The analytical tools to quantify CO₂RR products are often slow and have high limits of detection. As a result, researchers are forced to extend the duration of their experiments to accumulate sufficient product and surpass these detection limits. This slows down research considerably, and the research scope often remains limited. To help speed up CO₂RR catalyst studies, we have developed a new differential electrochemical mass spectrometer (DEMS) setup and cell design that enables the quantification of major gaseous and liquid products significantly faster than conventional analytical techniques. Special attention was given to the hydrodynamics of the cell to avoid mass transfer limitations and the calibration of the setup to accurately quantify the major CO₂ reduction products. As proof of concept of the methodology, the products formed during CO₂RR on a polycrystalline Ag and Cu electrode in a 0.1-M KHCO₃ electrolyte at different potentials were measured and quantified.

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Despite the huge efforts devoted to the development of the electrochemical reduction of CO2 (ECO2R) in the past decade, still many challenges are present, hindering further approaches to industrial applications. This paper gives a perspective on these challenges from a Process Systems Engineering (PSE) standpoint, while at the same time highlighting the opportunities for advancements in the field in the European context. The challenges are connected with: the coupling of these processes with renewable electricity generation; the feedstock (in particular CO2); the processes itself; and the different products that can be obtained. PSE can determine the optimal interactions among the components of such systems, allowing educated decision making in designing the best process configurations under uncertainty and constrains. The opportunities, on the other hand, stem from a stronger collaboration between the PSE and the experimental communities, from the possibility of integrating ECO2R into existing industrial productions and from process-wide optimisation studies, encompassing the whole production cycle of the chemicals to exploit possible synergies.@en

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

Electrochemical CO₂ reduction in non-aqueous solvents is promising due to the increased CO₂ solubility of organic-based electrolytes compared to aqueous electrolytes. Here the effect of nine different salts in propylene carbonate (PC) on the CO₂ reduction product distribution of polycrystalline Cu is investigated. Three different cations (tetraethylammonium (TEA), tetrabutylammonium (TBA), and tetrahexylammonium (THA)) and three different anions (chloride (Cl), tetrafluoroborate (BF₄), and hexafluorophosphate (PF₆)) were used. Chronoamperometry and in-situ FTIR measurements show that the size of the cation has a crucial role in the selectivity. A more hydrophobic surface is obtained when employing a larger cation with a weaker hydration shell. This stabilizes the CO₂⁻ radical and promotes the formation of ethylene. CO₂ reduction in 0.7 M THACl/PC shows the highest hydrocarbon formation. Lastly, we hypothesize that the hydrocarbon formation pathway is not through C−C coupling, as the CO solubility in PC is very high, but through the dimerization of the COH intermediate.

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Extending the lifetime of electrocatalytic materials is a major challenge in electrocatalysis. Here, we employ atomic layer deposition (ALD) to coat the surface of carbon black supported platinum nanoparticles (Pt/CB) with an ultra-thin layer of silicon dioxide (SiO2) to prevent deactivation of the catalyst during H2 evolution. Our results show that after an accelerated durability test (ADT) the current density at −0.2 V vs. reversible hydrogen electrode (RHE) of the unprotected Pt/CB catalyst was reduced by 34%. By contrast, after coating the Pt/CB catalyst with 2 SiO2 ALD cycles, the current density at the same potential was reduced by 7% after the ADT procedure, whereas when the Pt/CB sample was coated with 5 SiO2 ALD cycles, the current density was reduced by only 2% after the ADT. Characterization of the Pt particles after electrochemical testing shows that the average particle size of the uncoated Pt/CB catalyst increases by roughly 16% after the ADT, whereas it only increases by 3% for the Pt/CB catalyst coated with 5 cycles of SiO2 ALD. In addition, the coating also strongly reduces the detachment of Pt nanoparticles, as shown by a strong decrease in the Pt concentration in the electrolyte after the ADT. However, 20 cycles of SiO2 ALD coating results in an over-thick coating that has an inhibitory effect on the catalytic activity. In summary, we demonstrate that only a few cycles of SiO2 ALD can strongly improve the stability of Pt catalyst for the hydrogen evolution reaction.@en

Electrochemical CO₂ reduction is a promising way of closing the carbon cycle while synthesizing useful commodity chemicals and fuels. One of the possible routes to scale up the process is CO₂ reduction at elevated pressure, as this is a way to increase the concentration of poorly soluble CO₂ in aqueous systems. Yet, not many studies focus on this route, owing to the inherent challenges with high-pressure systems, such as leaks, product quantification, and ease of operation. In this study, we use a high-pressure flow cell setup to investigate the impact of CO₂ pressure on the electrochemical performance of a copper foam electrode for CO₂ reduction within a pressure range of 1 to 25 bar. Our initial findings using a 0.5 M potassium bicarbonate (KHCO₃) electrolyte show a consistent improvement in selectivity towards CO₂ reduction products, with HCOOH being the dominant product. By conducting a systematic exploration of operating parameters including applied current density, applied CO₂ pressure, cation effect, and electrolyte concentration, the selectivity towards formate (HCOOH) is optimized, achieving a remarkable 70 % faradaic efficiency (FE) under moderate conditions of 25 bar in a 0.5 M cesium bicarbonate (CsHCO₃) electrolyte. Additionally, we report the synthesis of isopropanol with a FE of 11 % at the 25 bar in 0.5 M KHCO₃ which is the highest reported selectivity towards isopropanol on copper using a bicarbonate system.

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In this study, the effect of halide anions on the selectivity of the CO₂ reduction reaction to CO was investigated in choline-based ethylene glycol solutions containing different halides (ChCl : EG, ChBr : EG, ChI : EG). The CO₂RR was studied using silver (Ag) and gold (Au) electrodes in a compact H-cell. Our findings reveal that chloride effectively suppresses the hydrogen evolution reaction and enhances the selectivity of carbon monoxide production on both Ag and Au electrodes, with relatively high selectivity values of 84 % and 62 %, respectively. Additionally, the effect of varying ethylene glycol content in the choline chloride-containing electrolyte (ChCl : EG 1 : X, X=2, 3, 4) was investigated to improve the current density during CO₂RR on the Ag electrode. We observed that a mole ratio of 1 : 4 exhibited the highest current density with a comparable faradaic efficiency toward CO. Notably, an evident surface reconstruction process took place on the Ag surface in the presence of Cl⁻ ions, whereas on Au, this phenomenon was less pronounced. Overall, this study provides new insights into anion-induced surface restructuring of Ag and Au electrodes during CO₂RR, and its consequences on the reduction performance on such surfaces in non-aqueous electrolytes.

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In this study, we experimentally screen a promising class of intermetallic alloys for the electrochemical reduction of CO₂ toward hydrocarbon products. Based on previous DFT-based screening papers, combinations of strongly CO-binding metals such as iron, cobalt, and nickel with weakly CO-binding metals such as gallium, aluminium or zinc were selected as potentially promising catalytic materials. Despite the challenging production of these alloys, we report a general two-step synthesis method for intermetallic alloys and discuss the specific synthesis conditions that must be taken into account when synthesising these materials. After their synthesis, we use a recently developed differential electrochemical mass spectrometry (DEMS) setup to rapidly quantify the CO₂ reduction products over a range of potentials. Almost all newly developed intermetallic catalysts are shown to produce methane and ethylene, while the CoSn catalyst showed higher selectivity towards formate production. However, all tested catalysts mostly produced hydrogen and only reduce CO₂ to a small extent, despite the favourable computational screening results. We discuss possible reasons for this discrepancy and outline a more holistic approach for linking future DFT studies with experiments.

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Electrolytic bicarbonate conversion holds the promise to integrate carbon capture directly with electrochemical conversion. Most research has focused on improving the faradaic efficiencies of the system, however, the stability of the system has not been thoroughly addressed. Here, we find that the bulk electrolyte pH has a large effect on the selectivity, where a higher pH results in a lower selectivity. However, the bulk electrolyte pH has no effect on the stability of the system. A decrease in CO selectivity of 30 % was observed within the first three hours of operation in an optimized system with 3 M KHCO₃ and gap between the membrane and electrode. Single-pass electrolyte experiments at various constant pH values (8.5, 9.0, 9.5, and 10.0), show that only at a pH of 10 the CO selectivity was stable during three hours, reaching a faradaic efficiency toward CO of only 18 % as compared to an initial 55 % at pH 8.5. Trace metal impurities present in the electrolyte were found to be the cause of the decrease in stability as these deposit on the electrode surface. By complexing the trace metal ions with ethylenediaminetetraacetic acid (EDTA), the metal deposition was avoided and a stable CO selectivity was obtained.

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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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Aqueous electrolytes used in CO2 electroreduction typically have a CO2 solubility of around 34 mM under ambient conditions, contributing to mass transfer limitations in the system. Non-aqueous electrolytes exhibit higher CO2 solubility (by 5–8-fold) and also provide possibilities to suppress the undesired hydrogen evolution reaction (HER). On the other hand, a proton donor is needed to produce many of the products commonly obtained with aqueous electrolytes. This work investigates the electrochemical CO2 reduction performance of copper in non-aqueous electrolytes based on dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), and acetonitrile (ACN). The main objective is to analyze whether non-aqueous electrolytes are a viable alternative to aqueous electrolytes for hydrocarbon production. Additionally, the effects of aqueous/non-aqueous anolytes, membrane, and the selection of a potential window on the electrochemical CO2 reduction performance are addressed in this study. Experiments with pure DMF and NMP mainly produced oxalate with a faradaic efficiency (FE) reaching >80%; however, pure ACN mainly produced hydrogen and formate due to the presence of more residual water in the system. Addition of 5% (v/v) water to the non-aqueous electrolytes resulted in increased HER and formate production with negligible hydrocarbon production. Hence, we conclude that aqueous electrolytes remain a better choice for the production of hydrocarbons and alcohols on a copper electrode, while organic electrolytes based on DMF and NMP can be used to obtain a high selectivity toward oxalate and formate.@en

Electrochemical carbon dioxide (CO₂) reduction is a promising route to convert intermittent renewable energy into fuels and valuable chemical products. Separation of CO₂ reduction products by ion-selective electrochemical technology may play a decisive role in the pursuit of commercially viable CO₂ reduction processes. Selective separation of formate, one of the main CO₂ reduction products, is assessed in the present study in an electrochemical flow cell with symmetric redox-active polyvinyl ferrocene (PVF) functionalized graphene oxide (GO) electrodes. First, experimental parameters such as the PVF/GO ratio, sonication time, and ultrasonic amplitude, were optimized in the electrode preparation process to improve the formate adsorption efficiency on a lab scale (1 × 2 cm electrodes) under static conditions. The electrochemical and morphological characteristics of the electrodes were investigated by cyclic voltammetry and scanning electron microscopy. To demonstrate continuous-flow operation, an electrosorption flow cell (8 × 8 cm) providing inline measurements was constructed. The flow cell results showed selectivity at > 5.5 toward the removal of formate from an electrolyte containing perchlorate at an excess of 30 times the normal value. The performance of the electrosorption cell was also tested using a mixture of methanol, ethanol, formate, and acetaldehyde produced in a CO₂ reduction electrolyzer. In this demonstration, formate separation was achieved with a selectivity of > 4.0. The results suggest that the optimized design of the electrochemical cell and operation conditions of the flow platform pave the way for scaling up selective formate separation with PVF/GO electrodes.

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Direct electroreduction of nitric oxide offers a promising avenue to produce valuable chemicals, such as ammonia, which is an essential chemical to produce fertilizers. Direct ammonia synthesis from NO in a polymer electrolyte membrane (PEM) electrolyzer is advantageous for its continuous operation and excellent mass transport characteristics. However, at a high current density, the faradaic efficiency of NO electroreduction reaction is limited by the competing hydrogen evolution reaction (HER). Herein, we report a CO-mediated selective poisoning strategy to enhance the faradaic efficiency (FE) towards ammonia by suppressing the HER. In the presence of only NO at the cathode, Pt/C and Pd/C catalysts showed a lower FE towards NH₃ than to H₂ due to the dominating HER. Cu/C catalyst showed a 78 % FE towards NH₃ at 2.0 V due to the stronger binding affinity to NO* compared to H*. By co-feeding CO, the FE of Cu/C catalyst towards NH₃ was improved by 12 %. More strikingly, for Pd/C, the FE towards NH₃ was enhanced by 95 % with CO co-feeding, by effectively suppressing HER. This is attributed to the change of the favorable surface coverage resulting from the selective and competitive binding of CO* to H* binding sites, thereby improving NH₃ selectivity.

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Aqueous electrolytes are most commonly used for the CO₂ reduction reaction (CO₂RR), but suffer from a low CO₂ solubility that limits the reaction. Electrochemical CO₂ reduction in nonaqueous electrolytes can provide a solution, due to the higher CO₂ solubility of organic solvent-based electrolytes. Herein, the product distribution of the electrochemical CO₂ reduction on polycrystalline Cu in 0.7 m tetraethylammonium chloride in propylene carbonate with different water additions (0, 10, and 90 v%), and for different operating conditions (10, 25, 40, and 60 °C), is investigated. It is found that CO₂ reduction on Cu in a propylene carbonate solution results in H₂, CO, and formic acid formation only, even though Cu is known to produce C₂₊ products such as ethylene and ethanol in aqueous electrolytes. Increasing the operating temperature increases the CO₂RR kinetics and shows an improvement in CO formation and decrease in H₂ formation. However, increasing the operating temperature also increases water transport through the membrane, resulting in an increase of H₂ formation over time when operating at 60 °C.

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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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Abstract: The electrochemical CO₂ reduction reaction (CO₂RR) has been proposed as a sustainable way of closing the carbon cycle while synthesizing useful commodity chemicals. One of the possible routes to scale up the process is the elevated pressure CO₂RR, as this increases the concentration of the poorly soluble CO₂ in aqueous systems. Yet, there are not many studies that focus on this route owing to the inherent challenges with high pressure systems. In this study, a novel high pressure flow cell setup has been designed and validated. The modular design uses a clamp system, which facilitates simple stacking of multiple cell parts while being capable of handling pressures up to 50 bar. The effects of CO₂ pressure on the reaction were investigated on a gold (Au) foil cathode in a 0.1 M KHCO₃ electrolyte. We successfully measured gaseous products produced during high pressure operation using an inline gas chromatograph. We find that the selectivity toward CO₂ reduction products is enhanced while that of H₂ evolution is suppressed as the pressure is increased from 2 to 30 bar. The reported setup provides a robust means to conduct high pressure electrolysis experiments in an easy and safe manner, making this technology more accessible to the electrochemical CO₂RR community. Graphical abstract: [Figure not available: see fulltext.].

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N-doped carbon materials can be efficient and cost-effective catalysts for the electrochemical CO₂ reduction reaction (CO₂RR). Activators are often used in the synthesis process to increase the specific surface area and porosity of these carbon materials. However, owing to the diversity of activators and the differences in physicochemical properties that these activators induce, the influence of activators used for the synthesis of N-doped carbon catalysts on their electrochemical performance is unclear. In this study, a series of bagasse-derived N-doped carbon catalysts is prepared with the assistance of different activators to understand the correlation between activators, physicochemical properties, and electrocatalytic performance for the CO₂RR. The properties of N-doped carbon catalysts, such as N-doping content, microstructure, and degree of graphitization, are found to be highly dependent on the type of activator applied in the synthesis procedure. Moreover, the overall CO₂RR performance of the synthesized electrocatalysts is not determined only by the N-doping level and the configuration of the N-dopant, but rather by the overall surface chemistry, where the porosity and the degree of graphitization are jointly responsible for significant differences in CO₂RR performance.

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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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Most research into electrochemical CO2 conversion focusses on improving electrode materials, but neglects the role of the electrolyte. We show the buffer influence on the selectivity of a bimetallic gold–palladium electrode in an effort to elucidate observed inconsistencies between different studies. While hydrocarbons are produced in the phosphate buffer, they remain absent in the bicarbonate buffer, showing that the electrolyte choice plays a crucial role in the selectivity of the electrode.@en