ni/Fe hybrid battery-electrolyser will bring both electrolysis and battery function forward at reduced material cost and energy loss.

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Direct electrolytic N2 reduction to ammonia (NH3) is a renewable alternative to the Haber-Bosch process. The activity and selectivity of electrocatalysts are evaluated by measuring the amount of NH3 in the electrolyte. Quantitative 1H nuclear magnetic resonance (qNMR) detection reduces the bench time to analyze samples of NH3 (present in the assay as NH4+) compared to conventional spectrophotometric methods. However, many groups do not have access to an NMR spectrometer with sufficiently high sensitivity. We report that by adding 1 mM paramagnetic Gd3+ ions to the NMR sample, the required analysis time can be reduced by an order of magnitude such that fast NH4+ detection becomes accessible with a standard NMR spectrometer. Accurate, internally calibrated quantification is possible over a wide pH range.

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Iron is a promising, earth-abundant material for future energy applications. In this study, we use a neutron diffractometer to investigate the properties of an iron electrode in an alkaline environment. As neutrons penetrate deeply into materials, neutron scattering gives us a unique insight into what is happening inside the electrode. We made our measurements while the electrode was charging or discharging. Our key questions are: Which phases occur for the first and second discharge plateaus? And why are iron electrodes less responsive at higher discharge rates? We conclude that metallic iron and iron hydroxide form the redox pair for the first discharge plateau. For the second discharge plateau, we found a phase similar to feroxyhyte but with symmetrical and equally spaced arrangement of hydrogen atoms. The data suggest that no other iron oxide or iron (oxy)hydroxide formed. Remarkable findings include the following: (1) substantial amounts of iron hydroxide are always present inside the electrode. (2) Passivation is mostly caused by iron hydroxide that is unable to recharge. (3) Iron fractions change as expected, while iron hydroxide fractions are delayed, resulting in substantial amounts of
amorphous, undetectable iron phases. About 40% of the participating iron of the first plateau and about 55% of the participating iron for the second plateau are undetectable. (4) Massive and unexpected precipitation of iron hydroxide occurs in the transition from discharging to charging. (2), (3), and (4) together cause accumulation of iron hydroxide inside the electrode.@en

Direct electrochemical nitrogen reduction holds the promise of enabling the production of carbon emission-free ammonia, which is an important intermediate in the fertilizer industry and a potential green energy carrier. Here we show a strategy for ambient condition ammonia synthesis using a hydrogen permeable nickel membrane/electrode that spatially separates the electrolyte and hydrogen reduction side from the dinitrogen activation and hydrogenation sites. Gaseous ammonia is produced catalytically in the absence of electrolyte via hydrogenation of adsorbed nitrogen by electrochemically permeating atomic hydrogen from water reduction. Dinitrogen activation at the polycrystalline nickel surface is confirmed with 15N2 isotope labeling experiments, and it is attributed to a Mars-van Krevelen mechanism enabled by the formation of N-vacancies upon hydrogenation of surface nitrides. We further show that gaseous hydrogen does not hydrogenate the adsorbed nitrogen, strengthening the benefit of having an atomic hydrogen permeable electrode. The proposed approach opens new directions toward green ammonia.

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Both daily and seasonal fluctuations of renewable power sources will require large-scale energy storage technologies. A recently developed integrated battery and electrolyzer system, called battolyser, fulfills both time-scale requirements. Here, we develop a macroscopic COMSOL Multiphysics model to quantify the energetic efficiency of the battolyser prototype that, for the first time, integrates the functionality of a nickel-iron battery and an alkaline electrolyzer. The current prototype has a rated capacity of 5 Ah, and to develop a larger, enhanced system, it is necessary to characterize the processes occurring within the battolyser and to optimize the individual components of the battolyser. Therefore, there is a need for a model that can provide a fast screening on how the properties of individual components influence the overall energy efficiency of the battolyser prototype. The model is validated using experimental results, and new configurations are compared, and the energy efficiency is optimized for the scale-up of this lab-scale device. Based on the modeling work, we find an optimum electrode thickness for the nickel electrode of 3 and 2.25 mm for the iron electrode with optimal electrode porosities in the range of void fraction of 0.15-0.35. Additionally, electrolyte conductivity and the gap thickness are found to have a small effect on the overall efficiency of the device.

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Mg attracts much research interest as anode material for Ni-MH batteries thanks to its lightweight, cost-effectiveness and high theoretical capacity (2200 mA h g⁻¹). However, its practical application is tremendously challenged by the poor hydrogen sorption kinetics, passivation from aggressive aqueous electrolytes, and insulating nature of MgH₂. Mg-based alloys exhibit enhanced hydrogen sorption kinetics and electrical conductivity, but significant amount of costly transition metal elements are required. In this work, we have, for the first time, utilized non-alloyed but catalyzed Mg as anode for Ni-MH batteries. 5 mol.% TiF₃ was added to nanosized Mg for accelerating the hydrogen sorption kinetics. Several strategies for preventing the problematic passivation of Mg have been studied, including protective encapsulation of the electrode and utilizing room-temperature/high-temperature ionic liquids and an alkaline polymer membrane as working electrolyte. Promising electrochemical performance has been achieved in this Mg–TiF₃ composite anode based Ni-MH batteries with room for further improvements.

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The commercial uptake of lithium-sulfur (Li-S) batteries is undermined by their rapid performance decay and short cycle life. These problems originate from the dissolution of lithium polysulfide in liquid electrolytes, causing charge and active material to shuttle between electrodes. The dynamics of intractable polysulfide migration at different length scales often tend to escape the probing ability of many analytical techniques. Spatial and temporal visualization of Li in Li-S electrodes and direct mechanistic understanding of how polysulfides are regulated across Li-S batteries starting from current collector and active layer coating to electrode-electrolyte interface are still lacking. To address this we employ neutron depth profiling across Li-S electrodes using the naturally occurring isotope, 6Li, which yields direct spatial information on Li-S electrochemistry. Using three types of Li-S electrodes, namely, carbon-sulfur, carbon-sulfur with 10% lithium titanium oxide (LTO), and carbon-sulfur with LTO membrane, we provide direct evidence for the migration, adsorption, and confinement of polysulfides in Li-S cells at work. Our findings further provide insights into the dynamics of polysulfide dissolution and re-utilization in relation to Li-S battery capacity and longevity to aid rational electrode designs toward high-energy, safe, and low-cost batteries.

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