Bypassing Formation of Oxide Intermediate via Chemical Vapor Deposition for the Synthesis of an Mn-N-C Catalyst with Improved ORR Activity
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Cullen, David A.
Publications and source records attributed to Cullen, David A..
Modular Iron–Bipyridine-Based Conjugated Aerogels as Catalysts for Oxygen Reduction Reaction
Aerogels have a large surface area and a porous structure, which make them an attractive catalyst support materials for fuel cells. Modifying the aerogels’ building blocks and introducing catalytic sites into their backbones allow them to function as both catalysts and supports, thereby increasing the density and distribution of catalyst active sites. In this work, we studied conjugated aerogels containing iron–bipyridine catalytic sites for the oxygen reduction reaction. To demonstrate the variation in physical and electrochemical properties of these aerogels, a series of aerogels were synthesized by a Glaser coupling reaction. Iron salt was added to the three-dimensional gel to produce iron–bipyridine complexes and obtain atomically dispersed catalytic sites. The electrocatalytic activity and electrical conductivity of the aerogels were increased after their heat treatment to yield Fe-doped carbon aerogels. The control of metal loadings was accomplished by changing the bipyridine content during the aerogel synthesis, resulting in 0.9–4.1 wt % Fe. In conclusion, the results show a correlation between Fe loading, aerogel structure, and catalytic activity, achieving high performance for the oxygen reduction reaction in both acidic and alkaline media.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomically Ordered PdCu Electrocatalysts for Selective and Stable Electrochemical Nitrate Reduction
Electrochemical nitrate reduction (NO 3 RR) has attracted attention as an emerging approach to mitigate nitrate pollution in groundwater. Here, we report that a highly ordered PdCu alloy-based electrocatalyst exhibits selective (91% N 2 ), stable (480 h), and near complete (94%) removal of nitrate without loss of catalyst. In situ and ex situ XAS provide evidence that structural ordering between Pd and Cu improves long-term catalyst stability during NO 3 RR. In contrast, we also report that a disordered PdCu alloy-based electrocatalyst exhibits non-selective (44% N 2 and 49% NH 4 + ), unstable, and incomplete removal of nitrate. The copper within disordered PdCu alloy is vulnerable to accepting electrons from hydrogenated neighboring Pd atoms. This resulted in copper catalyst losses which were 10× greater than that of the ordered catalyst. The design of stable catalysts is imperative for water treatment because loss of the catalyst adds to the system cost and environmental impacts.
36 MATERIALS SCIENCE↗
Ionomer-free nanoporous iridium nanosheet electrodes with boosted performance and catalyst utilization for high-efficiency water electrolyzers
Increasing the catalyst utilization efficiency and simplifying electrode fabrication processes are crucial to accelerate development of low-cost proton exchange membrane electrolyzer cells (PEMECs). Here, we develop a facile route to fabricate ionomer-free iridium nanosheet integrated electrodes, in which nanoporous iridium nanosheets (IrNS) with abundant exposed edges and nanopores are deposited on thin titanium liquid/gas diffusion layers (TT-LGDLs) via a low-temperature chemical synthesis strategy. Further, benefiting from high catalytic activity, good electrode conductivity and excellent liquid/gas transport properties, such nanoporous IrNS electrodes with low catalyst loadings require low cell voltages of 1.65 V and 1.78 V at 3000 and 6000 mA/cm 2 , respectively. More impressively, a stable performance can be well maintained under extremely high current density tests of 5000 mA/cm 2 , demonstrating the potential of low-loading nanoporous IrNS electrodes in solid-electrolyte based electrochemical conversion cells that require high current density operation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy
Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO 2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. In this study, focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies
Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Aging gracefully? Investigating iridium oxide ink's impact on microstructure, catalyst/ionomer interface, and PEMWE performance
Here, in this study, we conducted a thorough investigation of the impact of aging iridium oxide (IrO 2 ) perfluorosulfonic acid ionomer ink for up to 14 days on the properties of the ink and the resulting catalyst layers. We examined ink properties, such as zeta potential, dynamic light scattering (DLS), density, surface tension, and rheology, as functions of ink aging time. To evaluate the microstructure and catalyst/ionomer interface, we employed transmission electron microscopy (TEM), X-ray scattering, and X-ray photoelectron spectroscopy (XPS) techniques. Furthermore, we assessed the effect of ink aging on the performance of proton exchange membrane water electrolyzers (PEMWEs). Our findings reveal that most ink properties remain stable for 14 days. The variations in PEMWE cell performance are minimal, and no clear trend is observed in relation to ink aging time. This study demonstrates that the effects of aging the inks for 14 days on ink properties, catalyst layer structure, catalyst/ionomer interface, and PEMWE performance are negligible, indicating a substantial time window after ink preparation without any significant changes in its properties. These insights provide crucial guidance for the commercial production and coating processes of ink, which is necessary for scaling up PEM technologies to meet future demand.
30 DIRECT ENERGY CONVERSION↗
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. Here, this work explores the possible synergistic effect between single Mn site-rich carbon (Mn SA -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 MnN 4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN 4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L1 2 -Pt 3 Co nanoparticles (3.3 nm) were retained on the Mn SA -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@Mn SA -NC catalyst achieved a mass activity (MA) of 0.63 A mg Pt –1 at 0.9 V iR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L1 2 -Pt 3 Co@Mn SA -NC catalyst accomplished a much higher MA of 0.91 A mg Pt –1 and a current density of 1.63 A cm –2 at 0.7 V under traditional light-duty vehicle (LDV) H 2 –air conditions (150 kPa abs and 0.10 mg Pt cm –2 ). Furthermore, the same catalyst in an HDV MEA (250 kPa abs and 0.20 mg Pt 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.
25 ENERGY STORAGE↗
CO 2 -mediated oxidative dehydrogenation of propane enabled by Pt-based bimetallic catalysts
The greenhouse gas CO 2 is a promising soft oxidant for the oxidative dehydrogenation of light alkanes. However, the occurrence of side reactions including cracking, hydrogenolysis, and reforming results in lower olefin yields compared with direct dehydrogenation. Here, we report that Pt-M (M = Sn/In/Zn) bimetallic catalysts on non-redox-active silica support can break the equilibrium limit of direct propane dehydrogenation using CO 2 as a co-reactant to consume the hydrogen formed in propane dehydrogenation. Unlike the commonly postulated direct CO 2 -assisted dehydrogenation mechanism, we confirm that CO 2 -oxidative dehydrogenation of propane (ODHP) proceeds in two tandem steps on these bimetallic catalysts, i.e., propane dehydrogenation and reverse water-gas shift, with the latter being the rate-determining step. In situ X-ray absorption studies and density functional theory calculations suggest that the Pt m M n -MO x (e.g., Pt 3 Sn-SnO x ) interfaces are likely active sites.
03 NATURAL GAS↗
Failure to Fail: Recreating Real-life Nanoparticle Degradation in Model Environments
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Yu, Haoran↗
Cryogenic FIB and (S)TEM for Energy Storage and Conversion Materials Research
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Zachman, Michael↗
Understanding Interfacial Electrochemical Reactions through in situ ec-STEM and IL-Cryo-STEM
A major criterion in the design of next generation materials for electrical energy storage applications is a comprehensive understanding of interfacial electrochemical reactions as well as correlating the structure and chemistry across site-specific electrode/electrolyte interfaces with electron, charge, and mass transport processes as they govern performance characteristics. Scanning transmission electron microscopy (STEM) based techniques have emerged as an indispensable materials characterization tool that provides high spatial resolution imaging and chemical analysis and has been effectively utilized to obtain an atomic to nanoscale view of the interfacial structure before and after electrochemical cycling. More recently, there have been several advances that now allows us to obtain more detailed mechanistic insight into evolving reactions through in situ ec-STEM and electrical biasing platforms such as in the understanding of the mechanisms of solid electrolyte interphase formation, lithium dendrite nucleation and growth mechanisms and ionic transport mechanisms within intercalation, conversion, and alloying electrode materials. Several major advantages of the in situ ec-STEM approach is the quantitative electrochemical measurement of charge passed during cycling with simultaneous analysis of the electrochemical processes with STEM imaging and diffraction. Here, while spectroscopic analysis of the electrochemical reactions products has been performed, there is the issue of beam sensitivity and therefore, Cryo-STEM imaging combined with electron energy loss spectroscopy (EELS) techniques have been employed to analyze the chemistry of the SEI and Li dendrites. In this talk, we discuss the potential for combining identical location (IL) STEM techniques with Cryo-EM. The advantage of using this approach is that the sample is placed on a conventional TEM grid and the exact same location of the specimen can be analyzed before and after quantitative electrochemical measurements. Moreover, since the sample is on the TEM grid, the grid itself can be prepared for further Cryo-TEM experiments by plunge freezing in liquid nitrogen then transferred to the Cryo-TEM under liquid nitrogen. Results obtain from these experiments can be used to enhance our scientific understanding of interfacial chemistry at electrode/electrolyte interfaces and may be useful in the design of new materials.
36 MATERIALS SCIENCE↗
Reducing Artifacts in BF and HAADF-STEM Images of Pt/C Fuel Cells using MBIR-ARAR
Electron tomography is a powerful tool for characterization of three-dimensional (3D) nanoscale materials and devices. Bright-field (BF) and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) are two widely used imaging modes in electron tomography. These imaging modalities have proven to be useful for characterizing the structure of carbon-supported platinum (Pt/C) electrocatalysts used in fuel cells, which are an important class of clean energy conversion systems. BF and HAADF-STEM images are typically simultaneously acquired due to the complementary information they contain, as BF-STEM is more suitable for characterizing carbon due to its ability to detect lighter elements, while HAADF-STEM is more suitable for characterizing platinum due to its sensitivity to atomic number. However, the quality of BF- and HAADF-STEM images is often compromised by various artifacts, such as local blurring due to abrupt contrast changes as well as missing wedge artifacts which can severely impact the accuracy of the reconstructed 3D images. The traditional methods of reconstruction, such as Filtered Back-projection (FBP), Simultaneous Iterative Reconstruction Technique (SIRT), and Model-Based Iterative Reconstruction (MBIR), are often not suitable for removing these artifacts effectively. Here, to address this challenge, we present a novel approach called MBIR with Artifact Reduction and Adaptive Regularization (MBIR-ARAR).
25 ENERGY STORAGE↗
Investigation of Nanoparticle Degradation in Hydrogen Fuel Cell Systems through Automated Electron Microscopy
Proton exchange membrane fuel cells (PEMFC) are promising devices for the deployment of hydrogen-powered heavy-duty vehicles, providing a higher efficiency for similar driving range and fueling time than the existing ones. However, PEMFCs still encounter durability challenges mainly due to catalyst degradation in the cathode. Mitigating these performance losses requires a better understanding of the degradation mechanisms under heavy-duty accelerated stress tests (ASTs) [1]. Scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) are key tools for the analysis of Pt and PtCo nanoparticle size, spatial distribution and composition [2]. Electron tomography is also used to determine the rate and type of degradation of catalyst nanoparticles as a function of their position on the carbon support. In this work, automated data acquisition software, paired with a custom Python code, have been used to study the effect of different accelerated stress tests (ASTs) on nanoparticle coarsening [2]. Figure 1 shows high-angle annular dark-field (HAADF)-STEM images and EDS maps comparing the cathodes of membrane electrode assemblies (MEAs) following an electrocatalyst AST performed under H2/N2 with that of the heavy-duty AST performed under H2/air. We will discuss how AST conditions affect considerably the spatial distribution of the nanoparticles across the electrode between the membrane and microporous layer. Although the median particle size increased more in the MEA aged under the heavy-duty AST, as determined using a high-throughput image analysis, the quantitative EDS measurements demonstrate that the electrocatalyst AST resulted in more Pt and Co dissolution from the cathode, which is another important indicator of electrocatalyst degradation. We will further present the impact of the relative humidity (% RH) on the degradation mechanisms demonstrated using the same approach. Electron tomography has been used to distinguish the Pt nanoparticles residing on the carbon support surface (exterior) from those within the pore structure (interior) in order to determine the relative stability of interior and exterior nanoparticles. As shown in Figure 2, we will compare the Pt catalyst particle size at the beginning of test (BOT) and end of test (EOT), and discuss the importance of automating the electron tomography workflow, i.e. acquisition, reconstruction, and visualization, to increase sampling and determine the standard deviation of these measurement. The outlook for utilizing low-dose cryo-tomography for limiting damage to the catalyst, support, and especially proton-conducting ionomer will also be discussed [3].
Amichi, Lynda↗
Structural and Reactivity Effects of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction
While improved activity was recently reported for bimetallic iron-metal-nitrogen-carbon (FeMNC) catalysts for the oxygen reduction reaction (ORR) in acid medium, the nature of active sites and interactions between the two metals are poorly understood. Here, FeSnNC and FeCoNC catalysts were structurally and catalytically compared to their parent FeNC and SnNC catalysts. While CO cryo-chemisorption revealed a twice lower site density of M-N x sites for FeSnNC and FeCoNC relative to FeNC and SnNC, the mass activity of both bimetallic catalysts is 50–100% higher than that of FeNC due to a larger turnover frequency in the bimetallic catalysts. Electron microscopy and X-ray absorption spectroscopy identified the coexistence of Fe-N x and Sn-N x or Co-N x sites, while no evidence was found for binuclear Fe-M-N x sites. 57 Fe Mössbauer spectroscopy revealed that the bimetallic catalysts feature a higher D 1 /D 2 ratio of the spectral signatures assigned to two distinct Fe-N x sites, relative to the FeNC parent catalyst. Furthermore, the addition of the secondary metal favored the formation of D 1 sites, associated with the higher turnover frequency.
36 MATERIALS SCIENCE↗
Coaxial Nanowire Electrodes Enable Exceptional Fuel Cell Durability
Polymer-electrolyte-membrane fuel cells (PEMFCs) hold great promise for applications in clean energy conversion, but cost and durability continue to limit commercialization. This work presents a new class of catalyst/electrode architecture that does not rely on Pt particles or carbon supports, eliminating the primary degradation mechanisms in conventional electrodes, and thereby enabling transformative durability improvements. The coaxial nanowire electrode (CANE) architecture consists of an array of vertically aligned nanowires, each comprising an ionomer core encapsulated by a nanoscale Pt film. This unique design eliminates the triple-phase boundary and replaces it with two double-phase boundaries, increasing Pt utilization. It also eliminates the need for carbon support and ionomer binder, enabling improved durability and faster mass transport. Fuel cell membrane electrode assemblies based on CANEs demonstrate extraordinary durability in accelerated stress tests (ASTs), with only 2% and 5% loss in performance after 5000 support AST cycles and 30000 catalysts AST cycles, respectively. The high-power density and extremely high durability provided by CANEs can enable a paradigm shift from random electrodes based on unstable platinum nanoparticles dispersed on carbon to ordered electrodes based on durable Pt nanofilms, facilitating rapid deployment of fuel cells in transportation and other clean energy applications.
25 ENERGY STORAGE↗
Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution
Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings, high catalyst utilization and facile fabrication are urgently needed to enable cost-effective, green hydrogen production via proton exchange membrane electrolyzer cells (PEMECs). Herein, benefitting from a thin seeding layer, bottom-up grown ultrathin Pt nanosheets (Pt-NSs) were first deposited on thin Ti substrates for PEMECs via a fast, template- and surfactant-free electrochemical growth process at room temperature, showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies. Combined with an anode-only Nafion 117 catalyst-coated membrane (CCM), the Pt-NS electrode with an ultralow loading of 0.015 mg Pt cm -2 demonstrates superior cell performance to the commercial CCM (3.0 mg Pt cm -2 ), achieving 99.5% catalyst savings and more than 237-fold higher catalyst utilization. The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction. Overall, this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.
42 ENGINEERING↗
Grooved electrodes for high-power-density fuel cells
Proton exchange membrane fuel cells (PEMFCs) are leading candidates to decarbonize the transport sector, but widespread deployment will require improvements in lifetime, fuel economy and cost. Here we present the grooved electrode, an alternative electrode structure that enhances PEMFC performance and durability by coupling high ionomer (ion-conducting binder) content for improved H + transport with grooves for rapid O 2 transport. Grooved electrodes provide up to 50% higher performance than state-of-the-art conventional electrodes under standard operating conditions. Fuel cell diagnostics combined with multiphysics modelling demonstrate that grooved electrodes provide facile O 2 transport despite their high ionomer content, enabling improved reaction rate uniformity. Grooved electrodes also provide improved durability, with less performance loss after carbon corrosion compared with baseline electrodes. Machine learning analysis demonstrates the potential to further optimize grooved structures for next-generation PEMFCs with enhanced performance and durability, enabling smaller and cheaper fuel cell stacks with higher fuel efficiency.
25 ENERGY STORAGE↗