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At least 91 records · Page 5

Enhancing Acidic Oxygen Evolution Activity by Supporting Iridium Electrocatalysts on Tantalum Carbide

For a high-performance proton exchange membrane water electrolyzer (PEMWE), acidic oxygen evolution reaction (OER) electrocatalysts require highly dispersed iridium oxide (IrO x ) nanoparticles. Although carbon-based materials have been explored as promising supports for IrO x nanoparticles, their limited stability under harsh oxidative and acidic PEMWE conditions remains a significant challenge. Here, in this study, we report the synthesis and in situ characterization of active and durable IrOx electrocatalysts supported on electrochemically stable and electrically conducting tantalum carbide (TaC). When applied in a PEMWE, the IrO x /TaC electrocatalyst achieves a cell voltage of 1.71 V at 1.0 A cm –2 , outperforming the commercial IrO 2 catalyst (1.82 V at 1.0 A cm –2 ). Furthermore, the IrO x /TaC catalyst maintains a stable operation for 200 h at 0.5 A cm –2 with a low degradation rate of 36 μV h –1 . Density functional theory calculations further confirm that Ir–O–Ta bond formation at the IrO x /TaC interface reduces the overpotential of the OER compared to IrO 2 . This study underscores the pivotal role of supporting IrO x over stable and conducting metal carbides, providing guidance for the design of advanced acidic OER catalysts.

58 GEOSCIENCES↗

Lewis Acid Site Assisted Bifunctional Activity of Tin Doped Gallium Oxide and Its Application in Rechargeable Zn‐Air Batteries

The enhanced safety, superior energy, and power density of rechargeable metal‐air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost‐effective and stable bifunctional catalyst that can replace expensive platinum (Pt)‐based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, in this work, it is demonstrated that Tin (Sn) doped β‐gallium oxide (β‐Ga 2 O 3 ) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn‐air batteries. The Sn‐doped β‐Ga 2 O 3 sample with 15% Sn (Sn x =0.15 ‐Ga 2 O 3 ) displayed exceptional catalytic activity for a bulk, non‐noble metal‐based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Sn x =0.15 ‐Ga 2 O 3 leads to a prototype Zn‐air battery with a high‐power density of 138 mW cm −2 and improved cycling stability compared to devices with benchmark Pt‐based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in β‐Ga 2 O 3 aid in regulating the electron density distribution on the Sn‐doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

Lewis acid sites↗

The Influence of Transitional Metal Dopants on Reducing Chlorine Evolution during the Electrolysis of Raw Seawater

Electrocatalytic water splitting is a possible route to the expanded generation of green hydrogen; however, a long-term challenge is the requirement of fresh water as an electrolyzer feed. The use of seawater as a direct feed for electrolytic hydrogen production would alleviate fresh water needs and potentially open an avenue for locally generated hydrogen from marine hydrokinetic or off-shore power sources. One environmental limitation to seawater electrolysis is the generation of chlorine as a competitive anodic reaction. This work evaluates transition metal (W, Co, Fe, Sn, and Ru) doping of Mn-Mo-based catalysts as a strategy to suppress chlorine evolution while sustaining catalytic efficiency. Electrochemical evaluations in neutral chloride solution and raw seawater showed the promise of a novel Mn-Mo-Ru electrode system for oxygen evolution efficiency and enhanced catalytic activity. Subsequent stability testing in a flowing raw seawater flume highlighted the need for improved catalyst stability for long-term applications of Mn-Mo-Ru catalysts. This work highlights that elements known to be selective toward chlorine evolution in simple oxide form (e.g., RuO2) may display different trends in selectivity when used as isolated dopants, where Ru suppressed chlorine evolution in Mn-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrO x ) due to its superior performance and excellent stability. However, large scale applications using IrO x are impractical due to its low abundance and high cost. In this work, we report a highly active hafnium-modified iridium oxide (IrHf x O y ) electrocatalyst for OER. The IrHf x O y electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrO x electrocatalyst. The highest intrinsic mass activity of the IrHf x O y catalyst in acid conditions was calculated as 6950 A gIrO x -1 at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrO x and IrHf x O y catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, and shortening the bond lengths of Ir-O, and lowering free energies for OER intermediates to accelerate the OER process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cu-induced robust Ni 2+ /Ni 3+ transition on amorphous Ni hydroxide-based electrocatalysts for advancing electrochemical ammonia oxidation and hydrogen evolution

The electrochemical ammonia oxidation reaction (AOR) is a promising anodic reaction for hydrogen production, offering a lower theoretical potential compared to oxygen evolution reaction. Despite this thermodynamic advantage, AOR suffers from sluggish multi-electron transfer reaction kinetics and the regeneration of catalytically active Ni 3+ species, which limits both activity and durability. In this study, amorphous NiCu bimetallic catalysts were prepared via facile precipitating metal nitrate deposition (PMND) method. The addition of Cu induces a robust Ni 2+ /Ni 3+ transition, stabilizing catalytically active Ni 3+ species and modulating the electronic structure of Ni. It alters the oxidation and desorption behavior of nitrogen-containing intermediates and facilitating their conversions to NO x species, resulting in fast active site regeneration. Furthermore, amorphous structure provides abundant dangling bonds, which enhances the intrinsic reactivity and accessibility of active sites rather than increasing the number of active sites. As a result, these effects accelerate the overall reaction kinetics. The optimized NiCu 5:1 catalyst achieved an ammonia removal efficiency of ∼100 % and a hydrogen production rate of 2.45 mmol/(h∙cm 2 ) at 1.6 V RHE .

Amorphous electrocatalyst↗

Effect of porous transport layer properties on the anode electrode in anion exchange membrane electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over existing commercial water electrolysis technologies. However, AEM electrolyzers have not yet met performance and durability targets. One of the critical components in achieving high AEMEL performance is the porous transport layer (PTL) which serves many critical functions in the oxygen evolution reaction (OER) electrode. In this study, several OER PTL attributes were investigated, including: material of construction, fabrication method, feature size, porosity/density, and thickness. It was found that higher porosity helped facilitate multiphase (O 2 , H 2 O, etc.) transport; however, as the porosity increased, the catalyst layer adhesion to the PTL decreased, the contact resistance with the bipolar plate increased and the cell operating voltage increased. It was found that nickel-based PTLs allowed for lower operating voltages than similarly-structured stainless steel PTLs. Improved operating voltages were achieved with both fiber felts and sintered structures by porosity optimization. Furthermore, an increase in thickness did not affect transient voltage response, however, it had a negative effect on performance stability. As a result, the experimental findings presented here provide important insights for development of PTL materials and structures for efficient and low-cost water electrolysis.

08 HYDROGEN↗

Understanding Degradation Mechanisms in SrIrO 3 Oxygen Evolution Electrocatalysts: Chemical and Structural Microscopy at the Nanoscale

Designing acid-stable oxygen evolution reaction electrocatalysts is key to developing sustainable energy technologies such as polymer electrolyte membrane electrolyzers but has proven challenging due to the high applied anodic potentials and corrosive electrolyte. This work showcases advanced nanoscale microscopy techniques supported by complementary structural and chemical characterization to develop a fundamental understanding of stability in promising SrIrO 3 thin film electrocatalyst materials. Cross-sectional high-resolution transmission electron microscopy illustrates atomic-scale bulk and surface structure, while secondary ion mass spectrometry imaging using a helium ion microscope provides the nanoscale lateral elemental distribution at the surface. After accelerated degradation tests under anodic potential, the SrIrO 3 film thins and roughens, but the lateral distribution of Sr and Ir remains homogeneous. A layer-wise dissolution mechanism is hypothesized, wherein anodic potential causes the IrO x -rich surface to dissolve and be regenerated by Sr leaching. Finally, the characterization approaches utilized herein and mechanistic insights into SrIrO 3 are translatable to a wide range of catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Ni oxides and oxyhydroxides (NiO x ) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO x . Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO 2 layers. All the Ni 3+ cations in this structure exhibit an identical t g 6 e g 1 electronic configuration with an occupied 3d z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Yttrium-based Double Perovskite Nanorods for Electrocatalysis

In this work, we investigate the effect of chemical composition of double perovskite nanorods on their versatile electrocatalytic activity not only as supports for the oxidation of small organic molecules but also as catalysts for the oxygen evolution reaction. Specifically, Y 2 CoMnO 6 and Y 2 NiMnO 6 nanorods with average diameters of 300 nm were prepared by a two-step hydrothermal method, in which the individual effects of synthetic parameters, such as the pH, annealing temperature, and precursor ratios on both the composition and morphology, were systematically investigated. When used as supports for Pt nanoparticles, Y 2 CoMnO 6 /Pt catalysts exhibited an electrocatalytic activity for the methanol oxidation reaction, which is 2.1 and 1.3 times higher than that measured for commercial Pt/C and Y 2 NiMnO 6 /Pt. Similarly, the Co-based catalyst support material displayed an ethanol oxidation activity, which is 2.3 times higher than both Pt/C and Y 2 NiMnO 6 /Pt. This clear enhancement in the activity for Y 2 CoMnO 6 can largely be attributed to strong metal-support interactions, as evidenced by a downshift in the binding energy of the Pt 4f bands, measured by XPS, which is often correlated not only with a downshift in the d-band center but also to a decreased adsorption of poisoning adsorbates. Moreover, when used as catalysts for the oxygen evolution reaction, Y 2 CoMnO 6 displayed a much greater activity as compared with Y 2 NiMnO 6 . This behavior can largely be attributed not only to a preponderance of comparatively more favorable oxidation states and electronic configurations but also to the formation of an active layer on the surface of the Y 2 CoMnO 6 catalyst, which collectively give rise to improved performance metrics and greater stability as compared with both IrO 2 and Y 2 NiMnO 6 . Overall, these results highlight the importance of both the chemical composition and the electronic structure of double perovskites, especially when utilized in multi-functional roles as either supports or catalysts.

30 DIRECT ENERGY CONVERSION↗

Amorphous electrocatalysts for oxygen and hydrogen evolution reactions: Advances in hydrogen production

The electrochemical splitting of water into oxygen and hydrogen is fundamental for renewable energy storage and conversion. The development of cost-effective and highly efficient electrocatalysts remains essential for industrial-scale implementation of this technology. Recent advances have highlighted the superior activity, stability and structural adaptability of amorphous electrocatalysts compared to their crystalline counterparts. This review critically examines synthesis strategies, characterisation techniques, and the electrochemical performance of amorphous materials for both oxygen evolution (OER) and hydrogen evolution (HER) reactions. Key factors influencing catalytic efficiency, including electronic structure and surface chemistry, are discussed in detail and contextualised with established literature. The review also highlights the critical role of enthalpic contributions in governing reaction energetics and catalyst performance, which aids in understanding and optimising electrocatalytic efficiency. Notably, ongoing research continues to reveal that amorphous catalysts consistently deliver improved performance in water-splitting applications, highlighting their growing relevance in electrocatalysis. The rationale for employing amorphous catalysts in water splitting is articulated, emphasising their unique advantages. By integrating recent findings and outlining future research directions, this review underscores the pivotal role of amorphous materials in advancing sustainable hydrogen production and identifies promising avenues for catalyst innovation.

Amorphous catalysts↗

Ultrahigh Oxygen Evolution Reaction Activity Achieved Using Ir Single Atoms on Amorphous CoO x Nanosheets

Developing efficient electrocatalysts for an oxygen evolution reaction (OER) is important for renewable energy storage. Here, we design high-density Ir single-atom catalysts supported by CoO x amorphous nanosheets (ANSs) for the OER. Experimental results show that Ir single atoms are anchored by abundant surface-absorbed O in CoO x ANSs. Ir single-atom catalysts possess ultrahigh mass activity that is 160-fold of commercial IrO 2 . The OER of IrCoO x ANSs reached a record low onset overpotential of less than 30 mV. In situ X-ray absorption spectroscopy reveals that Ir-O-Co pairs directly boosted the OER efficiency and enhanced the Ir stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of a temporal multiscale method for efficient simulation of degradation in PEM Water Electrolysis under dynamic operating conditions

Hydrogen is emerging as a vital energy carrier, driven by the need to reduce carbon emissions. Proton Electrolyte Membrane Water Electrolysis (PEMWE) enables hydrogen production under fluctuating renewable power conditions but requires improved understanding and stability of the anode catalyst layer under dynamic operating conditions, especially with low noble metal loadings. Long-term degradation experiments are both time-consuming and costly; therefore, a systematic, model-aided approach is essential. In the present work, a temporal multiscale method is applied to reduce the computational effort of simulating long-term degradation processes in PEMWE, with an exemplary focus on catalyst dissolution. A mechanistic model incorporating the oxygen evolution reaction, catalyst dissolution, and hydrogen permeation from the cathode to the anode was hypothesized and implemented. In this way, the local periodicity of transport and reaction processes in dynamic PEMWE operation, which influence the gradual degradation of the catalyst layer, is captured. The temporal multiscale method significantly reduces the computational effort of simulation, decreasing processing time from hours to mere minutes. This efficiency gain is attributed to the limited evolution of Slow-Scale variables during each period of time P of the Fast-Scale variables. Consequently, simulation is required only until local periodicity is achieved within each Slow-Scale time step. Hence, the fully resolved dynamic problem is decoupled into these two scales, employing a heterogeneous multiscale technique. The developed approach effectively accelerates parameter estimation and predictive simulations, supporting systematic modeling of PEMWE degradation under dynamic conditions.

08 HYDROGEN↗

Constructing Highly Porous Low Iridium Anode Catalysts Via Dealloying for Proton Exchange Membrane Water Electrolyzers

Iridium (Ir) is the most active and durable anode catalyst for the oxygen evolution reaction (OER) for proton exchange membrane water electrolyzers (PEMWEs). However, their large-scale applications are hindered by high costs and scarcity of Ir. Lowering Ir loadings below 1.0 mgcm -2 causes significantly reduced PEMWE performance and durability. Therefore, developing efficient low Ir-based catalysts is critical to widely commercializing PEMWEs. Herein, an approach is presented for designing porous Ir metal aerogel (MA) catalysts via chemically dealloying IrCu alloys. In this study, the unique hierarchical pore structures and multiple channels of the Ir MA catalyst significantly increase electrochemical surface area (ECSA) and enhance OER activity compared to conventional Ir black catalysts, providing an effective solution to design low-Ir catalysts with improved Ir utilization and enhanced stability. An optimized membrane electrode assembly (MEA) with an Ir loading of 0.5 mg Ir cm -2 generated 2.0 A cm -2 at 1.79 V, higher than the Ir black at a loading of 2.0 mg Ir cm -2 (1.63 A cm -2 ). The low-Ir MEA demonstrated an acceptable decay rate of ≈40 µV h -1 during durability tests at 0.5 (>1200 h) and 2.0 A cm -2 (400 h), outperforming the commercial Ir-based MEA (175 µV h -1 at 2.0 mg Ir cm -2 ).

36 MATERIALS SCIENCE↗

Electrospun Ti–Zr Oxide Heterostructures Enable Strongly Anchored Ultralow-Ir Anodes for Durable Acidic Oxygen Evolution

Proton-exchange-membrane water electrolysis (PEMWE) requires acidic oxygen-evolution-reaction (OER) anodes that combine high activity, high durability, and low Ir loading. Here, we report a Ti-Zr composite electrospun oxide (ESO) nanorod support that enables ultralow-Ir anodes for high-performance PEMWE. Zr-containing Ti oxide heterostructures stabilize anatase-rich TiO2, tune the local oxygen-coordination environment, and strengthen interfacial anchoring of IrOx under acidic anodic conditions. The electrospun nanorod network further creates an open, mechanically coherent catalyst layer that improves Ir utilization, ionomer penetration, and mass transport. At an anode loading of 0.2 mgIr cm-2, the optimized Ir/TiZr20-ESO anode delivers a PEMWE mass activity of 0.99 A mgIr-1 at 1.45 V, 28.3 and 43.0 times higher than commercial Ir black and commercial IrO2/TiO2, respectively. The same anode reaches 3.0 and 4.0 A cm-2 at 1.75 and 1.83 V, respectively, and sustains 2000 h operation at 2.0 A cm-2. Also, accelerated stress tests up to 525 hours over 31,500 cycles confirm promising long-term durability, with an insignificant performance decay of 0.4 μV per cycle. Density functional theory indicates that the Ti-Zr oxide heterostructure suppresses Ti demetallation and strengthens IrO2 interfacial binding, rationalizing the improved high-current-density stability.

25 ENERGY STORAGE↗

Functionalized Metal–Organic Framework Thin Films for Stable and Efficient Electrochemical Water Oxidation under Near-Neutral Conditions

The development of molecularly modified metal− organic frameworks (MOFs) for electrochemical water oxidation has emerged as a promising strategy for efficient artificial photosynthesis. In this study, a ruthenium-based water oxidation catalyst (WOC) was incorporated into the UiO-67 framework, forming RuM−UiO-67 films grown directly on conductive FTO substrates. These modified films demonstrate efficient water oxidation activity at near-neutral pH (pH 6), operating at a low overpotential of ∼600 mV. The catalyst exhibits a turnover frequency (TOF) of (0.32 ± 0.02) s −1 at 1.5 V versus the normal hydrogen electrode (NHE) in buffered solution (pH 6) for the oxygen evolution reaction. Notably, incorporation into the MOF results in a 12-fold increase in electroactive surface coverage compared to a monolayer of the same catalyst on bare FTO. Faradaic efficiency analysis revealed incomplete conversion to O 2 , and follow-up iodometric analysis confirmed the formation of H 2 O 2 as a competing two-electron oxidation product during electrocatalysis. These results highlight the utility of MOF-based architectures for maximizing the catalyst accessibility and stability under electrochemical water oxidation conditions.

catalysts↗

Enhancing electrocatalytic performance of RuO 2 -based catalysts: mechanistic insights, strategic approaches, and recent advances

Abstract Electrochemical water splitting presents the ultimate potential of hydrogen and oxygen production; however, regulating the rate and efficiency of water splitting is highly dependent on the accessibility of extremely efficient electrode materials for slow performance kinetics and large overpotential of both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Ruthenium oxide (RuO 2 ) based materials display high performance for OER and HER because of their capacity to bind oxygen, eminent catalytic activity, low cost compared to other precious metals, and stability in a wide pH range. However, there is still much space to promote the OER and HER activity and stability of RuO 2 to fulfill the necessity for practical applications in water splitting. Different researchers applied multiple approaches that boosted the catalytic performance of RuO 2 -based electrocatalysts toward overall water splitting. Herein, this review provides a comprehensive overview of recent advancements in RuO 2 -based materials in the field of water electrolysis for the generation of alternative energies. It gives a general description of water splitting in acidic and alkaline settings, including reaction mechanisms as well as common evaluation elements for the catalytic function of the materials. Most of the reviews reported based on RuO 2 materials are only focused on OER performance, but this review highlighted comprehensive ideas on different strategies like morphology design, electronic structure, electrolytes, and compositions for optimizing both electrocatalytic HER and OER functioning of RuO 2 -based electrocatalysts.

KC, Binod Raj (ORCID:0009000885806906)↗

From Pure to Seawater Electrolysis: Unveiling the Impact of Ionic Species and Contaminants on Electrocatalysis

Water electrolysis, including seawater splitting to produce hydrogen and oxygen, stands as a promising approach for the efficient storage of intermittent energy. However, the half-reactions of water splitting, the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), are known to be very sensitive toward the quality of water employed and are susceptible to contaminants originating from various sources, including the electrolyte or the electrodes. Those contaminants have a profound impact on the activity of these reactions of water splitting by modifying the electronic and physical structures of electrocatalysts as well as electrode–electrolyte interfaces. For seawater electrolysis, the unintentional presence of impurities, such as anions, cations, and organic compounds, affects the catalyst stability, selectivity, and activity. Despite the existence of numerous comprehensive reviews that delve into various aspects of catalysts and their structure–property relationships for several electrocatalytic reactions, the impact of contaminants has often been ignored. This critical review endeavors to address this issue by providing an overview of the diverse sources of contaminants influencing electrocatalytic water splitting and seawater splitting reactions, delineating the trends in electrochemical parameters and detailing different characterization methods for elucidating the physical and electronic changes of the electrode and electrolyte.

HER↗

Non-Equilibrium Synthesis of Highly Active Nanostructured, Oxygen-Incorporated Amorphous Molybdenum Sulfide HER Electrocatalyst

Molybdenum sulfide emerged as promising hydrogen evolution reaction (HER) electrocatalyst thanks to its high intrinsic activity, however its limited active sites exposure and low conductivity hamper its performance. To address these drawbacks, the non-equilibrium nature of pulsed laser deposition (PLD) is exploited to synthesize self-supported hierarchical nanoarchitectures by gas phase nucleation and sequential attachment of defective molybdenum sulfide clusters. Furthermore, the physics of the process are studied by in situ diagnostics and correlated to the properties of the resulting electrocatalyst. The as-synthesized architectures have a disordered nanocrystalline structure, with nanodomains of bent, defective S-Mo-S layers embedded in an amorphous matrix, with excess sulfur and segregated molybdenum particles. Oxygen incorporation in this structure fosters the creation of amorphous oxide/oxysulfide nanophases with high electrical conductivity, enabling fast electron transfer to the active sites. The combined effect of the nanocrystalline pristine structure and the surface oxidation enhances the performance leading to small overpotentials, very fast kinetics (35.1 mV dec -1 Tafel slope) and remarkable long-term stability for continuous operation up to -1 A cm -2 . This work shows possible new avenues in catalytic design arising from a non-equilibrium technique as PLD and the importance of structural and chemical control to improve the HER performance of MoS-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗