Catalyst Degradation Research Articles

Bidentate NHC‐Containing Ligands for Copper Catalysed Synthesis of Functionalised Diaryl Ethers

Diaryl and heteroaryl ethers are important and common motifs in drug discovery and agrochemicals. Here we present a catalytic system for the copper catalysed arylation of phenols with aryl halides. Bidentate N‐heterocyclic carbene ligands provide a well‐defined catalytic system that enable low loading of copper in effective coupling reactions (0.5 mol% Cu or lower). The reaction scope of aryl iodides and aryl bromides is developed, that is tolerant of functional groups and a library of biaryl ethers with lead‐like properties is prepared. The presence of excess ligand (in a 1:3 ratio) is shown to be optimal to prevent catalyst degradation, presumably by avoiding decomplexation of the ligand. This is also supported by the catalytic results obtained with pre‐formed copper complexes. The kinetics of the reaction are examined and shown to be first order in copper, supportive of a well‐defined catalyst species, first order in phenol and aryl iodide, and zero order in base under the developed conditions. Computational studies performed using Minnesota MN15‐L parametrisation method support an oxidative addition–reductive elimination pathway. Reductive elimination would be turnover limiting and occurr through an intimate ion pair intermediate.

Deciphering Electrocatalytic Hydrogen Production in Water Through a Bioinspired Water-Stable Copper(II) Complex Adorned with (N2S2)-Donor Sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H2 generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-LN2S2]ClO4, featuring the N,S-type ligand, LN2S2 (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by H2O during electrochemical conditions yielding [H2O-Cu-LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s-1 for hydrogen generation. Controlled potential electrolysis at -1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2 %. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post-CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton-electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.

Performance and Durability of Heavy-Duty Fuel Cell Systems with an Advanced Ordered Intermetallic ORR Alloy Catalyst and Novel Support

Abstract Ordered PtCo intermetallic (OIM) catalyst (L10-PtCo/C) is a promising candidate as the oxygen reduction reaction (ORR) catalyst in hybrid fuel cell systems (FCS) for class-8 heavy duty (HD) trucks. Compared to a baseline annealed Pt on high surface area carbon (a-Pt/HSC) catalyst, its mass activity (MA) is 71% higher initially and 144% higher after 90,000 potential cycles in an accelerated stress test (AST). Analysis of the AST data indicates that the ORR kinetic constants do not change with aging and the degradation in the OIM catalyst activity is linearly proportional to the loss in the electrochemically active surface area (ECSA). Several operational strategies are investigated to mitigate catalyst degradation and achieve 25,000-h electrode lifetime and 2.5 kW/g Pt utilization on a HD truck duty cycle including load sharing with the hybrid battery, regulating the radiator fan power to maintain the coolant temperature close to 60oC, clipping the maximum cell voltage below 850 mV, limiting the ECSA loss to 55%, and oversizing the membrane active area by 20%. Drive cycle simulations indicate that the lifetime average voltage degradation rate is about 1.8 V/h and the integrated stack and FCS drive cycle efficiencies decrease by 3.5 to 3.9%.

Parallel and High Throughput Reaction Monitoring with Computer Vision

AbstractWe report the development and applications of a computer vision based reaction monitoring method for parallel and high throughput experimentation (HTE). Whereas previous efforts reported methods to extract bulk kinetics of one reaction from one video, this new approach enables one video to capture bulk kinetics of multiple reactions running in parallel. Case studies, in and beyond well‐plate high throughput settings, are described. Analysis of parallel dye‐quenching hydroxylations, DMAP‐catalysed esterification, solid‐liquid sedimentation dynamics, metal catalyst degradation, and biologically‐relevant sugar‐mediated nitro reduction reactions have each provided insight into the scope and limitations of camera‐enabled high throughput kinetics as a means of widening known analytical bottlenecks in HTE for reaction discovery, mechanistic understanding, and optimisation. It is envisaged that the nature of the multi‐reaction time‐resolved datasets made available by this analytical approach will later serve a broad range of downstream efforts in machine learning approaches to exploring chemical space.

Correlating Catalyst Growth with Liquid Water Distribution in Polymer Electrolyte Fuel Cells.

This study investigates the impact of liquid water distribution in a polymer electrolyte fuel cell (PEFC) on the spatially heterogeneous platinum (Pt) catalyst degradation. The membrane electrode assemblies (MEAs) are aged using accelerated stress tests (ASTs) in varied cathode gas environments (N2 and air) to instigate Pt catalyst degradation. The study employs high-resolution neutron imaging and synchrotron micro-X-ray diffraction (micro-XRD) to map liquid water distribution and Pt particle size, respectively. Neutron radiographs reveal liquid water accumulation primarily within the diffusion media, especially under flow field lands, due to thermal resistance differences between channels and lands. Aged MEAs exhibit increased water retention, likely due to increased hydrophilicity of the diffusion media with aging. Synchrotron micro-XRD maps unveil significant heterogeneity in Pt particle size distribution in the aged MEAs, correlated with preferential liquid water accumulation under flow field lands. This study highlights the critical role of flow field design and water distribution in catalyst degradation, underscoring the need for innovative strategies to enhance fuel cell durability and performance.

Modeling of Catalyst Degradation in Polymer Electrolyte Membrane Fuel Cells Applied to Three‐Dimensional Computational Fluid Dynamics Simulation

ABSTRACTIn a polymer electrolyte membrane (PEM) fuel cell, the following degradation mechanisms are associated with the catalyst particles and their support: carbon support corrosion triggered by carbon and platinum oxidation, platinum dissolution with redeposition, and particle detachment with agglomeration. In this work, an electrochemical model for those degradation effects is presented as well as its coupling with a three‐dimensional computational fluid dynamics PEM fuel cell performance model. The overall model is used to calculate polarization curves and current density distributions of a PEM fuel cell in a fresh and aged state as well as the degradation process during an accelerated stress test with 30 000 voltage cycles. The obtained simulation results are compared to measurements on a three‐serpentine channel PEM fuel cell with an active area of 25 cm2 under various temperatures and humidities. The experimental data are obtained with a segmented test cell using respective degradation protocols and test conditions proposed by the United States Department of Energy. In addition to the temperature and humidity changes, the influence of geometry and material parameters on the degree of degradation and the resulting fuel cell performance is explored in detail.

Optimizing the stability of NiFeOOH via oxyanion intercalation for water oxidation at large current densities

In alkaline water splitting, transition metals (Ni, Fe) have received extensive attention, and NiFe-oxyhydroxide (NiFeOOH) is regarded as an exceptionally active electrocatalysts for oxygen evolution reaction (OER). However, maintaining the long-term stability of NiFeOOH at high current densities is challenging due to Fe segregation and catalyst degradation. Herein, this study proposes an approach to enhancing the stability of the Ni/Fe-O covalent bond by intercalating oxyanions (NO3–, PO43-, SO42-, and SeO42-) into the NiFeOOH substrate, improving its resistance to bond breakage. And the NiFeOOH-NO3− electrocatalyst was found to be optimal, achieving an overpotential of 311 mV and stable performance at 1 A cm−2 for several hundred hours. Consequently, NiFeOOH-NO3– exhibited a significantly improved OER stability, with a mere 3.33 % stability attenuation after 100 h, compared to 13.19 % for pristine NiFeOOH. Notably, the presence of NO3– in NiFeOOH effectively mitigates Fe segregation, leading to a fourfold enhancement in long-term stability relative to that of NiFeOOH without NO3– modification. Theoretical calculations show that the introduction of NO3– effectively shifts metal 3d band centers of NiFeOOH closer to the Fermi level. It is suggested that the oxyanions lead to increased strength of the Ni/Fe-O bonds, thereby inhibiting the dissolution of Fe and enhancing the stability of NiFeOOH phase. This research represents a significant advance in controlling Fe segregation to stabilize NiFe-based electrocatalysts for high-current–density water oxidation.

Origins of Nanoalloy Catalysts Degradation during Membrane Electrode Assembly Fabrication

Origins of Nanoalloy Catalysts Degradation during Membrane Electrode Assembly Fabrication

Post mortem Study of Catalyst Degradations Occurring in High-Temperature Proton Exchange Membrane Fuel Cells Upon Start-Stop Operation

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) could replace fossil fuel-based technologies for applications which cannot involve bulky/heavy cooling systems, such as aeronautics. However, severe materials degradations upon operation prevent performance retention for acceptable lifetimes. While others have already reported degradations in HT-PEMFC, post mortem characterizations of used HT-PEMFC membrane electrode assemblies (MEAs) remain scarce. Herein, HT-PEMFC performance degradation is studied by applying a startup/shutdown protocol to a short-stack operated at 160 °C; one MEA is characterized using complementary physicochemical/electrochemical techniques to identify/understand the degradation mechanisms and their origin. This start/stop operation mode (co-flow gas reactants) leads to substantial degradation inhomogeneity. For the anode, migration, coalescence, and detachment of Pt nanoparticles are witnessed induced by high-surface-area carbon support functionalization and corrosion. The anode electrochemical surface area (ECSA) remains constant at the inlet and increases significantly at the outlet, following inhomogeneous degradation of the cathode catalyst: the Ptz+ ions formed at high potential/oxidizing conditions concentrate towards the outlet, where they redeposit locally or at the anode, after diffusion/migration across the PBI membrane. Hence, the cathode ECSA decreases significantly at the inlet. Furthermore, intense Ni-leaching from the initial PtNi alloy catalyst is reported as a result of O2 mass-transport and phosphoric acid dilution inhomogeneity.

Effect of High-Temperature Operation on Voltage Cycling Induced PEMFC Degradation: From Automotive Customer Drive Cycles to an Accelerated Stress Test

Degradation of the Pt catalyst during load cycling constitutes a major durability issue for proton exchange membrane fuel cells (PEMFCs) in automotive applications. In this study commercial 5 cm2 electrodes were exposed to 20 k voltage cycles between 0.6–0.9 VRHE at temperatures ranging from 75 to 120 °C. The electrochemical surface area (ECSA), the roughness factor (rf), and the oxygen transport resistance were investigated over the course of the test. The degradation was mainly governed by Pt agglomeration and was accelerated with increasing temperature. Interestingly, operation at high temperature (120 °C and 30% RH) caused the same ECSA loss as at standard conditions (90 °C and 90% RH), suggesting that when maintaining dry conditions high-temperature operation is not critical for the durability of the catalyst material. The experimental results were used to validate an existing 0D catalyst degradation model, which was then applied to an automotive customer drive cycle. The calculated degradation over the whole automotive lifetime (excluding startup shutdown and idle events) equals 20 k voltage cycles (0.6–0.9 V, 10 s hold time) at 90 °C and 30% RH, which provides a guideline for the assessment of the suitability of novel catalyst materials for automotive applications.

Durability of Highly Active PGM Catalyst MEA Tested Via Nitrogen and Air AST Cycling Under HDV Condition

PEMFCs are widely considered as the most promising power sources, particularly for heavy-duty vehicles (HDVs). Unfortunately, the degradation of MEAs under HDV condition remains insufficiently studied. In this work, we systematically investigated two MEAs with catalysts of Pt nanoparticles (NPs) supported over high surface area carbon black. These MEAs were tested for durability under HDV condition in nitrogen using a DOE AST protocol for 180,000 cycles, which is equivalent to 30,000 hours or 1 million miles of operation. The commercial Catalyst MEA also underwent 6,000 AST cycles in air under M2FCT condition. We comprehensively investigated the degradation of catalysts. Our results indicate that both MEAs undergo continuous performance degradation in H2/air and H2/O2 during the AST cycling in nitrogen, where analysis employing scanning transmission electron microscopy (STEM) and inductively coupled plasma mass spectrometry (ICP-MS) reveal significant degradation behavior for Pt catalysts. The MEA exhibits more significant degradation, especially within mass transfer region, during the AST process in air. This study describes the long-term degradation behavior and mechanism with AST cycling in nitrogen or air governing highly efficient and durable PGM-catalyst MEA design under HDV conditions.

Deciphering Anion Exchange Membrane Water Electrolysis: A Distribution of Relaxation Times Approach

Anion exchange membrane water electrolysis (AEM-WE) is a promising method for hydrogen production, offering advantages over proton exchange membrane water electrolysis (PEM-WE), such as the use of nonprecious metal catalysts and perfluorosulfonic acid free membranes. Despite achieving impressive current densities, challenges in efficiency and stability remain. This study employs electrochemical impedance spectroscopy (EIS), the equivalent circuit model (ECM) and distribution of relaxation times (DRT) analysis to investigate AEM-WE cells. DRT analysis identifies and quantifies five loss mechanisms within the AEM-WE system, including hydrogen and oxygen evolution reactions and ionic transport losses. Long-term experiments reveal catalyst degradation and its impact on performance, providing insights for targeted optimisation. The findings enhance understanding of the electrochemical processes in AEM-WE, offering pathways to improve stability and efficiency.

Deciphering Anion Exchange Membrane Water Electrolysis: A Distribution of Relaxation Times Approach

Anion exchange membrane water electrolysis (AEM-WE) is a promising method for hydrogen production, offering advantages over proton exchange membrane water electrolysis (PEM-WE), such as the use of nonprecious metal catalysts and perfluorosulfonic acid free membranes. Despite achieving impressive current densities, challenges in efficiency and stability remain. This study employs electrochemical impedance spectroscopy (EIS), the equivalent circuit model (ECM) and distribution of relaxation times (DRT) analysis to investigate AEM-WE cells. DRT analysis identifies and quantifies five loss mechanisms within the AEM-WE system, including hydrogen and oxygen evolution reactions and ionic transport losses. Long-term experiments reveal catalyst degradation and its impact on performance, providing insights for targeted optimisation. The findings enhance understanding of the electrochemical processes in AEM-WE, offering pathways to improve stability and efficiency.

Synthesis, Performance Measurement of Dy2EuSbO7/ZnBiDyO4 Heterojunction Composite Catalyst and Photocatalytic Degradation of Chlorpyrifos within Pesticide Wastewater under Visible Light Irradiation

For the first time, a novel catalyst named Dy2EuSbO7 was successfully synthesized via the high-temperature solid-state sintering method (HTSSM). Dy2EuSbO7/ZnBiDyO4 heterojunction photocatalyst (DZHP) was fabricated through the HTSSM for degrading chlorpyrifos (CPS) in the pesticide wastewater under visible light irradiation (VSLID). Under VSLID, DZHP could effectively degrade CPS in pesticide wastewater. The experimental outcomes suggested that the kinetic curve with the Dy2EuSbO7/ZnBiDyO4 heterojunction (DZH) as a photocatalyst for the reduction of CPS under VSLID conformed to the first-order kinetics (FOKT). After VSLID of 156 min, the photocatalytic degradation (PTD) removal rate of CPS using DZH as photocatalyst was 1.12 times, 1.21 times, or 2.96 times that using Dy2EuSbO7 as a photocatalyst, ZnBiDyO4 as a photocatalyst, or nitrogen-doped titanium dioxide as a photocatalyst. After VSLID of 156 min for four cycle degradation tests (FCDTS) with DZH as a photocatalyst, the removal rate of CPS reached 98.78%, 97.66%, 96.59%, and 95.69%, respectively. Above results indicated that the DZHP possessed high stability. Experiments with the addition of trapping agents showed that hydroxyl radicals (•OH) owned the strongest oxidative removal ability for degrading CPS compared with superoxide anions (•O2−) or holes (h+). The oxidation capacity of three oxidation radicals for eliminating CPS was ranked in the ascending order as follows: h+ < •OH < •O2−. Lastly, the possible degradation pathway and degradation mechanism of CPS were discussed in detail. A visible light responsive heterojunction catalyst with high catalytic activity and a photocatalytic reaction system which were capable of efficiently removing toxic organic pollutants from pesticide wastewater were obtained.

Effect of CO2 deficiency on the performance of membrane electrode CO2 electrolyzer

To mitigate greenhouse effects, carbon dioxide reduction reaction (CO2RR) has been used as an efficient means of carbon reduction. In CO2 electrolyzer, CO2 deficiency can happen and degrade the reaction efficiency. Herein, an efficient and long-lived formic acid three-cell electrolyzer is used to study the effect of CO2 deficiency, by operating the electrolyzer from full CO2 supply to CO2 deficiency. In addition, the effects of various CO2 fluxes and concentrations on the electrolyzer current, acid concentration and lifetime are investigated. This study quantitatively reveals the impact of CO2 deficiency on current density, product selectivity, and electrolyzer lifetime. The findings indicate that current density decreases by 12.74 %, while CO2 conversion efficiency drops by 92.5 %, demonstrating a significant reduction in the reactivity of CO2 conversion to formate ions. Conversely, the hydrogen evolution reaction is enhanced. Prolonged CO2 deficiency (below 13 ml/min) can also lead to catalyst degradation, including separation and dissolution within the cathode catalyst layer, ultimately diminishing overall performance. Compared with the CO2 flux, the CO2 concentration exerts a more pronounced influence. To ensure the electrolysis efficiency, the carbon dioxide concentration should not be less than 80 %.

In Situ Analysis of Binder Degradation during Catalyst-Accelerated Stress Test of Polymer Electrolyte Membrane Fuel Cells.

High-oxygen-permeability ionomers (HOPIs) are being actively developed to enhance the performance and durability of high-power polymer electrolyte membrane fuel cells (PEMFCs). While methods for evaluating binder performance are well-established, techniques for assessing binder durability and measuring its degradation in situ during the AST process remain limited. This study examines the distribution of relaxation times (DRT) and Warburg-like response (WLR) methods as in situ analysis techniques during the catalyst-accelerated stress test (AST) process. We conducted catalyst-ASTs (0.6-0.95 V cycling) for 20,000 cycles, monitoring changes using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Contrary to expectations, during the catalyst-AST, the ion transport resistance of the binder decreased, indicating no binder degradation. Scanning electron microscopy/energy dispersive spectrometer (SEM/EDS) analysis revealed that the degradation rate of the catalyst and the support was relatively higher than that of the binder, leading to a reduction in catalyst layer thickness and improved binder network formation. By applying the DRT method during the catalyst-AST process, we were able to measure the increase in oxygen reduction reaction (ORR) resistance and the decrease in proton transport resistance in situ. This allowed for the real-time detection of the reduction in catalyst layer thickness and improvements in ionomer networks due to catalyst and support degradation. These findings provide new insights into the complex interplay between catalyst degradation and binder performance, contributing to the development of more durable PEMFC components.

Parallel and High Throughput Reaction Monitoring with Computer Vision.

We report the development and applications of a computer vision based reaction monitoring method for parallel and high throughput experimentation (HTE). Whereas previous efforts reported methods to extract bulk kinetics of one reaction from one video, this new approach enables one video to capture bulk kinetics of multiple reactions running in parallel. Case studies, in and beyond well-plate high throughput settings, are described. Analysis of parallel dye-quenching hydroxylations, DMAP-catalysed esterification, solid-liquid sedimentation dynamics, metal catalyst degradation, and biologically-relevant sugar-mediated nitro reduction reactions have each provided insight into the scope and limitations of camera-enabled high throughput kinetics as a means of widening known analytical bottlenecks in HTE for reaction discovery, mechanistic understanding, and optimisation. It is envisaged that the nature of the multi-reaction time-resolved datasets made available by this analytical approach will later serve a broad range of downstream efforts in machine learning approaches to exploring chemical space.

Investigation of Iridium Catalyst Degradation in PEM Water Electrolyzers: Current Density or Cell Voltage?

Proton exchange membrane (PEM) water electrolyzers represent a cornerstone technology in the sustainable production of green hydrogen. However, their large-scale commercialization is hindered by catalyst degradation, particularly the iridium-based anode, which compromises the efficiency and durability of the stack. This study delves into the degradation mechanism(s) of the Ir-based catalyst in the anode of PEM electrolyzers, focusing on the influence of operating conditions such as current density and cell voltage. We have utilized the state-of-the-art R&D platform “PEMI” at Plug Power to construct a rainbow stack that contains several 50 cm2 membrane electrode assemblies (MEAs) with different membrane thicknesses. This innovative approach enables identical current densities across different MEAs while varying the cell voltage on the anode catalyst layer, thereby isolating the effect of cell voltage from current on catalyst degradation.Our investigation seeks to clarify the puzzle whether it is the current density or the cell voltage that determines the transition and degradation of iridium-based catalysts. Preliminary results indicate that different oxidation states of Iridium exhibit significantly different kinetics and conductivity at varied cell voltages. This is corroborated by our synchrotron-based in situ X-ray absorption spectroscopy experiments that unraveled evolution of the anode catalyst layer at elevated cell voltages. By systematically analyzing the degradation patterns of MEAs with different membrane thickness under controlled conditions, we pinpointed the operational parameter that drives catalyst degradation. The finding provides in-depth understanding of the underlying principles that govern the iridium-based catalyst durability and points to strategies mitigating the degradation. It will pave the way for more resilient and efficient PEM water electrolyzers. Acknowledgement. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory Contract DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium Grant DE-SC0012335.Keywords: PEM water electrolyzers, catalyst degradation, iridium, current density, cell voltage, MEAs.

Degradation and Protection Mechanisms of Platinum-Based Catalysts in Hydrogen-Bromine Flow Batteries

Cost-effective and large-scale electrical energy storage is pivotal in facilitating the assimilation of renewable energy sources like wind and solar, as well as enhancing the resilience of the future electricity grid. Hydrogen-Bromine flow battery (HBFB) technology is a candidate for a low cost and flexible system. Bromine is abundantly available on Earth. In addition, the reaction between bromine and bromide is characterized by rapid kinetic properties, thus no platinum group metals (PGMs) are required on the bromine side of the cell as a catalyst to sustain a high current density of >500 mA/cm2. Moreover, hydrogen-based flow batteries can be coupled with hydrogen pipelines & electrolyzers to boost the integration of new energy systems.However, the selection of bromine brings technical challenges that can limit the commercial deployment of such HBFB systems. We have proven a lifetime of more than 8,000 hours of continuous cycling at the lab scale. During this proof-of-concept validation, we found that bromine species (liquid) crosses through a dense proton exchange membrane to the hydrogen side of the cell. On this side, a Platinum-based catalyst layer is present to promote hydrogen oxidation-evolution reactions (HOR/HER). The crossover liquid interacts first with the catalyst layer before it crosses through the gas diffusion layer and exits the membrane electrode assembly (MEA). Chemical interactions between the crossover liquid and the catalyst can lead to catalyst migration, Ostwald ripening, or even permanent catalyst dissolution. This is a concern and must be addressed. The root of this concern is that the Platinum-based catalyst is highly reactive (high surface-active area respective to the loading, m2/g), and also the crossover bromine species are likely corrosive (highly acidic, pH <0, and contain polybromides). Therefore, chemical interaction cannot be fully avoided. Nevertheless, the cathodic protection reduces this interaction, which prolongs the lifetime of the electrochemical system. The cathodic protection consists of an applied positive potential and the presence of hydrogen gas on the catalyst nanoparticles. The catalyst degradation together with cathodic protection needs to be better understood and quantified to gain the confidence that the HBFB system fundamentally can last for more than 10 years of continuous operation. This confidence is essential to deliver a minimum viable product (MVP) of HBFB, e.g. on a 100 kW – 1 MW scale, to the market.To address the aforementioned scientific challenges, this work studies the liquid crossover phenomena and the interaction between the crossover liquid and platinum-based catalyst in depth. Liquid crossover rate, concentration, and bromine speciation from working electrochemical cells are quantified at different states of charge (SoCs) and different modes (charge or discharge). This information is used to set up further ex-situ experiments to understand and determine the chemical interaction between crossover liquid and catalyst. Electrochemical ex-situ tests for Pt dissolution measurement such as determination of the electrochemically active surface area (ECSA), are performed before and after soaking hydrogen electrodes in different concentrations of hydrogen bromide solutions that mimic the crossover liquid. These results are then combined with in-situ tests, where the catalyst dissolution rate is quantified in actual crossover liquid and electrolyte by the inductively coupled plasma (ICP) method. Finally, post-mortem analyses on the catalyst layer based on scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. will give quantitative and qualitative insights into the impact of cycling and liquid crossover on the catalyst performance, morphology, crystal structure, and chemical state of the catalyst.The goal of this work is to quantify the extrapolated lifetime of HBFB systems within a high confidence level. Then conclude if this technology is fundamentally sound and can be scaled up to an MVP to be deployed to the market. As a low cost energy storage solution, the HBFB’s lifetime should be at least 5 years and preferably more than 10 years to attract commercial attention. Moreover, the collective knowledge gained in this work about the catalyst degradation mechanisms will spark further ideas and guide the next generation of the system and its operating conditions to reduce the degradation rate. These presented ideas may also shine a light on catalyst degradation and protection mechanisms in other electrochemical applications that operate in corrosive conditions.Figure 1 Membrane electrode assembly architecture, incl. electrochemical reactions and species transport phenomena in the charge and discharge modes. Figure 1

Development of a Rotating Disk Electrode-Based Ru-Leaching AST for PEM Fuel Cell Reformate Anode Ru-Pt/C Catalysts

Extreme heavy-duty (e.g., maritime) applications of PEM fuel cells often require liquid hydrogen carriers as fuel.[1] In the case of methanol, it is mixed with steam and converted to hydrogen and CO2 in a catalytic reformation process.[2] While a multi-step approach, including the water-gas shift reaction and selective oxidation processes, is typically undertaken to fully convert methanol to hydrogen and CO2, low ppm-level amounts of CO remain in the resulting “reformate hydrogen” gas stream.[3] This CO concentration is significantly higher than deemed non-poisonous to the platinum catalyst on the anode (i.e., < 0.2 ppm),[4] and a more CO-tolerant anode catalyst is required. To address this issue, RuPt-alloy nanoparticles supported on carbon are employed, leading to CO-tolerance of the HOR-catalysts on the anode at reformate conditions.[3] However, previous works found that during operation, Ruthenium leaches from the anode catalyst layer and travels through the membrane, subsequently depositing on the platinum nanoparticles, effectively poisoning the cathode Pt/C catalyst and significantly reducing its activity towards the oxygen reduction reaction.[3,5] To eliminate or reduce Ru-leaching from RuPt/C catalysts while retaining its inherent CO-tolerance, efforts tuning the catalyst’s (surface) composition were made. However, as the leaching of Ru in fuel cells occurs over thousands of hours, the use of an accelerated stress test (AST) for reformate anodes is required. In one of our previous efforts, an AST for Ru-leaching in fuel cells was used to study RuPt/C degradation.[3] However, the amount of material, MEA preparation time and AST measurement time required for such a test was found to be too high for catalyst development. Additionally, fuel cell measurement capacity is limited due to its high cost and the quantification of the total amount of Ru-leached remained challenging.In light of this, in this work, we developed an AST aimed at achieving a reliable yet short and less material consuming protocol, enabling us to quantitatively investigate the Ru-leaching of RuPt-materials during catalyst development. This was achieved by using the rotating disk electrode (RDE) configuration, a well-established electrocatalyst characterization and pre-testing method.[6] The RDE-based AST-protocol was developed using three commercial RuPt-catalysts with varying Ru:Pt ratios of 1:1, 1.5:1, and 2:1 while possessing a comparable particle size and electrochemical surface area. Additionally, the commercial catalyst with a 2:1 atomic ratio catalyst was used in a heat-treated form leading to a larger particle size and lower ECSA.The AST-protocol was comprised of a series of voltammetric cycles aimed at aging the catalyst. During the protocol development, the number of aging cycles (100 – 1000), the scan rate (10 – 100 mV s-1), and the upper inversion potential (0.8 – 0.9 VRHE) of the cyclic voltammograms were varied to investigate their influence on catalyst degradation. This was achieved by collecting the electrolyte (Ar-saturated 0.1M H2SO4) after the AST-cycles and subsequent quantification of the dissolved Ru using inductively coupled plasma optical emission spectroscopy (ICP-OES). Furthermore, the change in the surface composition was qualitatively analyzed by comparing the CO-oxidation peak shape and position before and after the AST-cycling. Examples of the ICP-OES and CO-stripping results for the systematic investigation of the influence of cycle number and scan rate on the 1.5:1 Ru:Pt catalyst using an upper inversion potential of 0.85 VRHE are displayed in Figure 1. Based on this rigorous investigation of the parameters influencing Ru-dissolution in an RDE-environment and after the necessary validation of the results found using the finalized protocol in MEA-based testing,[5] the developed protocol could subsequently be applied to self-synthesized RuPt/C materials as well as RucorePtshell-catalysts.In summary, this contribution showcases the development of a reliable rotating disk electrode-based accelerated stress test protocol for Ru-leaching from RuPt/C catalysts. Furthermore, its validation with commercial catalysts as well as its application to self-synthesized PEM fuel cell anode catalysts for use with reformate hydrogen, is presented.