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We demonstrate pOH imaging with confocal microscopy to probe the microenvironment of an operating CO2 reduction gas diffusion electrode. We find that the micrometer-scale morphology plays an important role in defining the CO2 reduction performance.

Transport of protons and water through water-filled, phase-separated cation-exchange membranes occurs through a network of interconnected nanoscale hydrophilic aqueous domains. This paper uses numerical simulations and theory to explore the role of the mesoscale network on water, proton, and electrokinetic transport in perfluorinated sulfonic acid (PFSA) membranes, pertinent to electrochemical energy-conversion devices. Concentrated-solution theory describes microscale transport. Network simulations model mesoscale effects and ascertain macroscopic properties. An experimentally consistent 3D Voronoi-network topology characterizes the interconnected channels in the membrane. Measured water, proton, and electrokinetic transport properties from literature validate calculations of macroscopic properties from network simulations and from effective-medium theory. The results demonstrate that the hydrophilic domain size affects the various microscale, domain-level transport modes dissimilarly, resulting in different distributions of microscale coefficients for each mode of transport. As a result, the network mediates the transport of species nonuniformly with dissimilar calculated tortuosities for water, proton, and electrokinetic transport coefficients (i.e., 4.7, 3.0, and 6.1, respectively, at a water content of 8 H2O molecules per polymer charge equivalent). The dominant water-transport pathways across the membrane are different than those taken by the proton cation. Finally, the distribution of transport properties across the network induces local electrokinetic flows that couple water and proton transport; specifically, local electrokinetic transport induces water chemical-potential gradients that decrease macroscopic conductivity by up to a factor of 3. Macroscopic proton, water, and electrokinetic transport coefficients depend on the collective microscale transport properties of all modes of transport and their distribution across the hydrophilic domain network.

Carbon dioxide (CO2) must be removed from the atmosphere to mitigate the negative effects of climate change. However, the most scalable methods for removing CO2 from the air require heat from fossil-fuel combustion to produce pure CO2 and continuously regenerate the sorbent. Bipolar-membrane electrodialysis (BPM-ED) is a promising technology that uses renewable electricity to dissociate water into acid and base to regenerate bicarbonate-based CO2 capture solutions, such as those used in chemical loops of direct-air-capture (DAC) processes, and also in direct-ocean capture (DOC) to promote atmospheric CO2 drawdown via decarbonization of the shallow ocean. However, a lack of understanding of the mechanisms of reactive carbon species transport in BPMs has precluded industrial-scale deployment of BPM-ED. In this study, we develop an experimentally-validated 1D model for the electrochemical regeneration of CO2 from bicarbonate-based carbon capture solutions and seawater using BPM-ED. Our experimental and computational results demonstrate that out-of-equilibrium buffer reactions within the BPM drive the formation of CO2 at the BPM/electrolyte interface with energy-intensities of less than 150 kJ mol-1. However, high rates of bubble formation increase the energy intensity of CO2 recovery at current densities >100 mA cm−2. Sensitivity analyses show that optimizing the BPM and bubble removal could enable CO2 recovery from bicarbonate solutions at energy intensities 100 mA cm−2. These results provide design principles for industrial-scale CO2 recovery using BPM-ED.

Electrochemical CO2 reduction provides a promising route to the sustainable generation of valuable chemicals and fuels. Tandem catalysts enable sequential CO2-to-CO and CO-to-multicarbon (C2+) product conversions on complementary active sites, to produce high C2+ Faradaic efficiency (FE). Unfortunately, previous tandem catalysts exhibit poor management of CO intermediates, which diminishes C2+ FE. Here, we design segmented gas-diffusion electrodes (s-GDEs) in which a CO-selective catalyst layer (CL) segment at the inlet prolongs CO residence time in the subsequent C2+-selective segment, enhancing conversion. This phenomenon enables increases in both the CO utilization and C2+ current density for a Cu/Ag s-GDE compared to pure Cu, by increasing the *CO coverage within the Cu CL. Lastly, we develop a Cu/Fe-N-C s-GDE with 90% C2+ FE at C2+ partial current density (jC2+) exceeding 1 A cm−2. These results prove the importance of transport and establish design principles to improve C2+ FE and jC2+ in tandem CO2 reduction. [Figure not available: see fulltext.]

Photoelectrochemical carbon-dioxide reduction (PEC CO2R) is a potentially attractive means for producing chemicals and fuels using sunlight, water, and carbon dioxide; however, this technology is in its infancy. To date,...

Gas diffusion layers (GDL) have become a critical component in electrochemical CO2 reduction (CO2R) systems because they can enable high current densities needed for industrially relevant productivity. Besides this function,...

The biggest obstacle to the widespread implantation of polymer electrolyte membrane fuel cells (PEMFCs) is the cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity...

Bipolar membranes (BPMs) possess the potential to optimize pH environments for electrochemical synthesis applications when employed in reverse bias. Unfortunately, the performance of BPMs in revers...

Electrochemical carbon dioxide reduction (CO2R) provides a promising pathway for sustainable generation of fuels and chemicals. Copper (Cu) electrocatalysts catalyse CO2R to valuable multicarbon (C2+) products, but their selectivity depends on the local microenvironment near the catalyst surface. Here we systematically explore and optimize this microenvironment using bilayer cation- and anion-conducting ionomer coatings to control the local pH (via Donnan exclusion) and CO2/H2O ratio (via ionomer properties), respectively. When this tailored microenvironment is coupled with pulsed electrolysis, further enhancements in the local ratio of CO2/H2O and pH are achieved, leading to selective C2+ production, which increases by 250% (with 90% Faradaic efficiency and only 4% H2) compared with static electrolysis over bare Cu. These results underscore the importance of tailoring the catalyst microenvironment as a means of improving overall performance in electrochemical syntheses. Copper catalyses electrochemical reduction of CO2 to valuable multicarbon products, but its selectivity depends on the local microenvironment near the catalyst surface. Here, the authors explore and optimize this environment to improve performance using bilayer ionomer coatings to control the local pH and CO2/H2O ratio.

The development and characterization of active and selective catalysts is critical for the simulation and optimization of electrochemical synthesis of chemicals and fuels using renewable energy. The rate of electrochemical generation of a specific product as a function of electrode potential can be described by a Tafel equation, which depends on two parameters: the Tafel slope (or the related transfer coefficient) and the exchange current density. However, common methods for calculating Tafel slopes are subjective and limited by data insufficiency resulting from challenges associated with product quantification, and, as shown here, the effects of mass transport, bulk reaction occurring in the mass-transfer boundary layer, and the occurrence of competitive surface reactions. Errors in the Tafel slope extracted from experimental data can also lead to errors in the exchange current density estimation. To address these issues, we present a technique that leverages statistical learning methods informed by physics-based modeling to calculate kinetic parameters (the transfer coefficient and exchange current density) with quantified uncertainty. The method is applied to 21 sets of data for the electrochemical reduction of CO2 to CO and H2 on Ag catalysts acquired under similar experimental conditions. We find that fitted values for the transfer coefficient and exchange current density do not converge to a unique set of values, and that there is an apparent correlation of these parameters; however, the most probable value of the exchange coefficient for CO and H2 formation correspond reasonably well with the DFT-predicted values of this parameter. While the system explored is relatively simple, the techniques developed can be used to evaluate the transfer coefficient and exchange current density for many other electrochemical processes.

A variety of electrochemical energy conversion technologies, including fuel cells, rely on solution-processing techniques (via inks) to form their catalyst layers (CLs). The CLs are heterogeneous structures, often with uneven ion-conducting polymer (ionomer) coverage and underutilized catalysts. Various platinum-supported-on-carbon colloidal catalyst particles are used, but little is known about how or why changing the primary particle loading (PPL, or the weight fraction of platinum of the carbon-platinum catalyst particles) impacts performance. By investigating the CL gas-transport resistance and zeta (ζ)-potentials of the corresponding inks as a function of PPL, a direct correlation between the CL high current density performance and ink ζ-potential is observed. This correlation stems from likely changes in ionomer distributions and catalyst-particle agglomeration as a function of PPL, as revealed by pH, ζ-potential, and impedance measurements. These findings are critical to unraveling the ionomer distribution heterogeneity in ink-based CLs and enabling enhanced Pt utilization and improved device performance for fuel cells and related electrochemical devices.

Widespread use of hydrogen energy is contingent on the development of reliable and economical sources of hydrogen. Electrolysis from renewably-derived low-carbon electricity is a potentially viable method of hydrogen generation. Prime among the electrolysis technologies are those utilizing ion-conducting polymers (ionomers) including proton-exchange-membrane water electrolyzer (PEMWE). However, these technologies need to exhibit increased efficiency, performance, and durability to become commercially viable. Like most electrochemical devices, PEMWEs involve multiple components (e.g., catalyst, ionomer, transport layers, membrane, plates) and multiple phases, with phenomena occurring across different time and length scales. Furthermore, it is difficult to experimentally probe many of the species and phenomena during operation. Thus, mathematical modeling at the continuum level has been an invaluable aid in exploring, understanding, and optimizing PEMWE cell and components. This is especially true in the highly coupled and complex physics and chemistries that occur with the membrane-electrode assembly (MEA). The physics in a typical volume-averaged non-isothermal model include multiphase transport in porous media, concentrated-solution theory, Ohm’s Law, and Butler-Volmer kinetics, and ion, gas, and water transport in the ionomer. In this talk, different modeling approaches, governing equations, and constitutive relationships will be described, including the benefits and limits of modeling. While focus will be on continuum equations and macroscale effects, detailed submodels and approaches for scaling to full cells and specific components, respectively, will be introduced. For example, as shown in Figure 1, one can perform an applied voltage breakdown and describe the different mechanisms resulting in the necessary applied overpotentials, which is useful in identifying opportunities for improving cell performance by quantifying the potential losses associated with a specific mechanism. In the talk, the generation of such analysis will be discussed including various approaches. Also shown in Figure 1 is how modeling can be used to elucidate safety concerns and identify issues to be resolved, in this case, nonlinear hydrogen crossover. Finally, future directions for multiscale modeling and multi-model coupling will be discussed. Figure 1

Proton-exchange-membrane fuel cells (PEMFC) are a clean energy conversion alternative to traditional fossil-fuel combustion; however, transport resistances in the electrode pose a lower-limit to catalyst loading and commercialization of PEMFCs. PEMFCs consist of simultaneous hydrogen (H2) oxidation and oxygen (O2) reduction at the anode and cathode, respectively. While oxygen transport resistances in PEMFCs have been widely studied both experimentally and analytically, hydrogen transport resistances are less understood. Herein, we present a physics-based model that encompasses multi-scale transport within the anode side of the PEMFC. The O2 in the cathode here is omitted and replaced with H2 to deconvolute O2 transport resistance contributions, similar to that of a hydrogen pump. Replication of the hydrogen pump setup allows for comparison of the model against experimental analysis of H2 gas-transport resistance in H2 limiting-current experiments, which can also inform gas transport (including oxygen) in general. Herein, we present a multi-scale analytical model of the porous anode catalyst layers and individual catalyst agglomerates that enables determination of the effects of electrode morphology such as agglomerate size, catalyst loading, etc. on H2 transport resistance through the porous electrode to complement and better understand H2 limiting current experiments and deconvolute local H2 transport resistances. Electrodes within PEMFCs are heterogeneous porous structures formed by agglomerates of carbon particles containing Pt nanoparticles, held together by an ion-conducting polymer (ionomer). The gas transport hence involves transport through multiple phases and length-scales: (i) gas-phase transport through electrode pores at the length scale of electrode thickness (micrometer) and (ii) diffusion into the agglomerate through an ionomer film at the length scale of agglomerate radius (nanometer). Based on previous modeling efforts of varying length-scales of the catalyst layer, our analytical model adequately and simultaneously captures reaction-diffusion at all of the aforementioned scales (i.e., the electrode thickness and agglomerate radius) to better describe porous anode performance. A sensitivity analysis is subsequently performed to compare current generated against transport parameters for both scales. This work ultimately provides insight that will guide the design and engineering of future porous anodes for applications in hydrogen pumping and PEMFCs.

Electrochemical reduction of carbon dioxide (CO

The interaction between ionomer (ion-conducting polymer) and catalyst particles in porous electrodes of electrochemical energy-conversion devices is a critical yet poorly understood phenomenon that controls device performance. This interaction stems from that in the electrode precursor inks, which also governs porous-electrode morphology during formation. In this letter, we probe the origin of this interaction in solution to unravel the ionomer/particle agglomeration process. Quartz-crystal microbalance studies detail ionomer adsorption (with a range of charge densities) to model surfaces under a variety of solvent environments, and isothermal-titration-calorimetry experiments extract thermodynamic binding information to platinum- and carbon-black nanoparticles. Results reveal that under the conditions tested, ionomer binding to platinum is similar to carbon, suggesting that adsorption to platinum-on-carbon catalyst particles in inks is likely dictated mostly by hydrophobic interactions with the carbon surface. Furthermore, water-rich solvents (relative to propanol) promote ionomer adsorption. Finally, ionomer dispersions change with time, yielding dynamic binding interactions.

Author(s): Bui, JC; Kim, C; Weber, AZ; Bell, AT | Abstract: Pulsed electrolysis has been demonstrated to improve the faradaic efficiency (FE) to C2+ products during the electrochemical reduction of CO2 over a Cu catalyst, but the nature of this enhancement is poorly understood. Herein, we developed a time-dependent continuum model of pulsed CO2 electrolysis on Cu in 0.1 M CsHCO3 that faithfully represents the experimentally observed effects of pulsed electrolysis. This work shows that pulsing results in dynamic changes in the pH and CO2 concentration near the Cu surface, which lead to an enhanced C2+ FE as a consequence of repeatedly accessing a transient state of heightened pH and CO2 concentration at high cathodic overpotential. Using these insights, a variety of pulse shapes were explored to establish operating conditions that maximize the rate of C2+ product formation and minimize the rates of H2 and C1 product formation.

Nafion is an ion-containing random copolymer used as a solid electrolyte in many electrochemical applications thanks to its remarkable ionic conductivity and mechanical stability. Understanding the mechanism of ion transport in Nafion, which depends strongly on hydration, therefore requires a complete picture of its morphology in dry and hydrated form. Here we report on a nanoscale study of dry versus hydrated as-cast 100 nm Nafion membranes using analytical transmission electron microscopy (TEM) and cryogenic TEM tomography, respectively. For the dry membrane, spherical clusters ∼3.5 nm in diameter corresponding to the hydrophilic sulfonic-acid-containing phase are identified. In contrast, cryo TEM tomography of the hydrated membrane reveals an interconnected channel-type network, with a domain spacing of ∼5 nm, and presents the first nanoscale 3D views of the internal structure of hydrated Nafion obtained by a direct-imaging approach.

To develop new ionomers and optimize existing ones, there is a need to understand their structure/function relationships experimentally. In this letter, synchrotron X-ray microtomography is used to examine water distributions within Nafion, the most commonly used ionomer. Simultaneous high spatial (∼1 μm) and temporal (∼10 min) resolutions, previously unattained by other techniques, clearly show the nonlinear water profile across the membrane thickness, with a continuous transition from dynamic to steady-state transport coefficients with the requisite water-content dependence. The data also demonstrate the importance of the interfacial condition in controlling the water profile and help to answer some long-standing debates in the literature.

The ability of the Nafion membrane to absorb water rapidly and create a network of hydrated interconnected water domains provides this material with an unmatched ability to conduct ions through a chemically and mechanically robust membrane. The morphology and composition of these hydrated membranes significantly affects their transport properties and performance. This work demonstrates that differences in interfacial interactions between the membranes exposed to vapor or liquid water can cause significant changes in kinetics of water uptake. In situ small-angle X-ray scattering (SAXS) experiments captured the rapid swelling of the membrane in liquid water with a nanostructure rearrangement on the order of seconds. For membranes in contact with water vapor, morphological changes are four orders-of-magnitude slower than in liquid water, suggesting that interfacial resistance limits the penetration of water into the membrane. Also, upon water absorption from liquid water, a structural rearrangement from a distribution of spherical and cylindrical domains to exclusively cylindrical-like domains is suggested. These differences in water-uptake kinetics and morphology provide a new perspective into Schroeder's paradox, which dictates a different water content for vapor- and liquid-equilibrated ionomers at unit activity. The findings of this work provide critical insights into the fast kinetics of water absorption of the Nafion membrane, which can aid in the design of energy conversion devices that operate under frequent changes in environmental conditions.

We report an electrochemical reactor that converts 3.0 M KHCO3 into methane at the cathode, and oxidizes water at the anode. The molar ratio of methane product to unreacted CO2 gas (defined herein as "methane yield") was measured to be 34% at a partial current density of 120 mA cm-2. The highest previously reported CO2-to-methane yield is 3%. Our reactor achieved this improvement in methane yield because it is fed with 3.0 M KHCO3, a type of reactive carbon solution, rather than gaseous CO2. The reactor uses H+ delivered by a bipolar membrane to form CO2 at the cathode. This CO2 is subsequently reduced into methane. A cationic surfactant added to the catholyte suppressed hydrogen evolution and increased methane formation. A 1D continuum model confirmed that H+ from the membrane promotes the formation of methane over multicarbon products at the cathode. These findings present design principles for electrochemical methane synthesis.

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources to power the conversion of abundant feedstocks to value-added commodity chemicals and fuels. Of the potential system architectures for these processes, only systems employing 3-D structured porous electrodes have the capacity to achieve the high rates of conversion necessary for industrial scale. However, the phenomena and environments in these systems are not well understood and are challenging to probe experimentally. Fortunately, continuum modeling is well-suited to rationalize the observed behavior in electrochemical synthesis, as well as to ultimately provide recommendations for guiding the design of next-generation devices and components. In this review, we begin by presenting an historical review of modeling of porous electrode systems, with the aim of showing how past knowledge of macroscale modeling can contribute to the rising challenge of electrochemical synthesis. We then present a detailed overview of the governing physics and assumptions required to simulate porous electrode systems for electrochemical synthesis. Leveraging the developed understanding of porous-electrode theory, we survey and discuss the present literature reports on simulating multiscale phenomena in porous electrodes in order to demonstrate their relevance to understanding and improving the performance of devices for electrochemical synthesis. Lastly, we provide our perspectives regarding future directions in the development of models that can most accurately describe and predict the performance of such devices and discuss the best potential applications of future models.

Perfluorosulfonic acid (PFSA) ionomers are an important class of materials that many electrochemical devices rely on as their ion-conducting electrolyte. Often, PFSA films are prepared through solu...

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Finally, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

During operation, polymer-electrolyte fuel cells undergo mechanical and chemical degradation, which behave synergistically and lead to accelerated membrane deterioration over time. This study builds upon previous modeling work on mechanical degradation, as described by a pinhole in the membrane, and chemical degradation mitigation by using cerium. By combining these two models, analysis can be carried out on the coupled degradation methods and how the mitigation effects of cerium disrupt the degradation cycle. The model results show how the presence of a pinhole in the membrane changes the distribution of cerium in the cell and modifies chemical degradation rates. In addition, the model shows how cerium affects the rate of pinhole growth by slowing down the rate of change in mechanical properties due to chemical degradation. Finally, the model shows how cerium modifies the mechanical and chemical degradation rates of the membrane under humidity- and voltage-cycling conditions.

Direct conversion of methane to methanol has been a long-sought objective. Partial oxidation by thermal catalysis is possible but suffers from a rapid loss in methanol selectivity with increasing m...

A pore-network formulation is presented to model gas diffusion layers (GDLs) in polymer electrolyte fuel cells (PEFCs) using a continuum-based approach. The formulation can easily be integrated into macroscopic models in CFD codes, thus improving the modeling predictions while keeping a moderate computational cost. The continuum-based pore-network formulation is based on a cubic lattice [1], which is divided into control volumes (cubes) of prescribed size. Pores and throats are placed inside the control volumes, and “connectors” of negligible volume interconnect the control volumes. The “connectors” are used to regulate the invasion-percolation pattern according to the size of the throat that links the pores within neighboring control volumes. Hence, the formulation can account for both invasion-percolation between pores as well as evaporation/condensation in the pore volume inside each control volume. This is a major advantage compared to traditional pore-network models based on a fully discrete formulation where phase-change phenomena are difficult to implement. Local anisotropic effective transport properties (permeability and diffusivity) are determined using a 1D resistor network analogy inside each control volume according to the size of the pore and throats in it. The model is validated against capillary pressure curves and effective transport properties (effective diffusivity and permeability) measured ex situ. In addition, water saturation profiles are compared with distributions obtained using X-ray computed tomography [2]. [1] Jeff T. Gostick, Marios A. Ioannidis, Michael W. Fowler, Mark D. Pritzker, Pore network modeling of fibrous gas diffusion layers for polymer electrolyte membrane fuel cells, J. Power Sources 173 (2007) 277-290. [2] P.A. García-Salaberri, G. Hwang, M. Vera, A.Z. Weber, J.T. Gostick, Effective diffusivity in partially-saturated carbon-fiber gas diffusion layers: Effect of through-plane saturation distribution, International Journal of Heat and Mass Transfer 86 (2015) 319–333.

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. While the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.

Selectively tuning ion transport through redox flow battery separators is a promising approach toward increasing cell capacity, power density, and, ultimately, economic feasibility. However, this process is complex with numerous forces and coupled molecular interactions driving and impacting transport under different operating regimes. A fundamental description of ion transport in flow-battery separators can guide the development of new separators by identifying the nature of ion selectivity under given conditions. In this paper, we highlight different contributing factors of transport phenomena, explore how these factors influence cell performance, and the performance tradeoffs inherent in membrane design.

Author(s): Soniat, M; Tesfaye, M; Mafi, A; Brooks, DJ; Humphrey, ND; Weng, LC; Merinov, B; Goddard, WA; Weber, AZ; Houle, FA | Abstract: Glassy polymers are often used for gas separations because of their high selectivity. Although the dual-mode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reaction–diffusion modeling to characterize the time-dependent permeation of N2 and CO2 through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental time-dependent permeation data for both gases in the presteady-state and steady-state regimes show that both single- and dual-mode reaction–diffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environment-sensitive diffusion coefficients as a vital characteristic of transport in glassy polymers.

Exploring the origins of local transport resistance and characterizing the oxygen transport resistances in the catalyst layer (RCL) are critical for cost reduction. In this paper, a comprehensive mesoscopic model for simulating coupled transport processes of oxygen and water vapor for different structural parameters under different operating conditions in reconstructed microstructures is proposed. The local transport resistance is calculated after achieving the limiting current density and the effective diffusivity of oxygen. The results demonstrate that RCL increases greatly with decreasing platinum loading (LPt) and the transport resistances in other components of the cell dominate for high-loadings. Both the reduced oxygen permeation coefficient in the ionomer thin-film and the adsorption resistance account for the origins of local transport resistance. The local transport resistance increases with the bare carbon ratio for a constant LPt and Pt/C ratio due to the decreased effective ionomer surface, and increases with the I/C ratio due to the increased ionomer thickness and decreased Knudsen diffusivity. Due to the presence of liquid water, a slight decrease followed by an increase of the local transport resistance versus relative humidity is obtained. The contribution of ionomer thin-films to RCL is more sensitive to liquid saturation compared with that of pores. This journal is

Electrochemical CO2 reduction (CO2R) is one of several promising strategies to mitigate CO2 emissions. Electrochemical processes operate at mild conditions, can be tuned to selective products, allow modular design, and provide opportunities to integrate renewable electricity with CO2 reduction in carbon-intensive manufacturing industries such as iron and steel making. In recent years, significant advances have been achieved in the development of highly efficient and selective electrocatalysts for CO2R. However, to realize fully the potential benefits of new electrocatalysts in low cost, large scale CO2R electrolyzers requires advances in design and engineering of the CO2R process. In this review, we examine the state-of-the-art in electrochemical CO2R technologies, and highlight how the efficiency of CO2R processes can be improved through (i) electrolyzer configuration, (ii) electrode structure, (iii) electrolyte selection, (iv) pH control, and (v) the electrolyzer's operating pressure and temperature. Although a comprehensive review of catalytic materials is beyond this review's scope, we illustrate how other engineering and design decisions may also influence CO2R reaction pathways because of effects on mass transfer rates, the electrode surface chemistry, interactions with intermediate reaction species, and rates of charge transfer.

Copper-based membrane-electrode assemblies (Cu-MEAs) hold promise for increasing the energy efficiency for the electrochemical reduction of CO2 to C2+ products, while maintaining high current densities. However, fundamental understanding of Cu-MEAs is still limited compared to the wealth of knowledge available for aqueous-electrolyte Cu systems. Physics-based modeling can assist in the transfer of knowledge from aqueous to vapor-fed systems by deconvoluting the impacts of various physical processes and accelerating the optimization of Cu-MEAs. Here, we simulate Cu-MEA performance and describe how the change in cell architecture leads to changes in cell performance and optimization. Our results reveal nonuniformity of product distribution in the catalyst layer, allowing us to explore catalyst-layer properties as design parameters for increasing the energy efficiency of C2+ product formation. We discuss multiphase flow and water-management issues and show how membrane properties, specifically the electro-osmotic coefficient, affect the efficacy of feeding liquid water to hydrate the membrane. Finally, we explore tradeoffs associated with operating Cu-MEAs at 350 K in order to increase the supply of water and the preferential formation of products with higher activation energies (typically C2+ products).