Rutile-Type Co0.5Ti0.5NbO4-Based Cathode with In Situ Exsolved Metal Particles for Direct CO2 Electrolysis.

Rutile-type Co0.5Ti0.5NbO4 (CTO)-based materials doped with Fe3+ or Ni2+ were investigated as cathode electrodes to modify their electrical conductivity and electrocatalysis toward CO2 splitting. Higher electric conductivity was found in Co0.4Fe0.2Ti0.4NbO4 (CTO-Fe, 0.78 S cm-1) and Co0.25Ni0.25Ti0.5NbO4 (CTO-Ni, 2.10 S cm-1) compared to CTO (0.49 S cm-1) after the reduction at 800 °C in Ar-5% H2. Co and Co-Ni particles exsolved in situ from the surface of CTO, CTO-Fe, and CTO-Ni after reduction. CTO-Ni and CTO-Fe cathodes did better in the CO2 electrolysis at 800 °C than the CTO one, but the CTO-Ni cell was unstable after 10 h of operation due to the carbon deposition that blocked the electrode. The cell with CTO-Fe demonstrated a good stability for CO2 splitting in 100 h. This work demonstrates that rutile-type CTO-based cathodes are promising to provide an efficient and candidate oxide cathode for the electrolysis of CO2.

Lewis-base ligand-reshaped interfacial hydrogen-bond network boosts CO2 electrolysis.

Both the catalyst and electrolyte strongly impact the performance of CO2 electrolysis. Despite substantial progress in catalysts, it remains highly challenging to tailor electrolyte compositions and understand their functions at the catalyst interface. Here, we report that the ethylenediaminetetraacetic acid (EDTA) and its analogs, featuring strong Lewis acid-base interaction with metal cations, are selected as electrolyte additives to reshape the catalyst-electrolyte interface for promoting CO2 electrolysis. Mechanistic studies reveal that EDTA molecules are dynamically assembled toward interface regions in response to bias potential due to strong Lewis acid-base interaction of EDTA4--K+. As a result, the original hydrogen-bond network among interfacial H2O is disrupted, and a hydrogen-bond gap layer at the electrified interface is established. The EDTA-reshaped K+ solvation structure promotes the protonation of *CO2 to *COOH and suppressing *H2O dissociation to *H, thereby boosting the co-electrolysis of CO2 and H2O toward carbon-based products. In particular, when 5 mM of EDTA is added into the electrolytes, the Faradaic efficiency of CO on the commercial Ag nanoparticle catalyst is increased from 57.0% to 90.0% at an industry-relevant current density of 500 mA cm-2. More importantly, the Lewis-base ligand-reshaped interface allows a range of catalysts (Ag, Zn, Pd, Bi, Sn, and Cu) to deliver substantially increased selectivity of carbon-based products in both H-type and flow-type electrolysis cells.

Enhancing the CO2 Adsorption of the Cobalt-Free Layered Perovskite Cathode for Solid-Oxide Electrolysis Cells Gains Excellent Stability under High Voltages via Oxygen-Defect Adjustment.

Solid-oxide electrolysis cells are a clean energy conversion device with the ability to directly electrolyze the conversion of CO2 to CO efficiently. However, their practical applications are limited due to insufficient CO2 adsorption performance of the cathode materials. To overcome this issue, the A-site cation deficiency strategy has been applied in a layered perovskite PrBaFe1.6Ni0.4O6-δ (PBFN) cathode for direct CO2 electrolysis. The introduction of 5% deficiency at the Pr/Ba site leads to a significant increase in the concentration of oxygen vacancies (nonstoichiometric number δ of oxygen vacancies increased from 0.093 to 0.132), which greatly accelerates the CO2 adsorption performance as well as the O2- transport capacity toward the CO2 reduction reaction (CO2RR). CO2 temperature-programmed desorption indicates that A-site cation-deficient (PrBa)0.95Fe1.6Ni0.4O6-δ (PB95FN) shows a larger desorption peak area and a higher desorption temperature. PB95FN also exhibits a greater presence of carbonate in Fourier transform infrared (FT-IR) spectroscopy. The electrical conductivity relaxation test shows that the introduction of the 5% A-site deficiency effectively improves the surface oxygen exchange and diffusion kinetics of PB95FN. The current density of the electrolysis cell with the (PrBa)0.95Fe1.6Ni0.4O6-δ (PB95FN) cathode reaches 0.876 A·cm-2 under 1.5 V at 800 °C, which is 41% higher than that of PB100FN. Moreover, the PB95FN cathode demonstrates excellent long-term stability over 100 h and better short-term stability than PB100FN under high voltages, which can be ascribed to the enhanced CO2 adsorption performance. The PB95FN cathode maintains a porous structure and tightly binds to the electrolyte after stability testing. This study highlights the potential of regulating oxygen defects in layered perovskite PrBaFe1.6Ni0.4O6-δ cathode materials via incorporation of cation deficiency toward high-temperature CO2 electrolysis.

Anchoring Cs+ Ions on Carbon Vacancies for Selective CO2 Electroreduction to CO at High Current Densities in Membrane Electrode Assembly Electrolyzers.

Electrolyte cations have been demonstrated to effectively enhance the rate and selectivity of the electrochemical CO2 reduction reaction (CO2RR), yet their implementation in electrolyte-free membrane electrode assembly (MEA) electrolyzer presents significant challenges. Herein, an anchored cation strategy that immobilizes Cs+ on carbon vacancies was designed and innovatively implemented in MEA electrolyzer, enabling highly efficient CO2 electroreduction over commercial silver catalyst. Our approach achieves a CO partial current density of approximately 500 mA cm-2 in the MEA electrolyzer, three-fold enhancement compared to pure Ag. In situ Raman and theoretical analyses, combined with machine learning potentials, reveal anchored Cs induces an electric field that significantly promotes the adsorption of *CO2 - intermediates through performing muti-point energy calculations on each structure. Furthermore, reduced adsorption of *OH intermediates effectively hampers competing hydrogen evolution reaction, as clarified by disk electrode experiments and density functional theory studies. Additionally, coupling our system with commercial polysilicon solar cells yields a notable solar-to-CO energy conversion efficiency of 8.3 %. This study opens a new avenue for developing effective cation-promoting strategy in MEA reactors for efficient CO2RR.

Quantitative Analysis and Manipulation of Alkali Metal Cations at the Cathode Surface in Membrane Electrode Assembly Electrolyzers for CO2 Reduction Reactions.

The stable operation of the CO2 reduction reaction (CO2RR) in membrane electrode assembly (MEA) electrolyzers is known to be hindered by the accumulation of bicarbonate salt, which are derived from alkali metal cations in anolytes, on the cathode side. In this study, we conducted a quantitative evaluation of the correlation between the CO2RR activity and the transported alkali metal cations in MEA electrolyzers. As a result, although the presence of transported alkali metal cations on the cathode surface significantly contributes to the generation of C2+ compounds, the rate of K+ ion transport did not match the selectivity of C2+, suggesting that a continuous supply of high amount of K+ to the cathode surface is not required for C2+ formation. Based on these findings, we achieved a faradaic efficiency (FE) and a partial current density for C2+ of 77 % and 230 mA cm-2, respectively, even after switching the anode solution from 0.1 M KHCO3 to a dilute K+ solution (<7 mM). These values were almost identical to those when 0.1 M KHCO3 was continuously supplied. Based on this insight, we successfully improved the durability of the system against salt precipitation by intermittently supplying concentrated KHCO3, compared with the continuous supply.

Reference Electrode Types for Zero-Gap CO2 Electrolyzers: Benefits and Limitations.

Integrated reference electrodes allow to deconvolute voltage contributions of anode and cathode and contribute to a better understanding of CO2 electrolyzers. However, in zero-gap cell configurations, this integration can be challenging and obtaining error-free data with such a setup is a non-trivial task. This study compares five different methods to integrate a reference electrode into an alkaline zero-gap CO2 electrolysis cell. Sources of error and measures to circumvent them are investigated and finite-element simulation is used to gain a better understanding of observed effects. Placing a reference electrode into the inactive area of the cell is found to be a reliable method, as long as the placement of electrodes is sufficiently controlled. Sandwiching a wire quasi-reference electrode between two membranes is especially useful for electrochemical impedance spectroscopy; however, it can affect the overall cell performance. Contacting the catalyst layer from the backside with a salt-bridge is promising for localized measurements if sufficient reproducibility can be ensured.

In Situ Self-Assembled Active and Stable Ir@MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ Interfaces for CO2 Electrolysis.

Solid oxide electrolysis cells are prospective approaches for CO2 utilization but face significant challenges due to the sluggish reaction kinetics and poor stability of the fuel electrodes. Herein, we strategically addressed the long-standing trade-off phenomenon between enhanced exsolution and improved structural stability via topotactic ion exchange. The surface dynamic reconstruction of the MnOx/La0.7Sr0.3Cr0.9Ir0.1O3-δ (LSCIr) catalyst was visualized at the atomic scale. Compared with the Ir@LSCIr interface, the in situ self-assembled Ir@MnOx/LSCIr interface exhibited greater CO2 activation and easily removable carbonate intermediates, thus reached a 42 % improvement in CO2 electrolysis performance at 1.6 V. Furthermore, an improved CO2 electrolysis stability was achieved due to the uniformly wrapped MnOx shell of the Ir@MnOx/LSCIr cathode. Our approach enables a detailed understanding of the dynamic microstructure evolution at active interfaces and provides a roadmap for the rational design and evaluation of efficient metal/oxide catalysts for CO2 electrolysis.

Nonconductive Metal Oxide Gas Diffusion Layer for Mitigating Electrowetting during CO2 Electrolysis.

Gas diffusion electrodes (GDEs) are extensively used for high current density electrochemical CO2 electrolysis (ECO2R), enabled by significantly reducing mass transfer resistance of CO2 to the catalyst layer. Conventionally, these GDEs are based upon hydrophobic carbon-based gas-diffusion layers (GDLs) that facilitate the gas transport; however, these supports are prone to flood with electrolyte during electrolysis. This potential-induced flooding, known as electrowetting, is related to the inherent conductivity of carbon and limits the activity of ECO2R. To investigate the effect of electrical conductivity more carefully, a GDE is constructed based on a Cu mesh with a nonconductive microporous GDL applied to this substrate, the latter composed of a mixture of metal oxide and polytetrafluoroethylene. With alumina as the metal oxide, a stable operation is obtained at -200 mA cm-2 with 70% selectivity for ECO2R (with over half toward C2+ products) without flooding as observed by in situ microscopy. On the contrary, with a Vulcan carbon-based GDL, the initial activity is rapidly lost as severe flooding ensues. It is reasoned that electrowetting is averted by virtue of the nonconductive nature of alumina, providing a new perspective on alternative GDL compositions and their influence on ECO2R performance.

Structural Effects of 3D Inkjet-Printed Ni(O)-YSZ Pillared Electrodes on Performances of Solid Oxide Electrochemical Reactors.

Increasing densities of reaction sites for gaseous reactants in solid oxide electrochemical reactors (SOERs), is a key strategy for achieving enhanced performance in either fuel cell or electrolysis modes. Fabrication of 3D structured components in SOERs can enhance those densities of reaction sites, which is achieved by 3D inkjet printing with high reproducibility, having developed inks with appropriate properties. First, the effects of pillar geometries on SOER performances are predicted through numerical simulations, enabling subsequent 3D printing to focus on the more effective geometries. Herein, the study reports the results of experimental validation of those predictions by evaluating the electrochemical performances of cells with various heights of 3D inkjet-printed Ni(O)- yttria stabilized zirconia (YSZ) pillars and YSZ pillars. Those measurements prove that increasing pillar heights generally increases SOER peak power densities in fuel cell mode and increased current densities at the thermoneutral potential (1.285 V) in steam electrolysis mode, as predicted by simulations. With increasing pillar heights, more limitations in performance enhancement are found with YSZ electrolyte pillars than with Ni-YSZ pillars, again as predicted by simulations. The subsequent microstructural analysis of Ni-YSZ pillars proves the suitability of the Ni(O)-YSZ composite particle ink formulation and the reliability of 3D printing.

Fe-Doped Ceria-Based Ceramic Cathode for High-Efficiency CO2 Electrolysis in Solid Oxide Electrolysis Cell.

In the quest for sustainable energy solutions, solid oxide electrolysis cell (SOEC) emerges as a key technology for converting CO2 into fuels and valuable chemicals. This work focuses on pure ceramic Fex Sm0.2 Ce0.8 O2- δ (xFe-SDC) as the fuel electrodes, and Sr-free ceria-based ceramic electrodes can be successfully constructed for x ≤ 0.05. The incorporation of Fe into the ceria lattice increases the oxygen vacancy concentration and promotes the formation of catalytic sites crucial for the CO2 reduction reaction (CO2 RR). Density functional theory calculations indicate that Fe enhances electrochemical performance by decreasing the CO2 RR energy barrier and facilitating oxygen ion diffusion. At 800 °C and 1.5 V, single cells with 0.05Fe-SDC cathodes manifest attractive performance, attaining current densities of -1.98 and -2.26 A cm-2 under 50% CO2 /CO and pure CO2 atmospheres, respectively. These results suggest the great potential of xFe-SDC electrodes as promising avenues for high-performance fuel electrodes in SOEC.

Low cost 3D printable flow reactors for electrochemistry.

Transition to carbon neutrality requires the development of more sustainable pathways to synthesize the next generation of chemical building blocks. Electrochemistry is a promising pathway to achieve this goal, as it allows for the use of renewable energy to drive chemical transformations. While the electroreduction of carbon dioxide (CO2) and hydrogen evolution are attracting significant research interest, fundamental challenges exist in moving the research focus toward performing these reactions on scales relevant to industrial applications. To bridge this gap, we aim to facilitate researchers' access to flow reactors, which allow the characterization of electrochemical transformations under conditions closer to those deployed in the industry. Here, we provide a 3D-printable flow cell design (manufacturing cost < $5), which consists of several plates, offering a customizable alternative to commercially available flow reactors (cost > $6,000). The proposed design and detailed build instructions allow the performance of a wide variety of chemical reactions in flow, including gas and liquid phase electroreduction, electro(less)plating, and photoelectrochemical reactions, providing researchers with more flexibility and control over their experiments. By offering an accessible, low-cost reactor alternative, we reduce the barriers to performing research on sustainable electrochemistry, supporting the global efforts necessary to realize the paradigm shift in chemical manufacturing.

Impact of Anodic Oxidation Reactions in the Performance Evaluation of High-Rate CO2 /CO Electrolysis.

The membrane-electrode assembly (MEA) approach appears to be the most promising technique to realize the high-rate CO2 /CO electrolysis, however there are major challenges related to the crossover of ions and liquid products from cathode to anode via the membrane and the concomitant anodic oxidation reactions (AORs). In this perspective, by combining experimental and theoretical analyses, several impacts of anodic oxidation of liquid products in terms of performance evaluation are investigated. First, the crossover behavior of several typical liquid products through an anion-exchange membrane is analyzed. Subsequently, two instructive examples (introducing formate or ethanol oxidation during electrolysis) reveals that the dynamic change of the anolyte (i.e., pH and composition) not only brings a slight shift of anodic potentials (i.e., change of competing reactions), but also affects the chemical stability of the anode catalyst. Anodic oxidation of liquid products can also cause either over- or under-estimation of the Faradaic efficiency, leading to an inaccurate assessment of overall performance. To comprehensively understand fundamentals of AORs, a theoretical guideline with hierarchical indicators is further developed to predict and regulate the possible AORs in an electrolyzer. The perspective concludes by giving some suggestions on rigorous performance evaluations for high-rate CO2 /CO electrolysis in an MEA-based setup.

A High-Entropy Layered Perovskite Coated with In Situ Exsolved Core-Shell CuFe@FeOx Nanoparticles for Efficient CO2 Electrolysis.

Solid oxide electrolysis cells (SOECs) are promising energy conversion devices capable of efficiently transforming CO2 into CO, reducing CO2 emissions, and alleviating the greenhouse effect. However, the development of a suitable cathode material remains a critical challenge. Here a new SOEC cathode is reported for CO2 electrolysis consisting of high-entropy Pr0.8 Sr1.2 (CuFe)0.4 Mo0.2 Mn0.2 Nb0.2 O4-δ (HE-PSCFMMN) layered perovskite uniformly coated with in situ exsolved core-shell structured CuFe alloy@FeOx (CFA@FeO) nanoparticles. Single cells with the HE-PSCFMMN-CFA@FeO cathode exhibit a consistently high current density of 1.95 A cm-2 for CO2 reduction at 1.5 V while maintaining excellent stability for up to 200 h under 0.75 A cm-2 at 800 °C in pure CO2 . In situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations confirm that the exsolution of CFA@FeO nanoparticles introduces additional oxygen vacancies within HE-PSCFMMN substrate, acting as active reaction sites. More importantly, the abundant oxygen vacancies in FeOx shell, in contrast to conventional in situ exsolved nanoparticles, enable the extension of the triple-phase boundary (TPB), thereby enhancing the kinetics of CO2 adsorption, dissociation, and reduction.

Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes.

In this study, perovskite oxides La0.3 Ca0.6 Ni0.05 Mnx Ti0.95- x O3- γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 - 3% H2 O. The performance of La0.3 Ca0.6 Ni0.05 Ti0.95 O3-γ is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3 ) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.

Unlocking the Potential of A-Site Ca-Doped LaCo0.2Fe0.8O3-δ: A Redox-Stable Cathode Material Enabling High Current Density in Direct CO2 Electrolysis.

Massive carbon dioxide (CO2) emission from recent human industrialization has affected the global ecosystem and raised great concern for environmental sustainability. The solid oxide electrolysis cell (SOEC) is a promising energy conversion device capable of efficiently converting CO2 into valuable chemicals using renewable energy sources. However, Sr-containing cathode materials face the challenge of Sr carbonation during CO2 electrolysis, which greatly affects the energy conversion efficiency and long-term stability. Thus, A-site Ca-doped La1-xCaxCo0.2Fe0.8O3-δ (0.2 ≤ x ≤ 0.6) oxides are developed for direct CO2 conversion to carbon monoxide (CO) in an intermediate-temperature SOEC (IT-SOEC). With a polarization resistance as low as 0.18 Ω cm2 in pure CO2 atmosphere, a remarkable current density of 2.24 A cm-2 was achieved at 1.5 V with La0.6Ca0.4Co0.2Fe0.8O3-δ (LCCF64) as the cathode in La0.8Sr0.2Ga0.83Mg0.17O3-δ (LSGM) electrolyte (300 µm) supported electrolysis cells using La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) as the air electrode at 800 °C. Furthermore, symmetrical cells with LCCF64 as the electrodes also show promising electrolysis performance of 1.78 A cm-2 at 1.5 V at 800 °C. In addition, stable cell performance has been achieved on direct CO2 electrolysis at an applied constant current of 0.5 A cm-2 at 800 °C. The easily removable carbonate intermediate produced during direct CO2 electrolysis makes LCCF64 a promising regenerable cathode. The outstanding electrocatalytic performance of the LCCF64 cathode is ascribed to the highly active and stable metal/perovskite interfaces that resulted from the in situ exsolved Co/CoFe nanoparticles and the additional oxygen vacancies originated from the Ca2Fe2O5 phase synergistically providing active sites for CO2 adsorption and electrolysis. This study offers a novel approach to design catalysts with high performance for direct CO2 electrolysis.

Accumulation of Liquid Byproducts in an Electrolyte as a Critical Factor That Compromises Long-Term Functionality of CO2-to-C2H4 Electrolysis.

Electrochemical conversion of CO2 using Cu-based gas diffusion electrodes opens the way to green chemical production as an alternative to thermocatalytic processes and a storage solution for intermittent renewable electricity. However, diverse challenges, including short lifetimes, currently inhibit their industrial usage. Among well-studied determinants such as catalyst characteristics and electrode architecture, possible effects of byproduct accumulation in the electrolyte as an operational factor have not been elucidated. This work quantifies the influence of ethanol, n-propanol, and formate accumulation on selectivity, stability, and cell potential in a CO2-to-C2H4 electrolyzer. Alcohols accelerated flooding by degrading the hydrophobic electrode characteristics, undermining selective and stable ethylene formation. Furthermore, high alcohol concentrations triggered the catalyst layer's abrasion and structural disfigurements in the Nafion 117 membrane, leading to high cell potentials. Therefore, continuous removal of alcohols from the electrolyte medium or substantial modifications in the cell components must be considered to ensure long-term performing CO2-to-C2H4 electrolyzers.

In situ electrochemical reconstruction of Sr2Fe1.45Ir0.05Mo0.5O6-δ perovskite cathode for CO2 electrolysis in solid oxide electrolysis cells.

Solid oxide electrolysis cells provide a practical solution for the direct conversion of CO2 to other chemicals (i.e. CO), however, an in-depth mechanistic understanding of the dynamic reconstruction of active sites for perovskite cathodes during CO2 electrolysis remains a great challenge. Herein, we identify that iridium-doped Sr2Fe1.45Ir0.05Mo0.5O6-δ (SFIrM) perovskite displays a dynamic electrochemical reconstruction feature during CO2 electrolysis with abundant exsolution of highly dispersed IrFe alloy nanoparticles on the SFIrM surface. The in situ reconstructed IrFe@SFIrM interfaces deliver a current density of 1.46 A cm-2 while maintaining over 99% CO Faradaic efficiency, representing a 25.8% improvement compared with the Sr2Fe1.5Mo0.5O6-δ counterpart. In situ electrochemical spectroscopy measurements and density functional theory calculations suggest that the improved CO2 electrolysis activity originates from the facilitated formation of carbonate intermediates at the IrFe@SFIrM interfaces. Our work may open the possibility of using an in situ electrochemical poling method for CO2 electrolysis in practice.

Enhancing Electrochemical CO2 Reduction on Perovskite Oxide for Solid Oxide Electrolysis Cells through In Situ A-Site Deficiencies and Surface Carbonate Deposition Induced by Lithium Cation Doping and Exsolution.

Solid oxide electrolysis cells (SOECs) hold enormous potential for efficient conversion of CO2 to CO at low cost and high reaction kinetics. The identification of active cathodes is highly desirable to promote the SOEC's performance. This study explores a lithium-doped perovskite La0.6- x Lix Sr0.4 Co0.7 Mn0.3 O3-δ (x = 0, 0.025 0.05, and 0.10) material with in situ generated A-site deficiency and surface carbonate as SOEC cathodes  for CO2 reduction. The experimental results indicate that the SOEC with the La0.55 Li0.05 Sr0.4 Co0.7 Mn0.3 O3-δ cathode exhibits a current density of 0.991 A cm-2 at 1.5 V/800 °C, which is an improvement of ≈30% over the pristine sample. Furthermore, SOECs based on the proposed cathode demonstrate excellent stability over 300 h for pure CO2 electrolysis. The addition of lithium with high basicity, low valance, and small radius, coupled with A-site deficiency, promotes the formation of oxygen vacancy and modifies the electronic structure of active sites, thus enhancing CO2 adsorption, dissociation process, and CO desorption steps as corroborated by the experimental analysis and the density functional theory calculation. It is further confirmed that Li-ion migration to the cathode surface forms carbonate and consequently provides the perovskite cathode with an impressive anti-carbon deposition capability, as well as electrolysis activity.

Phase-Inversion Induced 3D Electrode for Direct Acidic Electroreduction CO2 to Formic acid.

Direct electrochemical CO2 reduction to formic acid (FA) instead of formate is a challenging task due to the high acidity of FA and competitive hydrogen evolution reaction. Herein, 3D porous electrode (TDPE) is prepared by a simple phase inversion method, which can electrochemically reduce CO2 to FA in acidic conditions. Owing to interconnected channels, high porosity, and appropriate wettability, TDPE not only improves mass transport, but also realizes pH gradient to build higher local pH micro-environment under acidic conditions for CO2 reduction compared with planar electrode and gas diffusion electrode. Kinetic isotopic effect experiments demonstrate that the proton transfer becomes the rate-determining step at the pH of 1.8; however, not significant in neutral solution, suggesting that the proton is aiding the overall kinetics. Maximum FA Faradaic efficiency of 89.2% has been reached at pH 2.7 in a flow cell, generating FA concentration of 0.1 m. Integrating catalyst and gas-liquid partition layer into a single electrode structure by phase inversion method paves a facile avenue for direct production of FA by electrochemical CO2 reduction.

The Role of Interfacial Water in CO2 Electrolysis over Ni-N-C Catalyst in a Membrane Electrode Assembly Electrolyzer.

CO2 electrolysis is a promising route for achieving net-zero emission through decarbonization. To realize CO2 electrolysis toward practical application, beyond catalyst structures, it is also critical to rationally manipulate catalyst microenvironments such as the water at the electrode/electrolyte interface. Here, the role of interfacial water in CO2 electrolysis over Ni-N-C catalyst modified with different polymers is investigated. Benefiting from a hydrophilic electrode/electrolyte interface, the Ni-N-C catalyst modified with quaternary ammonia poly(N-methyl-piperidine-co-p-terphenyl) shows a Faradaic efficiency of 95% and a partial current density of 665 mA cm-2 for CO production in an alkaline membrane electrode assembly electrolyzer. A scale-up demonstration using a 100 cm2 electrolyzer achieves a CO production rate of 514 mL min-1 at a current of 80 A. In-situ microscopy and spectroscopy measurements indicate that the hydrophilic interface significantly promotes the formation of the *COOH intermediate, rationalizing the high CO2 electrolysis performance.