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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Advanced Electrode Structures for Proton Exchange Membrane Fuel Cells: Current Status and Path Forward

Abstract Proton exchange membrane fuel cells (PEMFCs) have demonstrated their viability as a promising candidate for clean energy applications. However, performance of conventional PEMFC electrodes, especially the cathode electrode, suffers from low catalyst utilization and sluggish mass transport due to the randomly distributed components and tortuous transport pathways. Development of alternative architectures in which the electrode structure is controlled across a range of length scales provides a promising path toward overcoming these limitations. Here, we provide a comprehensive review of recent research and development of advanced electrode structures, organized by decreasing length-scale from the millimeter-scale to the nanometer-scale. Specifically, advanced electrode structures are categorized into five unique architectures for specific functions: (1) macro-patterned electrodes for enhanced macro-scale mass transport, (2) micro-patterned electrodes for enhanced micro-scale mass transport, (3) electrospun electrodes with fiber-based morphology for enhanced in-plane proton transport and through-plane O 2 transport, (4) enhanced-porosity electrodes for improved oxygen transport through selective inclusion of void space, and (5) catalyst film electrodes for elimination of carbon corrosion and ionomer poisoning. The PEMFC performance results achieved from each alternative electrode structure are presented and tabulated for comparison with conventional electrode architectures. Moreover, analysis of mechanisms by which new electrode structures can improve performance is presented and discussed. Finally, an overview of current limitations and future research needs is presented to guide the development of electrode structures for next generation PEMFCs. Graphical Abstract Development of improved electrode architectures with the control of structure on length scales ranging from millimeters to nanometers could enable a new generation of fuel cells with increased performance and reduced cost. This paper presents an in-depth review and critical analysis of recent developments and future outlook on the design of advanced electrode structures.

25 ENERGY STORAGE↗
DOE OSTI2026

Selective CO 2 Reduction by Bis(bipyridine)cobalt(II) Catalysts: The Role of Pendant Pyridine as a Proton Acceptor

Electrochemical CO 2 reduction reaction (CO 2 RR) catalyzed by molecular earth-abundant metal catalysts is a promising strategy to convert CO 2 into value-added products. One recent trend in this field has been focusing on the rational design of catalysts by incorporating redox-active ligands and modifying the secondary coordination sphere (SCS) to achieve efficient and selective CO 2 RR. Herein, we report a series of Co bis­(bipyridine) catalysts featuring various dangling groups, such as pyridine, tertiary amine, or butyl, in the secondary coordination sphere (Co-PyMe, Co-Py, Co-PrN, and Co-Bu). Efficient, selective electrocatalytic CO 2 RR was achieved by the complexes after the generation of triply reduced intermediate consisting of a Co I center and a dianionic ligand, producing CO as the major product and trace amount of H 2 . Strong correlations with the identity of dangling groups and turnover frequency (TOF) have been observed, in which Co-PyMe displayed the highest TOF (1086 s –1 in MeCN/H 2 O). Mechanistic studies indicated that the acceleration of CO 2 RR with pyridine-functionalized catalysts were derived from the protonation of pyridine dangling groups which participated as weak acids in the H-bonding network with exogenous proton sources, stabilizing CO 2 -bound intermediates and facilitating proton transfer. In addition, precatalytic CO 2 binding and activation at the third reduction (−2.1 V) was revealed by CV and SEC-IR studies. The resultant doubly reduced CO-bound species acted as a trapping state which inhibited CO 2 RR electrocatalysis. Regeneration of active species was accessed via reductive dissociation of CO at a more negative potential. In conclusion, this study highlights the combined effects of redox-active ligands and pyridine/pyridinium as SCS groups on CO 2 RR catalysis and provides design principles for future development of CO 2 RR catalysts utilizing pyridine/pyridiniums as SCS functional groups to fine-tune the catalytic activity.

CO2 reduction↗
DOE OSTI2025

Effect of cell compression on the performance and the structure of proton exchange membrane water electrolyzer (PEMWE) assembly

Here, in the field of water electrolysis, the proton exchange membrane water electrolyzer (PEMWE) is currently the most advanced technology for producing hydrogen without emitting CO 2 . Although PEMWE plants are already in operation, further research is needed to improve cell efficiency and reduce the use of rare materials, such as iridium oxide catalysts for the oxygen evolution reaction (OER). One of the main causes of performance loss in PEMWE is the relatively low electric conductivity of the porous transport layer (PTL) and of the anode catalyst layer, which results in ohmic losses and low catalyst utilization during high current density operation. The objective of this study is to investigate how optimization of the PTL and electrode interface can increase the cell performance. To this end, we tested different cell assemblies using fibrous and sintered PTLs, decreasing membrane thickness, reducing iridium loading, and inserting a microporous layer to increase contact surface area. Electrochemical characterization of each cell configuration was systematically performed at various compression levels as the pressure is a crucial parameter influencing the electrode/PTL contact area. In parallel, X-ray microcomputed tomography (micro-CT) was employed to investigate the effects of cell hydration and compression on the structure of PEMWE components. This study combining electrochemistry and micro-CT imaging presents how optimizing the electrode/PTL contact surface area, minimizes ohmic losses, and enables PEMWE operation with low iridium loading at high current densities.

Catalyst - PTL interface↗
DOE OSTI2026

Intrinsic kinetics of water-inhibited ultra-lean methane oxidation over PtPd-Mg/ θ -Al 2 O 3 catalyst

Here, this study develops intrinsic methane oxidation kinetics for ultra-lean methane conditions in the presence of water over a highly active and stable PtPd–Mg/θ-Al 2 O 3 catalyst. Comprehensive laboratory experiments were conducted over a wide range of methane concentrations (150–1200 ppm CH 4 ), water contents (1–5% H 2 O), and industrially relevant space velocities (80,000 ≤ GHSV ≤ 160,000 h -1 ). These systematic experiments informed a two-dimensional, axisymmetric, multiscale reactor model that was used to develop and validate methane oxidation kinetics under practically relevant conditions, including non-isothermal operation and high conversion regimes. Combined experimental and modeling results revealed significant intraparticle diffusion resistance and transport-induced reaction exotherm at elevated temperatures, which limited catalyst utilization despite high intrinsic activity. These transport effects were explicitly incorporated into the reactor model, enabling accurate estimation of intrinsic kinetic parameters without reliance on conventional effectiveness-factor corrections. The resulting kinetic model successfully captured both kinetically controlled and mass-transfer-limited regimes and reliably predicted CH 4 conversion across broad ranges of temperature, methane concentration, and water content

Heat and mass transfer limitations↗
DOE OSTI2022

Evaluating the effect of ionomer chemical composition in silver-ionomer catalyst inks toward the oxygen evolution reaction by half-cell measurements and water electrolysis

The effect of anion exchange ionomer (AEI) chemistry on the kinetics of the oxygen evolution reaction (OER) was systematically studied in both half-cell and single-cell electrolysis experiments. OER was studied in 1 M K 2 CO 3 at 50°C using an array of ionomer-silver catalyst inks deposited on Ni foam. Different ionomer modifications were investigated to optimize the OER performance. The AEI used in this work features a block copolymer backbone of polychloromethylstyrene-b-polycyclooctene-b-polychloromethylstyrene which was functionalized with either benzyltrimethylammonium (TMA) or benzylmethylpiperidinium (MPRD) quaternary ammonium cations. Here, using an MPRD quaternary ammonium cation shifted the rate determining step at high overpotentials, ultimately providing enhanced performance. Increasing the catalyst ink dilution was also found to substantially improve mass activity and catalyst utilization (increase from 35 to 88 A g –1 Ag), likely by reducing the ionomer thickness and decreasing transport resistances. In the final ionomer modification, the Ni foam substrate was leveraged to partially hydrogenate the polycyclooctene midblock to be polyethylene-like at the Ni interface. A significant increase in the electrochemical surface area (Cdl increased from 8.8 to 20.8 mF cm –2 ) and performance (by 47 mA cm –2 or 29 A g –1 Ag) was observed with the incorporation of polyethylene. Kinetic results from half-cell experiments were validated via single-cell anion exchange membrane electrolysis experiments, where the optimized electrode displayed enhanced performance in both 1 M K 2 CO 3 and DI H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Favorable morphology and electronic conductivity of functional sublayers for highly efficient water splitting electrodes

Low electronic conductivities and improper morphologies of anode electrodes greatly limit the reaction area, catalyst utilization and efficiency in proton exchange membrane water electrolyzers. In this study, conductive sublayers with different conductivities and morphologies were introduced into anode electrodes in membrane-based water electrolyzers. In-situ and ex-situ investigation results showed that conductive sublayers (Au mesh and carbon nanotube (CNT) film) augmented the sheet conductivity of anode electrodes by up to 4000 times (from 2000 to 0.5 ohm square -1 ), and the ohmic resistance of water electrolyzers was reduced to 1/3 when inserting conductive sublayers. In addition, CNT film provided a higher electrochemical active area than Au mesh, because of favorable morphologies (large porosity and surface area) of CNT fibers on CNT films. Therefore, the current density of water splitting was increased by 3 times (from 4.55 mA cm -2 to 14.83 mA cm -2 ) at 2.5 V compared to a conventional anode electrode. Visualizations on bubble dynamics showed improved performances with conductive sublayers; this was mainly due to greatly increased number of reaction sites, highly spread reaction area (from 50 to 1000 um), and reduced activation overpotential. Therefore, a balance between high electronic conductivity and nanoporous morphology is essential to the anode electrode for larger reaction sites and areas in highly efficient water electrolyzers.

25 ENERGY STORAGE↗
DOE OSTI2025

Synthesis of multicomponent oxygen evolution reaction coatings via block copolymer templating with vapor- and solution-phase precursors

Porous mixed transition metal oxide heterostructures are promising electrocatalysts due to their high surface area. However, achieving conformal multicomponent oxide coatings with controlled nanoscale architectures remains challenging. Here, we report a synthesis strategy that integrates solution-based swelling infiltration (SBI) with gas-phase sequential infiltration synthesis (SIS) in a block copolymer template to fabricate porous, high-surface-area, conformal mixed-oxide electrocatalytic coatings. In this approach, a PS75-P4VP25 block copolymer (BCP) film is first infiltrated with transition metal acetylacetonate precursors via SBI, followed by exposure to gas phase precursors of ZnO via SIS process. Thermal annealing of the infiltrated BCP films converts them into all-inorganic Fe–ZnO, Fe–Co–ZnO, and Fe–Ni–ZnO coatings. Electrochemical testing on 70 nm thick conformal coatings demonstrates promising oxygen evolution reaction (OER) activity in alkaline media, with mass-specific current densities up to 1.0 × 10 5 mA/g at an overpotential of 330 mV (vs. RHE) at ultralow loading (~0.005 g/cm 2 ). Among the compositions, Fe–Co–ZnO and amorphous Fe–Ni–ZnO show the best OER performance, delivering current densities of 2.00 and 3.04 mA/cm 2 , respectively, compared to 1.52 mA/cm 2 for Fe–ZnO.. This work establishes SBI–SIS as a versatile route for fabricating nm-thin, high-performance multicomponent oxide heterostructures on cost-efficient supports, enabling efficient catalyst utilization in electrochemical energy conversion application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Stable, high-performing bifunctional electrodes for anion exchange membrane-based unitized regenerative fuel cells

Anion exchange membrane unitized regenerative fuel cells (AEM-URFCs) are a promising technology for energy storage and electricity production; however, their efficiency is limited by the kinetics of the bifunctional oxygen electrode (BOE) where the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) occur. A particular concern when designing the BOE is that the OER and ORR have differing catalytic requirements, which make it challenging to develop effective bifunctional electrocatalysts with single active sites. In this study, we focus on advancing the BOE performance using Pt-IrO x and Pt-NiCoO x electrocatalysts. Here, single-layer and dual-layer Pt-IrO x BOEs were made, with the dual-layer electrode leading to improved performance due to efficient catalyst utilization in both modes. Using the dual-layer oxygen electrode paired with a PtRu/C hydrogen electrode, a round trip efficiency (RTE) as high as 50% (62 %iR-free) was achieved at 500 mA/cm 2 and operation for more than 24 h, which included five one-hour-long H 2 generation and consumption cycles followed by one eight-hour-long cycle. To the best of our knowledge, this is the highest performance for AEM-URFCs reported to date. Lastly, the approach is extended to electrodes with a Pt loading of 0.5 mg/cm 2 and the IrO x substituted by NiCoO x .

25 ENERGY STORAGE↗
DOE OSTI2021

All-in-one bipolar electrode: A new concept for compact and efficient water electrolyzers

Highly compact and efficient proton exchange membrane electrolyzer cells (PEMECs) are strongly desired for commercializing hydrogen production. Here, a novel concept of all-in-one bipolar electrode (AIOBE) is proposed for high-efficiency and compact PEMECs with the help of 3D printing and sputtering coating. AIOBE ideally integrated catalyst layer (CL)/gas diffusion layer/bipolar plate/current distributor/gasket, which significantly reduced component quantity on the cathode side of PEMECs from 5 to 1, cut down on part weight and volume, and drastically accelerated the fabrication and maintenance processes. Moreover, AIOBE with the micro-scale flat surface and nano-scale rough CL provided an ultralow ohmic resistance (~100 mOhm cm 2 ) and a high catalyst utilization. Finally, AIOBE delivered a practical voltage of 1.62 V and a high energy efficiency of 91% at 1000 mA/cm 2 , and its mass activity (4.48 A/mg Pt ) was 14 times higher than conventional PEMECs. In conclusion, this work provides a new route for developing highly compact electrochemical devices, such as fuel cells, electrolyzers for N 2 reduction and CO 2 conversion, and many more.

3D printing↗
DOE OSTI2023

Mechanism and Dynamics of Photodecarboxylation Catalyzed by Lactate Monooxygenase

Photoenzymes are a rare class of biocatalysts that use light to facilitate chemical reactions. Many of these catalysts utilize a flavin cofactor to absorb light, suggesting that other flavoproteins might have latent photochemical functions. Lactate monooxygenase is a flavin-dependent oxidoreductase previously reported to mediate the photodecarboxylation of carboxylates to afford alkylated flavin adducts. While this reaction holds a potential synthetic value, the mechanism and synthetic utility of this process are unknown. Here, we combine femtosecond spectroscopy, site-directed mutagenesis, and a hybrid quantum-classical computational approach to reveal the active site photochemistry and the role the active site amino acid residues play in facilitating this decarboxylation. Light-induced electron transfer from histidine to flavin was revealed, which has not been reported in other proteins. These mechanistic insights enable the development of catalytic oxidative photodecarboxylation of mandelic acid to produce benzaldehyde, a previously unknown reaction for photoenzymes. Furthermore, our findings suggest that a much wider range of enzymes have the potential for photoenzymatic catalysis than has been realized to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of Carbon Support Heat Treatment on the Performance of Ion-Pair High-Temperature PEM Fuel Cells

Heat treatment can significantly alter the physical and chemical properties of carbon supports, thereby influencing the performance of proton exchange membrane (PEM) fuel cells. This study explores how varying carbon heat treatment temperatures—from 1,000 °C to 2,200 °C—affect the structure and performance of platinum-based catalysts in high-temperature PEM fuel cells. Increasing the heat treatment temperature led to a notable decrease in surface area, along with increases in carbon grain size and hydrophobicity. Although the catalyst supported on carbon treated at 1,000 °C exhibited the highest catalyst activity, the MEA using carbon treated at 1,500 °C delivered the best overall fuel cell performance. This is attributed to an optimized balance between hydrophobicity and accessible surface area, which enhances water management and catalyst utilization. These findings underscore the importance of carbon support engineering in improving the efficiency of ion-pair high-temperature PEM fuel cells.

08 HYDROGEN↗
DOE OSTI2021

Easier Access to Functional Furans

Traditional furan alkylation utilizes catalyst materials are unsafe, produce hazardous waste, and yield low reaction products. Researchers at Los Alamos National Laboratory have developed a new method to enable industries to produce valuable chemicals from biomass more safely with higher yields and less waste. This method has been successfully demonstrated on the benchtop, and is ready for testing to scale up for industrial synthesis applications. Los Alamos is seeking a licensee to scale this technology in-house, or a Cooperative Research and Development Agreement (CRADA) partner to scale the method within the Laboratory for a specific purpose.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Catalyst Layer Resistance and Utilization in PEM Electrolysis

Improving utilization, performance, and stability of low iridium (Ir)-loaded anodes is a key goal to enable widespread adoption of polymer electrolyte membrane water electrolysis (PEMWE) for clean hydrogen production. A potential limitation is high ionic or electronic resistance of the anode catalyst layer, which leads to poor catalyst utilization, increased voltage losses, and high local overpotentials that can accelerate degradation. While catalyst layer resistance is relatively well-understood in fuel cells and other porous electrode systems, characterization of these effects is not as well established in PEMWE research. Here we present in-situ methods for measuring catalyst layer resistance in electrolysis cells using a non-faradaic H 2 /H 2 O condition as well as methods for calculating the associated voltage losses. These methods are applied to anode catalyst layers based on IrO 2 nanoparticles as well as dispersed nano-structured thin film (NSTF) Ir catalysts. Trends with anode catalyst loading and interactions between the porous transport layer and catalyst layer are investigated for IrO 2 anodes. Post-mortem microscopic analysis of durability-tested anodes is also presented, showing uneven degradation of the catalyst layer caused by catalyst layer resistance.

08 HYDROGEN↗
DOE OSTI2022

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. Here, this review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗
DOE OSTI2021

Nanoporous Iridium Nanosheets for Polymer Electrolyte Membrane Electrolysis

The growth of the hydrogen economy is predicated on advancements in electrochemical energy technologies, with water electrolysis as a key component to the technological portfolio. Much of the focus on anode catalyst development for polymer electrolyte membrane water electrolyzers (PEMWE) is centered on activity as controlled by compositional and morphological impacts on reactant/intermediate/product adsorption. However, the effectiveness of this strategy is found to be limited upon integration of these materials into PEMWE membrane electrode assemblies (MEA). Regardless of catalyst activity, the combination of electrode inhomogeneity, ionomer integration, and high density of oxide-oxide interfaces yields significant performance losses associated with poor catalytic electrode conductivity. Here many of these limitations are addressed through the development of a unique catalyst morphology composed of nanoporous Ir nanosheets (npIr(x)-NS) that exhibit high catalytic activity for the anodic oxygen evolution reaction and superior electrode electronic conductivity in comparison to a commercial IrO2 nanoparticle catalyst. The utility of the npIr(x)-NS is demonstrated through incorporation into PEMWE MEAs where their performance exceeds that of commercial catalyst coated membranes at loadings as low as 0.06 mg(Ir) cm(-2) while exhibiting a negligible loss in performance following 50 000 accelerated stress test cycles.

Polymer Electrolyte Membrane Electrolysis↗