Regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-Metal Site-Rich Carbon and Pt.

Developing low platinum-group-metal (PGM) catalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles (HDVs) remains a great challenge due to the highly demanded power density and long-term durability. This work explores the possible synergistic effect between single Mn site-rich carbon (MnSA-NC) and Pt nanoparticles, aiming to improve intrinsic activity and stability of PGM catalysts. Density functional theory (DFT) calculations predicted a strong coupling effect between Pt and MnN4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L12-Pt3Co nanoparticles (3.3 nm) were retained on the MnSA-NC support after indispensable high-temperature annealing up to 800 °C, suggesting enhanced thermal stability. Both PGM catalysts were thoroughly studied in membrane electrode assemblies (MEAs), showing compelling performance and durability. The Pt@MnSA-NC catalyst achieved a mass activity (MA) of 0.63 A mgPt-1 at 0.9 ViR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L12-Pt3Co@MnSA-NC catalyst accomplished a much higher MA of 0.91 A mgPt-1 and a current density of 1.63 A cm-2 at 0.7 V under traditional light-duty vehicle (LDV) H2-air conditions (150 kPaabs and 0.10 mgPt cm-2). Furthermore, the same catalyst in an HDV MEA (250 kPaabs and 0.20 mgPt cm-2) delivered 1.75 A cm-2 at 0.7 V, only losing 18% performance after 90,000 cycles of the AST, demonstrating great potential to meet the DOE targets.

Chemical vapour deposition of Fe-N-C oxygen reduction catalysts with full utilization of dense Fe-N4 sites.

Replacing scarce and expensive platinum (Pt) with metal-nitrogen-carbon (M-N-C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low oxygen reduction reaction activity of M-N-C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe-N-C by flowing iron chloride vapour over a Zn-N-C substrate at 750 °C, leading to high-temperature trans-metalation of Zn-N4 sites into Fe-N4 sites. Characterization by multiple techniques shows that all Fe-N4 sites formed via this approach are gas-phase and electrochemically accessible. As a result, the Fe-N-C catalyst has an active site density of 1.92 × 1020 sites per gram with 100% site utilization. This catalyst delivers an unprecedented oxygen reduction reaction activity of 33 mA cm-2 at 0.90 V (iR-corrected; i, current; R, resistance) in a H2-O2 proton exchange membrane fuel cell at 1.0 bar and 80 °C.

Dynamically Unveiling Metal-Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN4 Active Sites.

We elucidate the structural evolution of CoN4 sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)-8-derived carbon host as an ideal model for Co2+ ion adsorption. Subsequent in situ X-ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co-OH and Co-O species into active CoN4 sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four-electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal-induced compressive strain of Co-N bonds in CoN4 active sites formed at 900 °C. Further, we developed a two-step (i.e., Co ion doping and adsorption) Co-N-C catalyst with increased CoN4 site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

Evolution Pathway from Iron Compounds to Fe1(II)-N4 Sites through Gas-Phase Iron during Pyrolysis.

Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe-N-C catalyst improvement. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe1(II)-N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that diffuses into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor-phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via "noncontact pyrolysis" wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.

Effect of Dispersion Medium Composition and Ionomer Concentration on the Microstructure and Rheology of Fe-N-C Platinum Group Metal-free Catalyst Inks for Polymer Electrolyte Membrane Fuel Cells.

We present an investigation of the microstructure and rheological behavior of catalyst inks consisting of Fe-N-C platinum group metal-free catalysts and a perfluorosulfonic acid ionomer in a dispersion medium (DM) of water and 1-propanol (nPA). The effects of the ionomer-to-catalyst (I/C) ratio and weight percentage of water (H2O %) in the DM on the ink microstructure were studied. Steady-shear and dynamic-oscillatory-shear rheology, in combination with synchrotron X-ray scattering, was utilized to understand interparticle interactions and the level of agglomeration of the inks. In the absence of the ionomer, the inks were significantly agglomerated, approaching a gel-like microstructure for catalyst concentrations as low as 2 wt %. The effect of H2O % in the DM on particle agglomeration was found to vary with particle concentration. In concentrated inks (≥2 wt % catalyst), increasing H2O % was found to increase agglomeration because of the hydrophobic nature of the catalysts. In dilute inks (<1 wt % catalyst), the trend was reversed with increasing H2O %, suggesting that electrostatic interactions are dominating the behavior. In inks with 5 wt % catalyst, the addition of an ionomer was found to significantly stabilize the catalyst against agglomeration. Maximum stability was observed at 0.35 I/C for all DM H2O % studied. At high ionomer concentrations (I/C > 0.35), interesting differences were observed between nPA-rich inks (H2O % ≤ 50%) and H2O-rich (82% H2O) inks. The nPA-rich inks remained predominantly stable-ink viscosity only weakly increased with I/C and the Newtonian behavior was maintained for I/C up to 0.9. In contrast, the H2O-rich inks exhibited a significant increase in viscoelasticity with increasing I/C, suggesting flocculation of the catalyst by the ionomer. These differences suggest that the nature of the interactions between the ionomer and catalyst is highly dependent on the H2O % in the DM.

Insight into the Catalytic Mechanism of Bimetallic Platinum-Copper Core-Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions.

The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt-Cu core-shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li-O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt-Cu core-shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

Evidence for lithium superoxide-like species in the discharge product of a Li-O2 battery.

We report on the use of a petroleum coke-based activated carbon (AC) with very high surface area for a Li-O(2) battery cathode without the use of any additional metal catalysts. Electrochemical measurement in a tetra(ethylene) glycol dimethyl ether-lithium triflate (TEGDME-LiCF(3)SO(3)) electrolyte results in two voltage plateaus during charging at 3.2-3.5 and 4.2-4.3 V versus Li(+)/Li. Herein we present evidence from Raman and magnetic measurements that the lower plateau corresponds to a form of lithium peroxide with superoxide-like properties characterized by a low temperature magnetic phase transition and a high O-O stretching frequency (1125 cm(-1)). The magnetic phase transition and the high O-O stretching frequency disappear when charged to above 3.7 V. Theoretical calculations indicate that a surface superoxide structure on lithium peroxide clusters and some lithium peroxide surfaces have an unpaired electron and a high O-O stretching frequency that help explain the observations. These results provide evidence that the form of the lithium peroxide discharge product is important to obtaining a low charge overpotential, and thus improving the round-trip efficiency between discharge and charge.

Bypassing Formation of Oxide Intermediate via Chemical Vapor Deposition for the Synthesis of an Mn-N-C Catalyst with Improved ORR Activity.

A significant barrier to the commercialization of proton exchange membrane fuel cells (PEMFCs) is the high cost of the platinum-based oxygen reduction reaction (ORR) cathode electrocatalysts. One viable solution is to replace platinum with a platinum-group metal (PGM) free catalyst with comparable activity and durability. However, PGM-free catalyst development is burdened by a lack of understanding of the active site formation mechanism during the requisite high-temperature synthesis step, thus making rational catalyst design challenging. Herein we demonstrate in-temperature X-ray absorption spectroscopy (XAS) to unravel the mechanism of site evolution during pyrolysis for a manganese-based catalyst. We show the transformation from an initial state of manganese oxides (MnOx) at room temperature, to the emergence of manganese-nitrogen (MnN4) site beginning at 750 °C, with its continued evolution up to the maximum temperature of 1000 °C. The competition between the MnOx and MnN4 is identified as the primary factor governing the formation of MnN4 sites during pyrolysis. This knowledge led us to use a chemical vapor deposition (CVD) method to produce MnN4 sites to bypass the evolution route involving the MnOx intermediates. The Mn-N-C catalyst synthesized via CVD shows improved ORR activity over the Mn-N-C synthesized via traditional synthesis by the pyrolysis of a mixture of Mn, N, and C precursors.

A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid.

The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO2 utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H2 electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm2 in a 25 cm2 cell. More critically, a 55-hour stability test at 200 mA/cm2 shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods.

In situ anomalous small-angle X-ray scattering studies of platinum nanoparticle fuel cell electrocatalyst degradation.

Polymer electrolyte fuel cells (PEFCs) are a promising high-efficiency energy conversion technology, but their cost-effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed Pt nanoparticle growth during potential cycling of the electrocatalyst in an aqueous acidic environment using in situ anomalous small-angle X-ray scattering (ASAXS). ASAXS patterns were analyzed to obtain particle size distributions (PSDs) of the Pt nanoparticle electrocatalysts at periodic intervals during the potential cycling. Oxide coverages reached under the applied potential cycling protocols were both calculated and determined experimentally. Changes in the PSD, mean diameter, and geometric surface area identify the mechanism behind Pt nanoparticle coarsening in an aqueous environment. Over the first 80 potential cycles, the dominant Pt surface area loss mechanism when cycling to 1.0-1.1 V was found to be preferential dissolution or loss of the smallest particles with varying extents of reprecipitation of the dissolved species onto existing particles, resulting in particle growth, depending on potential profile. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSD and ECA resulting from various voltage profiles to a response dependent on oxide coverage.

Tracking Nanoparticle Degradation across Fuel Cell Electrodes by Automated Analytical Electron Microscopy.

Nanoparticles are an important class of materials that exhibit special properties arising from their high surface area-to-volume ratio. Scanning transmission electron microscopy (STEM) has played an important role in nanoparticle characterization, owing to its high spatial resolution, which allows direct visualization of composition and morphology with atomic precision. This typically comes at the cost of sample size, potentially limiting the accuracy and relevance of STEM results, as well as the ability to meaningfully track changes in properties that vary spatially. In this work, automated STEM data acquisition and analysis techniques are employed that enable physical and compositional properties of nanoparticles to be obtained at high resolution over length scales on the order of microns. This is demonstrated by studying the localized effects of potential cycling on electrocatalyst degradation across proton exchange membrane fuel cell cathodes. In contrast to conventional, manual STEM measurements, which produce particle size distributions representing hundreds of particles, these high-throughput automated methods capture tens of thousands of particles and enable nanoparticle size, number density, and composition to be measured as a function of position within the cathode. Comparing the properties of pristine and degraded fuel cells provides statistically robust evidence for the inhomogeneous nature of catalyst degradation across electrodes. These results demonstrate how high-throughput automated STEM techniques can be utilized to investigate local phenomena occurring in nanoparticle systems employed in practical devices.

Recreating Fuel Cell Catalyst Degradation in Aqueous Environments for Identical-Location Scanning Transmission Electron Microscopy Studies.

The recent surge in interest of proton exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles increases the demand on the durability of oxygen reduction reaction electrocatalysts used in the fuel cell cathode. This prioritizes efforts aimed at understanding and subsequently controlling catalyst degradation. Identical-location scanning transmission electron microscopy (IL-STEM) is a powerful method that enables precise characterization of degradation processes in individual catalyst nanoparticles across various stages of cycling. Recreating the degradation processes that occur in PEMFC membrane electrode assemblies (MEAs) within the aqueous cell used for IL-STEM experiments is vital for generating an accurate understanding of these processes. In this work, we investigate the type and degree of catalyst degradation achieved by cycling in an aqueous cell compared to a PEMFC MEA. While significant degradation is observed in IL-STEM experiments performed on a traditional Pt catalyst using the standard accelerated stress test potential window (0.6-0.95 VRHE), degradation of a PtCo catalyst designed for heavy-duty vehicle use is very limited compared to that observed in MEAs. We therefore explore various experimental parameters such as temperature, acid type, acid concentration, ionomer content, and potential window to identify conditions that reproduce the degradation observed in MEAs. We find that by extending the cycling potential window to 0.4-1.0 VRHE in an electrolyte containing Pt ions, the degraded particle size distribution and alloy composition better match that observed in MEAs. In particular, these conditions increase the relative contribution of Ostwald ripening, which appears to play a more significant role in the degradation of larger alloy particles supported on high-surface-area carbons than coalescence. Results from this work highlight the potential for discrepancies between ex situ aqueous experiments and MEA tests. While different catalysts may require a unique modification to the AST protocol, strategies provided in this work enable future in situ and identical-location experiments that will play an important role in the development of robust catalysts for heavy-duty vehicle applications.

Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study.

To increase the commercialization of fuel cell electric vehicles, it is imperative to improve the activity and performance of electrocatalysts through combined efforts focused on material characterization and device-level integration. Obtaining fundamental insights into the ongoing structural and compositional changes of electrocatalysts is crucial for not only transitioning an electrode from its as-prepared to functional state, also known as "conditioning", but also for establishing intrinsic electrochemical performances. Here, we investigated several oxygen reduction reaction (ORR) electrocatalysts via in situ and ex situ characterization techniques to provide fundamental insights into the interfacial phenomena that enable peak ORR mass activity and high current density performance. A mechanistic understanding of a fuel cell conditioning procedure is described, which encompasses voltage cycling and subsequent voltage recovery (VR) steps at low potential. In particular, ex situ membrane electrode assembly characterization using transmission electron microscopy and ultra-small angle X-ray scattering were performed to determine changes in carbon and Pt particle size and morphology, while in situ electrochemical diagnostics were performed either during or after specific points in the testing protocol to determine the electrochemical and interfacial changes occurring on the catalyst surface responsible for oxygen transport resistances through ionomer films. The results demonstrate that the voltage cycling (break-in) step aids in the removal of sulfate and fluoride and concomitantly reduces non-Fickian oxygen transport resistances, especially for catalysts where Pt is located within the pores of the carbon support. Subsequent low voltage holds at low temperature and oversaturated conditions, i.e., VR cycles, serve to improve mass activities by a factor of two to three, through a combined removal of contaminants, surface-blocking species (e.g., oxides), and rearrangement of the catalyst atomic structure (e.g., Pt-Pt and Pt-Co coordination).

Investigation of the Microstructure and Rheology of Iridium Oxide Catalyst Inks for Low-Temperature Polymer Electrolyte Membrane Water Electrolyzers.

We present an investigation of the structure and rheological behavior of catalyst inks for low-temperature polymer electrolyte membrane water electrolyzers. The ink consists of iridium oxide (IrO2) catalyst particles and a Nafion ionomer dispersed in a mixture of 1-propanol and water. The effects of ionomer concentration and catalyst concentration on the microstructure of the catalyst ink were studied. Studies on dilute inks (0.1 wt % IrO2) using zeta potential and dynamic light scattering measurements indicated a strong adsorption of the ionomer onto the catalyst particles which resulted in an increase in the ζ-potential and the z-average diameter. Steady-shear and dynamic-oscillatory-shear rheological measurements of concentrated IrO2 dispersions (35 wt % IrO2) indicated that the particles are strongly agglomerated in the absence of the ionomer. The addition of even a small amount of the ionomer (2.4 wt % with respect to total solids) caused the rheology to transition from shear thinning to Newtonian because of the reduction in agglomerated structure due to stabilization of the aggregates by the ionomer, consistent with the behavior of dilute inks. At intermediate ionomer loadings, between 2.4 and 9 wt %, the viscosity increased with increasing ionomer wt %, though remained Newtonian, predominantly due to the increasing ionomer volume fraction in the ink. For ionomer loadings greater than 9 wt %, the particles were found to be flocculated, likely induced by a dispersed ionomer. The flocculated inks exhibited strong shear-thinning and gel-like behaviors in steady-shear and oscillatory-shear rheology. The onset of flocculation was found to be sensitive to the catalyst concentration, where below 35 wt % of IrO2, flocculation was not observed. The rheological observations were further verified by ultra-small-angle X-ray scattering.

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.

In situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena.

In situ small-angle X-ray scattering observation of Pt catalyst particle growth during potential cycling.

A unique type of inorganic-organic hybrid semiconductor bulk material is capable of emitting direct white light. Their photoluminescence properties can be tuned precisely and systematically by modifying structures and composition. They could be used as a single-material light-emitting source in high efficiency white-light-emitting diodes.

Rheological Investigation on the Microstructure of Fuel Cell Catalyst Inks.

We present a rheological investigation of fuel cell catalyst inks. The effects of ink parameters, which include carbon black-support structure, Pt presence on carbon support (Pt-carbon), and ionomer (Nafion) concentration, on the ink microstructure of catalyst inks were studied using rheometry in combination with ultrasmall-angle X-ray scattering (USAXS) and dynamic light scattering (DLS). Dispersions of a high-surface-area carbon (HSC), or Ketjen black type, demonstrated a higher viscosity than Vulcan XC-72 carbon due to both a higher internal porosity and a more agglomerated structure that increased the effective particle volume fraction of the inks. The presence of Pt catalyst on both the carbon supports reduced the viscosity through electrostatic stabilization. For carbon-only dispersions (without Pt), the addition of ionomer up to a critical concentration decreased the viscosity due to electrosteric stabilization of carbon agglomerates. However, with Pt-carbon dispersions, the addition of ionomer showed contrasting behavior between Vulcan and HSC supports. In the Pt-Vulcan dispersions, the effect of ionomer addition on the rheology was qualitatively similar to Vulcan dispersions without Pt. The Pt-HSC dispersions showed an increased viscosity with ionomer addition and a strong shear-thinning nature, indicating that Nafion likely flocculated the Pt-HSC aggregates. These results were verified using DLS and USAXS. Further, the observations of the effect of ionomer:carbon ratio and a comparison between carbons of different surface areas provided insights on the microstructure of the catalyst ink corresponding to the optimized I/ C ratio for fuel cell performance reported in the literature.

A carbon-nanotube-supported graphene-rich non-precious metal oxygen reduction catalyst with enhanced performance durability.

A non-precious metal catalyst for oxygen reduction in acid media, enriched in graphene sheets/bubbles during a high-temperature synthesis step, has been developed from an Fe precursor and in situ polymerized polyaniline, supported on multi-walled carbon nanotubes. The catalyst showed no performance loss for 500 hours in a hydrogen/air fuel cell. The improved durability is correlated with the graphene formation, apparently enhanced in the presence of carbon nanotubes.