Synergizing Fe2O3 Nanoparticles on Single Atom Fe-N-C for Nitrate Reduction to Ammonia at Industrial Current Densities.

The electrochemical reduction of nitrates (NO3 -) enables a pathway for the carbon neutral synthesis of ammonia (NH3), via the nitrate reduction reaction (NO3RR), which has been demonstrated at high selectivity. However, to make NH3 synthesis cost-competitive with current technologies, high NH3 partial current densities (jNH3) must be achieved to reduce the levelized cost of NH3. Here, the high NO3RR activity of Fe-based materials is leveraged to synthesize a novel active particle-active support system with Fe2O3 nanoparticles supported on atomically dispersed Fe-N-C. The optimized 3×Fe2O3/Fe-N-C catalyst demonstrates an ultrahigh NO3RR activity, reaching a maximum jNH3 of 1.95 A cm-2 at a Faradaic efficiency (FE) for NH3 of 100% and an NH3 yield rate over 9 mmol hr-1 cm-2. Operando XANES and post-mortem XPS reveal the importance of a pre-reduction activation step, reducing the surface Fe2O3 (Fe3+) to highly active Fe0 sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe2O3 particles and Fe-Nx sites at highly cathodic potentials, maintaining a current of -1.3 A cm-2 over 24 hours. This work exhibits an effective and durable active particle-active support system enhancing the performance of the NO3RR, enabling industrially relevant current densities and near 100% selectivity.

A general-purpose tool for modeling multifunctional thin porous media (POREnet): From pore network to effective property tensors.

POREnet, a novel approach to model effective properties of thin porous media, TPM, is presented. The methodology allows the extraction of local effective property tensors by volume averaging from discrete pore networks, PNs, built on the tessellated continuum space of a TPM. The gradient theorem is used to describe 3D transport in bulk tessellated space, providing an appropriate metric to normalize network fluxes. Implemented effective transport properties include diffusivity, permeability, solid-phase conductivity, and entry capillary pressure and contact angle under two-phase conditions, considering multi-component materials with several solid phases and local contact resistances. Calculated property tensors can be saved on 3D image stacks, where interfacial and sub-CV scale features can be added before exporting data to CFD meshes for simulation. Overall, POREnet provides a general-purpose, versatile methodology for modeling TPM in an ample range of conditions within a single CFD framework. Among other advantages, coupling of PN and continuum models at TPM-channel interfaces is simplified, interfacial contact resistances can be included using robin boundary conditions, and transient multiphysics simulations can be implemented more easily using CFD. The code is tested against a miscellaneousness of examples extracted from electrochemical applications.

Influence of Microporous Layers on Interfacial Properties, Oxygen Flow Distribution, and Durability of Proton Exchange Membrane Water Electrolyzers.

The efficient and cost-effective production of green hydrogen is essential to decarbonize heavily polluting sectors such as transportation and heavy manufacturing industries such as metal refining. Polymer electrolyte membrane water electrolysis (PEMWE) is the most promising and rapidly maturing technology for producing green hydrogen at a scale and on demand. However, substantial cost reduction by lowering precious metal catalyst loadings and efficiency improvement is necessary to lower the cost of the produced hydrogen. Porous transport layers (PTLs) play a major role in influencing the PEMWE efficiency and catalyst utilization. Several studies have projected that the use of microporous layers (MPLs) on PTLs can improve the efficiency of PEMWEs, but very limited literature exists on how MPLs affect anodic interfacial properties and oxygen transport in PTLs. In this study, for the first time, we use X-ray microtomography and innovative image processing techniques to elucidate the oxygen flow patterns in PTLs with varying MPL thicknesses. We used stained water to improve contrast of oxygen in PTLs and demonstrate visualization of time averaged oxygen flow patterns. The results show that PTLs with MPLs significantly improve interfacial contact by almost 20% as compared to single layer sintered PTL. For the single layer PTL without MPL, the pore volume utilization for oxygen flow is low and the oxygen follows a viscous fingering flow regime. With MPLs, the pore volume utilization is higher, and the number of oxygen transport pathways is increased significantly. MPLs were also shown to suppress capillary fingering and transition oxygen flow to the viscous fingering regime, which has been proven to decrease site masking effects. Finally, durability tests showed the least voltage degradation for thin MPL and thicker MPLs run into mass transport limitations. Based on these findings, PTL/MPL design optimization strategies are proposed for enabling low catalyst loadings and improving durability.

X-ray Tomography Applied to Electrochemical Devices and Electrocatalysis.

X-ray computed tomography (CT) is a nondestructive three-dimensional (3D) imaging technique used for studying morphological properties of porous and nonporous materials. In the field of electrocatalysis, X-ray CT is mainly used to quantify the morphology of electrodes and extract information such as porosity, tortuosity, pore-size distribution, and other relevant properties. For electrochemical systems such as fuel cells, electrolyzers, and redox flow batteries, X-ray CT gives the ability to study evolution of critical features of interest in ex situ, in situ, and operando environments. These include catalyst degradation, interface evolution under real conditions, formation of new phases (water and oxygen), and dynamics of transport processes. These studies enable more efficient device and electrode designs that will ultimately contribute to widespread decarbonization efforts.

Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites.

Electrocatalytic reduction of waste nitrates (NO3-) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO3- reduction to NH3 in neutral media, with a specific focus on deciphering the role of the NO2- intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO2- reduction activity and NO3- reduction selectivity for NH3. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO2- evolution, over the normal M-N4 sites and their oxo-form (O-M-N4) for oxyphilic metals. This work provides a platform for designing multi-element NO3RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.

Lithium Metal Battery Quality Control via Transformer-CNN Segmentation.

Lithium metal battery (LMB) has the potential to be the next-generation battery system because of its high theoretical energy density. However, defects known as dendrites are formed by heterogeneous lithium (Li) plating, which hinders the development and utilization of LMBs. Non-destructive techniques to observe the dendrite morphology often use X-ray computed tomography (XCT) to provide cross-sectional views. To retrieve three-dimensional structures inside a battery, image segmentation becomes essential to quantitatively analyze XCT images. This work proposes a new semantic segmentation approach using a transformer-based neural network called TransforCNN that is capable of segmenting out dendrites from XCT data. In addition, we compare the performance of the proposed TransforCNN with three other algorithms, U-Net, Y-Net, and E-Net, consisting of an ensemble network model for XCT analysis. Our results show the advantages of using TransforCNN when evaluating over-segmentation metrics, such as mean intersection over union (mIoU) and mean Dice similarity coefficient (mDSC), as well as through several qualitatively comparative visualizations.

Understanding Lithium Dendrite Suppression by Hybrid Composite Separators: Indentation Measurements Informed by Operando X-ray Computed Tomography.

This study investigates the significance of the mechanics of hybrid particle-polymer separators in the stabilization of lithium metal interfaces by probing these properties in realistic conditions informed by X-ray microcomputed tomography (micro-CT). Elastic properties and viscoelastic behavior of inorganic microparticle-filled poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) films are characterized using a nanoindentation experiment whose displacement simulates the interfacial response seen in operando micro-CT. It is determined that the dominating mechanical behavior in this hybrid separator relevant to lithium metal cell conditions is comprised of viscoelasticity. Consistent with this finding, along with correlations across other physicochemical properties, a mechanism describing the improvement of lithium metal cycling performance according to inorganic filler type and content is proposed.

Revealing the role of ionic liquids in promoting fuel cell catalysts reactivity and durability.

Ionic liquids (ILs) have shown to be promising additives to the catalyst layer to enhance oxygen reduction reaction in polymer electrolyte fuel cells. However, fundamental understanding of their role in complex catalyst layers in practically relevant membrane electrode assembly environment is needed for rational design of highly durable and active platinum-based catalysts. Here we explore three imidazolium-derived ionic liquids, selected for their high proton conductivity and oxygen solubility, and incorporate them into high surface area carbon black support. Further, we establish a correlation between the physical properties and electrochemical performance of the ionic liquid-modified catalysts by providing direct evidence of ionic liquids role in altering hydrophilic/hydrophobic interactions within the catalyst layer interface. The resulting catalyst with optimized interface design achieved a high mass activity of 347 A g-1Pt at 0.9 V under H2/O2, power density of 0.909 W cm-2 under H2/air and 1.5 bar, and had only 0.11 V potential decrease at 0.8 A cm-2 after 30 k accelerated stress test cycles. This performance stems from substantial enhancement in Pt utilization, which is buried inside the mesopores and is now accessible due to ILs addition.

Effect of Commercial Gas Diffusion Layers on Catalyst Durability of Polymer Electrolyte Fuel Cells in Varied Cathode Gas Environment.

Gas diffusion layers (GDLs) play a crucial role in heat transfer and water management of cathode catalyst layers in polymer electrolyte fuel cells (PEFCs). Thermal and water gradients can accelerate electrocatalyst degradation and therefore the selection of GDLs can have a major influence on PEFC durability. Currently, the role of GDLs in electrocatalyst degradation is poorly studied. In this study, electrocatalyst accelerated stress test studies are performed on membrane electrode assemblies (MEAs) prepared using three most commonly used GDLs. The effect of GDLs on electrocatalyst degradation is evaluated in both nitrogen (non-reactive) and air (reactive) gas environments at 100% relative humidity. In situ electrochemical characterization and extensive physical characterization is performed to understand the subtle differences in electrocatalyst degradation and correlated to the use of different GDLs. Overall, no difference is observed in the electrocatalyst degradation due to GDLs based on polarization curves at the end of life. But interestingly, MEA with a cracked microporous layer (MPL) in the GDL exhibited a higher electrocatalyst loading loss, which resulted in a lower and more heterogeneous increase in the average electrocatalyst nanoparticle size.

Continuum Modeling of Porous Electrodes for Electrochemical 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.

Insights into Interfacial and Bulk Transport Phenomena Affecting Proton Exchange Membrane Water Electrolyzer Performance at Ultra-Low Iridium Loadings.

Interfacial and bulk properties between the catalyst layer and the porous transport layer (PTL) restrict the iridium loading reduction for proton exchange membrane water electrolyzers (PEMWEs), by limiting their mass and charge transport. Using titanium fiber PTLs of varying thickness and porosity, the bulk and interface transport properties are investigated, correlating them to PEMWEs cell performance at ultra-low Ir loadings of ≈0.05 mgIr cm-2 . Electrochemical experiments, tomography, and modeling are combined to study the bulk and interfacial impacts of PTLs on PEMWE performance. It is found that the PEMWE performance is largely dependent on the PTL properties at ultra-low Ir loadings; bulk structural properties are critical to determine the mass transport and Ohmic resistance of PEMWEs while the surface properties of PTLs are critical to govern the catalyst layer utilization and electrode kinetics. The PTL-induced variation in kinetic and mass transport overpotential are on the order of ≈40 and 60 mV (at 80 A mgIr -1 ), respectively, while a nonnegligible 35 mV (at 3 A cm-2 ) difference in Ohmic overpotential. Thus at least 150 mV improvement in PEMWE performance can be achieved through PTL structural optimization without membrane thickness reduction or advent of new electrocatalysts.

Linking Perfluorosulfonic Acid Ionomer Chemistry and High-Current Density Performance in Fuel-Cell Electrodes.

Transport phenomena are key in controlling the performance of electrochemical energy-conversion technologies and can be highly complex, involving multiple length scales and materials/phases. Material designs optimized for one reactant species transport however may inhibit other transport processes. We explore such trade-offs in the context of polymer-electrolyte fuel-cell electrodes, where ionomer thin films provide the necessary proton conductivity but retard oxygen transport to the Pt reaction site and cause interfacial resistance due to sulfonate/Pt interactions. We examine the electrode overall gas-transport resistance and its components as a function of ionomer content and chemistry. Low-equivalent-weight ionomers allow better dissolved-gas and proton transport due to greater water uptake and low crystallinity but also cause significant interfacial resistance due to the high density of sulfonic acid groups. These effects of equivalent weight are also observed via in situ ionic conductivity and CO displacement measurements. Of critical importance, the results are supported by ex situ ellipsometry and X-ray scattering of model thin-film systems, thereby providing direct linkages and applicability of model studies to probe complex heterogeneous structures. Structural and resultant performance changes in the electrode are shown to occur above a threshold sulfonic-group loading, highlighting the significance of ink-based interactions. Our findings and methodologies are applicable to a variety of solid-state energy-conversion devices and material designs.

Measurement of Contact Angles at Carbon Fiber-Water-Air Triple-Phase Boundaries Inside Gas Diffusion Layers Using X-ray Computed Tomography.

Gas diffusion layers (GDLs) are porous carbonaceous layers that are widely used in energy conversion and storage devices. Simulation of water transport through GDLs, in a polymer electrolyte fuel cell (PEFC), for example, typically uses goniometer-measured external contact angles. Until now, there is no well-developed method to obtain contact angles inside the GDLs. AlRatrout et al. developed an open-source code to compute local contact angles at triple-phase contact points from segmented micro-X-ray computed tomography (X-ray CT) images of porous rocks. We apply it, for the first time, to micro-X-ray CT images of water-filled commercial GDLs and compute local contact angles at internal GDL fiber-water-air triple-phase contact points. We obtain a state of mixed wettability (hydrophilic and hydrophobic) inside all GDL samples, with a broad range of contact angles, instead of one hydrophobic contact angle found from goniometer experiments. Lattice Boltzmann water transport simulations performed with these distributed contact angles produce results that are in better agreement with experimental data. We also obtain high-resolution X-ray photoelectron spectroscopy (XPS) data of the GDL samples and find that the concentration of oxide species correlates strongly with the measured hydrophilicity. The method introduced here can help rationally design GDLs and directly quantify their internal surface wettability that is needed for accurate predictions of their functionality in energy technology devices.

Observation of Preferential Pathways for Oxygen Removal through Porous Transport Layers of Polymer Electrolyte Water Electrolyzers.

Understanding the relationships between porous transport layer (PTL) morphology and oxygen removal is essential to improve the polymer electrolyte water electrolyzer (PEWE) performance. Operando X-ray computed tomography and machine learning were performed on a model electrolyzer at different water flow rates and current densities to determine how these operating conditions alter oxygen transport in the PTLs. We report a direct observation of oxygen taking preferential pathways through the PTL, regardless of the water flow rate or current density (1-4 A/cm2). Oxygen distribution in the PTL had a periodic behavior with period of 400 µm. A computational fluid dynamics model was used to predict oxygen distribution in the PTL showing periodic oxygen front. Observed oxygen distribution is due to low in-plane PTL tortuosity and high porosity enabling merging of oxygen bubbles in the middle of the PTL and also due to aerophobicity of the layer.

Pathway to Complete Energy Sector Decarbonization with Available Iridium Resources using Ultralow Loaded Water Electrolyzers.

We present ultralow Ir-loaded (ULL) proton exchange membrane water electrolyzer (PEMWE) cells that can produce enough hydrogen to largely decarbonize the global natural gas, transportation, and electrical storage sectors by 2050, using only half of the annual global Ir production for PEMWE deployment. This represents a significant improvement in PEMWE's global potential, enabled by careful control of the anode catalyst layer (CL), including its mesostructure and catalyst dispersion. Using commercially relevant membranes (Nafion 117), cell materials, electrocatalysts, and fabrication techniques, we achieve at peak a 250× improvement in Ir mass activity over commercial PEMWEs. An optimal Ir loading of 0.011 mgIr cm-2 operated at an Ir-specific power of ∼100 MW kgIr-1 at a cell potential of ∼1.66 V versus RHE (85% higher heating value efficiency). We further evaluate the performance limitations within the ULL regime and offer new insights and guidance in CL design relevant to the broader energy conversion field.

Using operando techniques to understand and design high performance and stable alkaline membrane fuel cells.

There is a need to understand the water dynamics of alkaline membrane fuel cells under various operating conditions to create electrodes that enable high performance and stable, long-term operation. Here we show, via operando neutron imaging and operando micro X-ray computed tomography, visualizations of the spatial and temporal distribution of liquid water in operating cells. We provide direct evidence for liquid water accumulation at the anode, which causes severe ionomer swelling and performance loss, as well as cell dryout from undesirably low water content in the cathode. We observe that the operating conditions leading to the highest power density during polarization are not generally the conditions that allow for long-term stable operation. This observation leads to new catalyst layer designs and gas diffusion layers. This study reports alkaline membrane fuel cells that can be operated continuously for over 1000 h at 600 mA cm-2 with voltage decay rate of only 32-µV h-1 - the best-reported durability to date.

Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts - Part I: High-loading Pt/C and Pt Extended Surface.

The front cover artwork is provided by the groups of Prof. Atanassov and Prof. Zenyuk (University of California Irvine, USA). The image shows rate-determining step of oxygen reduction reaction on platinum nanoparticle supported by carbon, which requires electron transfer but no proton. Read the full text of the Article at 10.1002/cphc.201901091.

Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts - Part I: High-loading Pt/C and Pt Extended Surface.

Kinetic isotope effect (KIE) was used to study the rate-determining step for oxygen reduction reaction (ORR) on dispersed Pt/C electrocatalyst and polycrystalline Pt (Pt-poly). KIE is defined as the ratio of the kinetic current measured in protonated electrolyte versus deuterated electrolyte, with KIE values larger than one indicating proton participation in the rate-determining step. The effect of poisoning anions on the platinum rate determining step is investigated by assessing the KIE in perchloric (non-poisoning) and sulfuric acid-based electrolytes. The kinetics currents were calculated using the Koutechy-Levich and Tafel analysis. A KIE of 1 was observed for Pt/C (with a 40 wt.% Pt loading) and Pt-poly, thus indicating that, on 40 wt. % Pt/C and Pt-poly, the rate determining step is proton independent.

Unique selectivity trends of highly permeable PAP[5] water channel membranes.

Artificial water channels are a practical alternative to biological water channels for achieving exceptional water permeability and selectivity in a stable and scalable architecture. However, channel-based membrane fabrication faces critical barriers such as: (1) increasing pore density to achieve measurable gains in permeability while maintaining selectivity, and (2) scale-up to practical membrane sizes for applications. Recently, we proposed a technique to prepare channel-based membranes using peptide-appended pillar[5]arene (PAP[5]) artificial water channels, addressing the above challenges. These multi-layered PAP[5] membranes (ML-PAP[5]) showed significantly improved water permeability compared to commercial membranes with similar molecular weight cut-offs. However, due to the distinctive pore structure of water channels and the layer-by-layer architecture of the membrane, the separation behavior is unique and was still not fully understood. In this paper, two unique selectivity trends of ML-PAP[5] membranes are discussed from the perspectives of channel geometry, ion exclusion, and linear molecule transport.