Catalyst Degradation Research Articles

Extrinsic hydrophobicity-controlled silver nanoparticles as efficient and stable catalysts for CO2 electrolysis.

To realize economically feasible electrochemical CO2 conversion, achieving a high partial current density for value-added products is particularly vital. However, acceleration of the hydrogen evolution reaction due to cathode flooding in a high-current-density region makes this challenging. Herein, we find that partially ligand-derived Ag nanoparticles (Ag-NPs) could prevent electrolyte flooding while maintaining catalytic activity for CO2 electroreduction. This results in a high Faradaic efficiency for CO (>90%) and high partial current density (298.39 mA cm‒2), even under harsh stability test conditions (3.4 V). The suppressed splitting/detachment of Ag particles, due to the lipid ligand, enhance the uniform hydrophobicity retention of the Ag-NP electrode at high cathodic overpotentials and prevent flooding and current fluctuations. The mass transfer of gaseous CO2 is maintained in the catalytic region of several hundred nanometers, with the smooth formation of a triple phase boundary, which facilitate the occurrence of CO2RR instead of HER. We analyze catalyst degradation and cathode flooding during CO2 electrolysis through identical-location transmission electron microscopy and operando synchrotron-based X-ray computed tomography. This study develops an efficient strategy for designing active and durable electrocatalysts for CO2 electrolysis.

Deactivation mechanism for water splitting: Recent advances

AbstractHydrogen (H2) has been regarded as a promising alternative to fossil‐fuel energy. Green H2 produced via water electrolysis (WE) powered by renewable energy could achieve a zero‐carbon footprint. Considerable attention has been focused on developing highly active catalysts to facilitate the reaction kinetics and improve the energy efficiency of WE. However, the stability of the electrocatalysts hampers the commercial viability of WE. Few studies have elucidated the origin of catalyst degradation. In this review, we first discuss the WE mechanism, including anodic oxygen evolution reaction (OER) and cathodic hydrogen evolution reaction (HER). Then, we provide strategies used to enhance the stability of electrocatalysts. After that, the deactivation mechanisms of the typical commercialized HER and OER catalysts, including Pt, Ni, RuO2, and IrO2, are summarized. Finally, the influence of fluctuating energy on catalyst degradation is highlighted and in situ characterization methodologies for understanding the dynamic deactivation processes are described.

Photoilluminated Redox-Processed Rh2P Nanoparticles on Photocathodes for Stable Hydrogen Production in Acidic Environments.

While photoelectrochemical (PEC) cells show promise for solar-driven green hydrogen production, exploration of various light-absorbing multilayer coatings has yet to significantly enhance their hydrogen generation efficiency. Acidic conditions can enhance the hydrogen evolution reaction (HER) kinetics and reduce overpotential losses. However, prolonged acidic exposure deactivates noble metal electrocatalysts, hindering their long-term stability. Progress requires addressing catalyst degradation to enable stable, efficient, and acidic PEC cells. Here, we proposed a process design based on the photoilluminated redox deposition (PRoD) approach. We use this to grow crystalline Rh2P nanoparticles (NPs) with a size of 5-10 on 30 nm-thick TiO2, without annealing. Atomically precise reaction control was performed by using several cyclic voltammetry cycles coincident with light irradiation to create a system with optimal catalytic activity. The optimized photocathode, composed of Rh2P/TiO2/Al-ZnO/Cu2O/Sb-Cu2O/ITO, achieved an excellent photocurrent density of 8.2 mA cm-2 at 0 VRHE and a durable water-splitting reaction in a strong acidic solution. Specifically, the Rh2P-loaded photocathode exhibited a 5.3-fold enhancement in mass activity compared to that utilizing just a Rh catalyst. Furthermore, in situ scanning transmission electron microscopy (STEM) was performed to observe the real-time growth process of Rh2P NPs in a liquid cell.

Revealing the critical role of low voltage excursions in enhancing PEM fuel cell catalyst degradation by automotive hydrogen/air potential cycling experiments

The durability of Polymer Electrolyte Membrane Fuel Cells under dynamic operation still needs to be improved. To understand the automotive voltage cycling-induced catalyst degradation, the loss of the electrochemically active surface area (ECSA) is investigated through an experimental campaign on Membrane Electrode Assemblies. Ad-hoc hydrogen/air accelerated protocols were designed to evaluate the voltage profile impact in a range relevant for both automotive and heavy duty transport application (<0.90 V). Besides the well-known aging dependence on the upper potential limit, this work evidences the critical role of the short-stops, characterized by low voltage transients. Effort was spent in studying this procedure parameters (voltage level, duration, scan rate, humidification). The accelerated ECSA loss is due to Pt nanoparticles coarsening as proved by transmission electron microscopy and is suspected dominated by Pt cathodic dissolution, incentivized during excursions towards very low potentials (<0.4 V). These findings help the development of system mitigation strategies.

Engineering the orbital splitting and electronic reoccupation at alkali-metal-doped perovskites with face-shared IrO6 octahedral dimers

The intriguing catalysts with excellent catalytic activity and durable stability in acidic oxygen evolution reaction (OER) are extremely desirable for efficient energy conversion. Herein, engineering the orbital splitting and electronic reoccupation at metal sites of alkali-metal-doped perovskites with face-shared IrO6 octahedral dimers is realized through structural distortion and symmetry breaking in an effort to boost the sluggish reaction kinetics and mitigate the degradation of the Ir-based catalysts in acidic electrolyte as well. Doping Na or K element can increase the oxidation state of Ir at IrO6 octahedral dimers, which not only displaces the Ir d-band centers for higher catalytic activity but also leads to a good stability of Ir centers with higher dissolution potentials. This work provides a new insight into enhancing the reactive activity by doping alkali metals.

Numerical simulation for non-uniform PtCo catalyst degradation under different coolant conditions and its effect on PEMFC performance

Long-term non-uniform temperature, pressure and reaction rates distributions in the proton exchange membrane fuel cells (PEMFCs) may result in local catalyst degradation and deteriorate PEMFC performance. However, the problem of non-uniform catalyst degradation in PEMFC stacks is still incompletely understood due to the lacking of advanced experimental methods and three-dimensional (3D) catalyst aging models. In this study, a 3D PtCo alloy catalyst degradation model under voltage cycles is built and a 25 cm2 PEMFC stack containing realistic cathode, anode as well as coolant flow fields is used as the computational domain to analyze in detail the influence of non-uniform catalyst degradation on the performance of the PEMFC during different coolant conditions. The simulation results show that the non-uniform catalyst degradation is strongly dependent on the cathode flow field structure. It can alleviate non-uniform catalyst degradation as well as contribute to improving PEMFC performance when the coolant flow direction is the same as the air, and both coolant flow rate and inlet temperature also are found to significantly affect the local catalyst degradation behavior. Therefore, an optimally designed cathode flow fields structure as well as good water and heat management during operation can help to extend the service life of the PEMFC.

Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions.

Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer.

Antioxidant-driven activity and stability enhancement in multiphase bicarbonate hydrogenation catalysis with a Ru-PNP pincer complex

Herein, we present a practical strategy to enhance the performance of a multiphase system for bicarbonate hydrogenation based on a molecular Ru-PNP pincer catalyst. This study demonstrates that the use of organic antioxidants not only mitigates catalyst degradation but also significantly boosts its intrinsic activity. This enables efficient catalyst recycling at ultra-low concentrations. Systematic screening and optimization of a range of organic antioxidants has identified TDTBP (tris(2,4-di-tert-butylphenyl) phosphite) as being exceptionally efficient in stabilizing and enhancing the performance of the Ru-PNP catalyst. With the optimized system an unprecedented integral turnover frequency (TOF) of 115,000 h−1 and a total turnover number (TTON) of 9.43×106 across four recycling tests were demonstrated, conducted at a reaction temperature of 90 ºC and H2 pressure of 50 bar. These findings represent a substantial advancement in sustainable formate/formic acid production, offering a scalable and highly efficient method suitable for industrial-scale application.

Observation on Microenvironment Changes of Dynamic Catalysts in Acidic CO2 Reduction.

Electrochemical CO2 reduction reaction (CO2RR) in acid can solve alkalinity issues while highly corrosive and reductive acidic electrolytes usually cause catalyst degradation. Inhibiting catalyst degradation is crucial for the stability of acidic CO2RR. Here, we reveal the microenvironment changes of dynamic Bi-based catalysts and develop a pulse chronoamperometry (CA) strategy to improve the stability of acidic CO2RR. In situ fluorescence mappings show that the local pH changes from neutral to acid, and the in situ Raman spectra reveal the dynamic evolution of interfacial water structures in the microenvironment. We propose that the surface charge properties of dynamic catalysts affect the competitive adsorption of K+ and protons, thereby causing the differences in local pH and CO2RR intermediate adsorption. We also develop a pulse CA strategy to reactivate catalysts, and the stability of acidic CO2RR is improved by 2 orders of magnitude for 100 h operation, which is higher than most reports on the stability of acidic CO2RR. This work gives insights on how microenvironment changes affecting the stability of acidic CO2RR, and provides guidance for designing stable catalysts in acidic electrolytes.

A small angle X-ray scattering approach for investigating fuel cell catalyst degradation for both ex situ and in operando analyses

Detailed multi-technique characterization of catalyst layer degradation is fundamental for improving catalyst stability and performances in Proton Exchange Membrane Fuel Cells (PEMFCs), and Small Angle X-Ray Scattering (SAXS) coupled to chemical and/or electrochemical analysis can provide important insights of processes involved in catalyst coarsening. In this extent, we present an approach to SAXS analysis able to describe all of the layers composing the Membrane Electrode Assembly (MEA): electrolyte, catalyst support, catalyst nanoparticles, and gas diffusion layers. This approach was used to compare morphological evolution of small clusters formed by catalyst nanoparticles in pristine and aged MEAs in both ex situ and in operando conditions, on a standard SAXS beamline, without exploiting the advantages of anomalous SAXS. Twin MEAs were aged with two different types of Accelerated Stress Tests (AST): one addressed to the catalyst support (s-AST) and one targeting the catalyst layer (c-AST). Limited growth of catalyst nanoparticle size was found when running s-AST, while remarkable evolution was revealed once applying c-AST. Such a difference was mainly reconducted to the disconnection of catalyst nanoparticles from the electrical paths, as supported by analysis of specific Electrochemically Active Surface Area (ECSA). In both cases, the small clusters were found becoming more compact after AST were run.

Experimental and numerical analysis of the effects of thermal degradation on carbon monoxide oxidation characteristics of a three-way catalyst

This work investigates oxygen-storage capacity (OSC) changes during thermal degradation in modern three-way catalysts. Two experiments are performed using catalysts with different degradation degrees to evaluate OSC and reaction rates. The CO2 production test, where CO and O2 are supplied at a constant temperature, shows decreased CO2 production with more degraded catalysts and reduced purification. The CO2 production test is conducted using transient temperature increases, showing that the maximum CO2 production temperature increases with catalyst degradation. The results reveal an increase in activation energy in the oxygen desorption reaction caused by thermal degradation progresses and a decrease in OSC, resulting in temperature increases in the oxygen storage reaction. In the surface reaction and mass transport model considering the 30 elementary reactions, the predicted results are well-validated for CO2 production, enabling good oxygen storage predictions based on actual data. These results can be used to predict OSC by formulating the changes in active site density and activation energy due to degradation.

Capacitance Determination for the Evaluation of Electrochemically Active Surface Area in a Catalyst Layer of NiFe-Layered Double Hydroxides for Anion Exchange Membrane Water Electrolyser.

The determination of the electrochemically active surface area (ECSA) of a catalyst layer (CL) of a non-precious metal catalyst is of fundamental importance in optimizing the design of a durable CL for anion exchange membrane (AEM) water electrolysis, but has yet to be developed. Traditional double layer capacitance (Cdl), measured by cyclic voltammetry (CV), is not suitable for the estimation of the ECSA due to the nonconductive nature of Ni-based oxides and hydroxides in the non-Faradaic region. This paper analyses the applicability of electrochemical impedance spectroscopy (EIS) compared to CV in determining capacitances for the estimation of the ECSA of AEM-based CLs in an aqueous KOH electrolyte solution. A porous electrode transmission line (TML) model was employed to obtain the capacitance-voltage dependence from 1.0 V to 1.5 V at 20 mV intervals, covering both non-Faradic and Faradic regions. This allows for the identification of the contribution of a NiFe-layered double hydroxide (LDH) catalyst and supports in a CL, to capacitances in both non-Faradic and Faradic regions. A nearly constant double layer capacitance (Qdl) observed in the non-Faradic region represents the interfaces between catalyst supports and electrolytes. The capacitance determined in the Faradic region by EIS experiences a peak capacitance (QF), which represents the maximum achievable ECSA in an AEMCL during reactions. The EIS method was additionally validated in durability testing. An approximate 30% loss of QF was noted while Qdl remained unchanged following an eight-week test at 1 A/cm2 constant current density, implying that QF, determined by EIS, is sensitive to and therefore suitable for assessing the loss of ECSA. This universal method can provide a reasonable estimate of catalyst utilization and enable the monitoring of catalyst degradation in CLs, in particular in liquid alkaline electrolyte water electrolysis systems.

High-capacity CO/CO2 methanation reactor design strategy based on 1D PFR modelling and experimental investigation

An in-depth analysis of oil-cooled and naturally ambient air-cooled fixed bed reactors for catalytic methanation of a feedgas containing CO and CO2 has been performed. Combined investigation of modelling and experiments showed, that small tube-to-pellet diameters ratios and optimized reactor cooling are beneficial for high-capacity CO/CO2 methanation. Very good model accuracy was proven with a 1D approach for small diameter reactor pipes. It is shown that the reactor design sweet spot under consideration of input gas capacity, methane output concentration, catalyst degradation and pressure loss can be assessed by the experimentally validated reactor model. The study reveals insights to the mechanism of combined CO and CO2 methanation showing that initial CO methanation is kinetically limited, while subsequent CO2 methanation is ruled by the kinetics of the reverse water gas shift reaction. Finally, this works aim is to provide a design strategy for effective and cheap high-capacity CO/CO2 methanation reactors for industrial scale using commercial pellet catalysts in oil-cooled tube-bundle-reactors.

Detecting performance degradation in a dead-ended hydrogen-oxygen proton exchange membrane fuel cell used for an unmanned underwater vehicle

Hydrogen-oxygen proton exchange membrane fuel cells (HO-PEMFCs) play a crucial role in the unmanned underwater vehicle (UUV) transportation field due to their distinct advantages of zero emission and low infrared radiation intensity. Effective water management is essential for the stable operation and performance output of HO-PEMFC. However, the vital role of increasing gas velocity to mitigate performance issues and catalyst degradation during prolonged fuel cell operation is frequently overlooked. The objective of this study is to systematically enhance both catalyst durability and overall system efficiency in dead-ended HO-PEMFCs by manipulating cathode flow velocities. The research findings demonstrate that a recirculation pump speed of 200 rpm (corresponding to a gas flow rate of approximately 0.4 m/s) can enhance cell performance by 58.39% at a current density of 1200 mA cm−2 compared to the dead-ended mode. With the gradual increase in pump speed, the flow pattern of liquid water at the cathode outlet transitions from film flow to droplet flow. Moreover, a weight coefficient is proposed to characterize the Pt oxidation states. Electrochemical and morphological characterization show that the increased gas flow rate mitigates water accumulation at the fuel cell outlet. In addition, the degradation of the catalyst due to dehydration of the membrane in the reactant gas inlet area is also mitigated by exhaust gas recirculation.

Dynamic modeling of chemical membrane degradation in polymer electrolyte membrane fuel cells: Effect of precipitated Pt particles

Chemical membrane degradation in polymer electrolyte membrane fuel cells operated under real conditions is often accompanied and affected by Pt catalyst degradation. This study investigates the effects of both artificially impregnated Pt particles and Pt migration on chemical membrane degradation are numerically investigated. For the first time, the impact of Pt migration is numerically analyzed. Membrane structural changes with coupled chemical membrane and Pt degradations are proposed. For Pt particles that are artificially impregnated in the membrane, yielding a Pt content of up to 50 mol% Pt, the membrane degrades at the fastest rate at moderate Pt contents (2 mol% Pt). The impregnated Pt particles promote the conversion of Fe3+ to Fe2+, which adversely impacts the membrane durability. The decrease in Pt content leads to reduction in both the Fe2+ conversion time and trend. In comparison, the naturally precipitated Pt particles in the membrane from the degraded Pt catalysts in the CL, have demonstrated a Pt content consistently lower than 2 mol% Pt. As a result, the chemical degradation rate of real fuel cells accelerates significantly with increasing Pt particle concentration. The chemical degradation rate increases with the gas solubility at the pore/electrolyte interface. With higher gas solubility, the peak location of chemical membrane degradation shifts from the anode side to the cathode side.

Benchmarking Stability of Iridium Oxide in Acidic Media under Oxygen Evolution Conditions: A Review: Part I

State-of-the-art proton exchange membrane (PEM) electrolysers employ iridium-based catalysts to facilitate oxygen evolution at the anode. To enable scale-up of the technology to the terawatt level, further improvements in the iridium utilisation are needed, without incurring additional overpotential losses or reducing the device lifetime. The research community has only recently started to attempt systematic benchmarking of catalyst stability. Short term electrochemical methods alone are insufficient to predict catalyst degradation; they can both underestimate and overestimate catalyst durability. Complementary techniques, such as inductively coupled plasma-mass spectrometry (ICP-MS), are required to provide more reliable assessment of the amount of catalyst lost through dissolution. In Part I, we critically review the state of the art in probing degradation of iridium-based oxide catalysts.

New trends in nanoparticle exsolution.

Many relevant high-temperature chemical processes require the use of oxide-supported metallic nanocatalysts. The harsh conditions under which these processes operate can trigger catalyst degradation via nanoparticle sintering, carbon depositions or poisoning, among others. This primarily affects metallic nanoparticles created via deposition methods with low metal-support interaction. In this respect, nanoparticle exsolution has emerged as a promising method for fabricating oxide-supported nanocatalysts with high interaction between the metal and the oxide support. This is due to the mechanism involved in nanoparticle exsolution, which is based on the migration of metal cations in the oxide support to its surface, where they nucleate and grow as metallic nanoparticles partially embedded in the oxide. This anchorage confers high robustness against sintering or coking-related problems. For these reasons, exsolution has attracted great interest in the last few years. Multiple works have been devoted to proving the high catalytic stability of exsolved metallic nanoparticles in several applications for high-temperature energy storage and conversion. Additionally, considerable attention has been directed towards understanding the underlying mechanism of metallic nanoparticle exsolution. However, this growing field has not been limited to these types of studies and recent discoveries at the forefront of materials design have opened new research avenues. In this work, we define six new trends in nanoparticle exsolution, taking a tour through the most important advances that have been recently reported.

Real-time investigation of reactive oxygen species and radicals evolved from operating Fe-N-C electrocatalysts during the ORR: potential dependence, impact on degradation, and structural comparisons.

Improving the stability of platinum-group-metal-free (PGM-free) catalysts is a critical roadblock to the development of economically feasible energy storage and conversion technologies. Fe-N-C catalysts, the most promising class of PGM-free catalysts, suffer from rapid degradation. The generation of reactive oxygen species (ROS) during the oxygen reduction reaction (ORR) has been proposed as a central cause of this loss of activity. However, there is insufficient understanding of the generation and dynamics of ROS under catalytic conditions due to the difficulty of detecting and quantifying short-lived ROS such as the hydroxyl radical, OH˙. To accomplish this, we use operando scanning electrochemical microscopy (SECM) to probe the production of radicals by a commercial pyrolyzed Fe-N-C catalyst in real-time using a redox-active spin trap methodology. SECM showed the monotonic production of OH˙ which followed the ORR activity. Our results were thoroughly backed using electron spin resonance confirmation to show that the hydroxyl radical is the dominant radical species produced. Furthermore, OH˙ and H2O2 production followed distinct trends. ROS studied as a function of catalyst degradation also showed a decreased production, suggesting its relation to the catalytic activity of the sample. The structural origins of ROS production were also probed using model systems such as iron phthalocyanine (FePc) and Fe3O4 nanoparticles, both of which showed significant generation of OH˙ during the ORR. These results provide a comprehensive insight into the critical, yet under-studied, aspects of the production and effects of ROS on electrocatalytic systems and open the door for further mechanistic and kinetic investigation using SECM.

Pt/C catalysts synthesized in a commercial particle atomic layer deposition system enabling improved durability in fuel cells.

Particle atomic layer deposition (ALD) is an emerging method for engineering 3D materials, such as powders, for energy applications. In our study, we employ a commercially available and scalable particle ALD system to synthesize Pt/C electrocatalysts for fuel cells. Our method yields Pt/C catalysts characterized by highly dispersed platinum nanoparticles with a narrow particle size distribution of 2.2 ± 0.5 nm for 30 wt% Pt and 2.6 ± 0.6 nm for 40 wt% Pt, as verified through transmission electron microscopy and X-ray diffraction analysis. The performance of the ALD-synthesized catalysts is benchmarked against a state-of-the-art catalyst (TEC10V50E), with both catalysts exhibiting similar beginning-of-test performance (1.6 A cm-2 at 0.65 V) under application-relevant operation conditions (80 °C, 50% relative humidity). After 30 000 voltage cycles, conducted in accordance with the U.S. Department of Energy's accelerated catalyst degradation test, the ALD catalysts demonstrate up to 64% greater electrochemical active surface areas and superior retention of cell performance, with a 34% higher current density at 0.65 V, compared to the reference. Given the scalability of the commercial particle ALD system, these promising results encourage the use of particle ALD as a novel synthesis approach for fuel cell catalyst materials in the industry.

Benchmarking Stability of Iridium Oxide in Acidic Media under Oxygen Evolution Conditions: A Review: Part II

Part I () introduced state-of-the-art proton exchange membrane (PEM) electrolysers with iridium-based catalysts for oxygen evolution at the anode in green hydrogen applications. Aqueous model systems and full cell testing were discussed along with proton exchange membrane water electrolyser (PEMWE) catalyst degradation mechanisms, types of iridium oxide, mechanisms of iridium dissolution and stability studies. In Part II, we highlight considerations and best practices for the investigation of activity and stability of oxygen evolution catalysts via short term testing.