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Oxygen evolution

Oxygen evolution is the chemical process by which molecular oxygen (O₂) is generated, primarily through the oxidation of water (H₂O), releasing O₂ along with protons and electrons.^[1] This fundamental reaction underpins life-sustaining biological processes like photosynthesis and enables key technologies in renewable energy production, such as water electrolysis for hydrogen generation.^[2] It can also occur via purely chemical means, such as the decomposition of oxygen-rich compounds in controlled environments.^[3] In biological systems, oxygen evolution is a cornerstone of oxygenic photosynthesis, carried out by cyanobacteria, algae, and plants. It takes place within the oxygen-evolving complex (OEC)—a manganese-calcium (Mn₄Ca) cluster in photosystem II (PSII) of chloroplasts—where two water molecules are oxidized in a light-driven, four-electron process: 2H₂O → O₂ + 4H⁺ + 4e⁻.^[1] This mechanism, which cycles through five intermediate states (S-states) activated by photon absorption, supplies electrons to the photosynthetic electron transport chain, enabling the reduction of NADP⁺ to NADPH and the generation of ATP for carbon dioxide fixation into sugars.^[1] The evolution of this process around 3.4 to 2.9 billion years ago transformed Earth's atmosphere, enabling aerobic respiration and the rise of complex life.^[4] In electrochemical applications, oxygen evolution manifests as the oxygen evolution reaction (OER), the rate-limiting anodic half-reaction in water splitting for clean hydrogen fuel production. The OER follows the same net equation as in photosynthesis (2H₂O → O₂ + 4H⁺ + 4e⁻ in acidic media or 4OH⁻ → O₂ + 2H₂O + 4e⁻ in alkaline media) but requires an overpotential due to its kinetically sluggish, multi-step nature involving proton-coupled electron transfers and unstable intermediates like *OH, *O, *OOH, and *OO.^[2] Efficient catalysts are crucial to overcome these barriers; in acidic electrolyzers, rare iridium-based oxides provide stability but at high cost, while alkaline systems favor earth-abundant nickel- and cobalt-based oxides, though durability remains a challenge.^[2] Advances in OER electrocatalysis are vital for scaling up proton exchange membrane (PEM) and alkaline electrolyzers to store intermittent renewable energy as hydrogen.^[2] Beyond biology and electrochemistry, oxygen evolution occurs through chemical decomposition reactions for practical oxygen supply. A prominent example is the thermal decomposition of sodium chlorate (NaClO₃) in oxygen candles or chlorate generators, where heat (often initiated by a primer) drives the exothermic reaction 2NaClO₃ → 2NaCl + 3O₂, producing breathable oxygen for emergency use in submarines, aircraft, and spacecraft.^[3] Catalysts like iron powder lower the required temperature from ~600°C, enhancing safety and efficiency in these self-contained devices.^[3] Such methods provide a reliable, non-electrical alternative for isolated environments, distinct from large-scale industrial cryogenic air separation.^[5]

Fundamentals

Definition and Reaction

Oxygen evolution refers to the chemical process of generating molecular oxygen (O₂) through the oxidation of water (H₂O), releasing O₂ along with protons and electrons. In the context of electrochemical water splitting, it corresponds to the anodic half-reaction.^[6] In acidic media, this process follows the stoichiometry:

$2\mathrm{H_2O} \rightarrow \mathrm{O_2} + 4\mathrm{H^+} + 4\mathrm{e^-}

^[6] In alkaline media, the reaction is:

$4\mathrm{OH^-} \rightarrow \mathrm{O_2} + 2\mathrm{H_2O} + 4\mathrm{e^-}

^[7] The oxygen evolution reaction (OER) specifically refers to this process as an electrochemical oxidation, distinguishing it from non-electrochemical methods of oxygen production, such as chemical decomposition.^[8] The process of oxygen evolution occurs in both natural systems, such as oxygenic photosynthesis, and artificial systems, like water electrolysis, where it is known as the OER.^[8] Under standard conditions at pH 0, the theoretical reversible potential for the OER is 1.23 V versus the reversible hydrogen electrode (RHE).^[9]

Thermodynamics and Kinetics

The oxygen evolution reaction (OER) is thermodynamically governed by the standard reversible potential of 1.23 V versus the standard hydrogen electrode (SHE) for the half-reaction $2H_2O \rightarrow O_2 + 4H^+ + 4e^- in acidic media, derived from the free energy change of water oxidation.^[10] In the context of overall water splitting, combining the OER with the hydrogen evolution reaction (HER) yields a theoretical cell voltage of 2.46 V, though practical systems require higher voltages due to additional energetic losses.^[11] The overpotential (\eta), defined as \eta = E_\text{applied} - E_\text{theoretical}, quantifies these losses and typically ranges from 300 to 400 mV at a current density of 10 mA cm^{-2} for benchmark catalysts like IrO_2, reflecting the inherent inefficiency of the process.^[12] Kinetic challenges arise primarily from the multi-step, four-electron transfer nature of the OER, which imposes high activation barriers and results in intrinsically slow reaction rates compared to two-electron processes like the HER.^[13] These barriers are exacerbated by pH-dependent mechanisms: in acidic media, proton-coupled electron transfers dominate, while alkaline conditions favor hydroxide-mediated pathways, often leading to lower overpotentials in basic electrolytes due to altered intermediate stabilities.^[11] Pourbaix diagrams illustrate these effects by delineating the stability regions of water, where potentials above the oxygen evolution line (approximately 1.23 V at pH 0, sloping with -59 mV/pH) favor O_2 formation over water stability, guiding the operational windows for OER to avoid excessive side reactions like corrosion.^[14] The Tafel equation, \eta = [a + b](/page/List_of_French_composers) \log([j](/page/Log)), where [j](/page/Log) is the current density, a is a constant, and [b](/page/List_of_French_composers) is the Tafel slope, provides a framework for quantifying OER kinetics, with typical slopes around 60 mV per decade indicating rate-limiting steps involving single electron transfers after initial proton-coupled processes.^[15] Activation energies for OER, often exceeding 50 kJ mol^{-1} on common catalysts, underscore the need for thermal or catalytic assistance to overcome these barriers, though exact values vary with material and conditions.^[16]

Biological Oxygen Evolution

Oxygenic Photosynthesis

Oxygenic photosynthesis is the primary biological process responsible for oxygen evolution on Earth, occurring in the thylakoid membranes of chloroplasts in plants and algae, as well as in cyanobacteria. In this light-dependent reaction, photosystem II (PSII) absorbs photons to drive the oxidation of water molecules, releasing oxygen gas, protons, and electrons. The electrons generated replenish the oxidized primary donor in PSII and flow through the photosynthetic electron transport chain to ultimately reduce NADP⁺ to NADPH, while the protons contribute to the proton gradient used for ATP synthesis; this provides the reducing power and energy needed for CO₂ fixation in the Calvin-Benson-Bassham cycle.^[17] At the heart of this process lies the oxygen-evolving complex (OEC), a hetero-multinuclear Mn₄CaO₅ cluster anchored within the PSII reaction center by amino acid residues from the D1 and CP43 proteins. The OEC catalyzes the challenging four-electron oxidation of two water molecules (2H₂O → O₂ + 4H⁺ + 4e⁻), accumulating oxidizing equivalents through a series of light-induced steps to overcome the kinetic barriers of O-O bond formation. High-resolution crystal structures have revealed the cluster's distorted chair-like configuration, with the Mn ions in oxidation states ranging from Mn(III)/Mn(IV) in the dark-stable S₁ state, and bound water ligands that serve as substrates or proton shuttles.^[18] The mechanism proceeds via the Kok cycle, a five-state sequence (S₀ to S₄) first proposed by Bessel Kok, where each photon absorption advances the OEC by one S-state through proton-coupled electron transfer events, often mediated by the redox-active tyrosine residue Yz. The cycle accumulates four oxidizing equivalents, with the transient S₄ state triggering O-O bond formation—likely via nucleophilic attack by a Ca-bound water on an oxo radical on Mn₄ or through oxo-oxo coupling—followed by rapid O₂ release and relaxation back to S₀. This rhythmic progression ensures efficient charge separation while minimizing damaging reactive intermediates.^[17] The emergence of oxygenic photosynthesis around 3.4 to 2.9 billion years ago, driven by ancient cyanobacteria, marked a pivotal evolutionary milestone, culminating in the Great Oxidation Event around 2.4 billion years ago that transformed Earth's anaerobic atmosphere into an oxygen-rich one, paving the way for aerobic respiration and the diversification of complex multicellular life.^[4] Under optimal conditions, the quantum yield for oxygen evolution approaches 0.125 (one O₂ per eight photons absorbed by PSII), reflecting near-unity charge separation efficiency but thermodynamic losses in the multi-step process. However, this efficiency is modulated by environmental factors: high light intensity can induce photoinhibition by damaging the OEC, while low CO₂ levels limit downstream electron acceptance, reducing overall rates and increasing non-photochemical quenching to protect the system.^[18]

Historical Discovery

The discovery of oxygen evolution began with experiments in the late 18th century that revealed plants' ability to produce a gas essential for respiration and combustion. In 1771, Joseph Priestley conducted pivotal experiments in England, placing a sprig of mint in a sealed jar containing "air infected with animal respiration" or air depleted by a burning candle. After exposure to sunlight, the air was restored, allowing a mouse to breathe comfortably or a flame to reignite, which Priestley termed "dephlogisticated air"—later identified as oxygen.^[19] These findings demonstrated that green plants release oxygen under light conditions, challenging prevailing phlogiston theories of combustion and air quality.^[20] Building on Priestley's work, Jan Ingenhousz, a Dutch physician, refined the understanding in 1779 by showing that oxygen release occurs exclusively from the green parts of plants and requires sunlight. Using aquatic plants like Elodea, Ingenhousz observed gas bubbles forming only on illuminated green leaves, with no production in darkness or from non-green tissues, establishing light as indispensable for the process.^[19] This specificity linked oxygen evolution to what would later be termed photosynthesis. In the early 1800s, Swiss scientists Jean Senebier and Nicolas-Théodore de Saussure advanced quantification: Senebier demonstrated in 1782 that plants absorb fixed air (carbon dioxide) in sunlight to release oxygen, while de Saussure in 1804 measured that the volume of oxygen evolved equals the carbon dioxide consumed, providing early stoichiometric evidence for the reaction.^[21] These insights shifted views from early theories suggesting plants absorbed oxygen to a mechanism where carbon dioxide fixation drives oxygen production in light.^[22] The 20th century brought isotopic confirmation of oxygen's source. In 1941, Samuel Ruben and Martin Kamen at the University of California used the heavy isotope ¹⁸O to label water and carbon dioxide separately in algal suspensions, revealing that evolved oxygen derived from water, not CO₂, via mass spectrometry analysis.^[23] This resolved a long-standing debate and confirmed water photolysis as central to oxygen evolution. By the 1970s, the oxygen-evolving complex (OEC) within photosystem II was identified as a manganese cluster essential for water oxidation, through spectroscopic studies including X-ray absorption spectroscopy that detected the metal's redox changes during oxygen release.^[24] These milestones solidified the biochemical basis of oxygen evolution in natural systems.

Artificial Oxygen Evolution

Electrochemical Water Splitting

Electrochemical water splitting involves the electrolysis of water, where electrical energy drives the decomposition of water into hydrogen and oxygen gases, with oxygen evolution occurring at the anode as the oxygen evolution reaction (OER).^[25] This process is coupled with the hydrogen evolution reaction (HER) at the cathode, requiring an input of electricity typically from renewable sources to produce green hydrogen.^[25] The overall reaction is 2H₂O → 2H₂ + O₂, with the OER half-reaction (2H₂O → O₂ + 4H⁺ + 4e⁻ in acidic media or equivalent in alkaline) demanding higher overpotentials due to its sluggish kinetics compared to HER.^[26] The minimum theoretical voltage is approximately 1.23 V under standard conditions, though practical systems operate at 1.6–2.0 V to account for overpotentials and resistances.^[25] Alkaline electrolysis, the most mature technology, employs a liquid potassium hydroxide (KOH) electrolyte, typically 25–40% concentration, with nickel-based electrodes for both anode and cathode.^[27] It operates at moderate temperatures of 60–80°C, enabling current densities up to 0.5 A/cm² in commercial systems, though advanced designs can exceed this.^[27] This configuration benefits from the use of abundant, non-precious materials, making it cost-effective for large-scale deployment. Proton exchange membrane (PEM) electrolysis utilizes a solid polymer electrolyte membrane, such as Nafion, which conducts protons in an acidic environment.^[28] At the anode, iridium or ruthenium oxides serve as catalysts due to their stability in acidic conditions, achieving high current densities of 1–2 A/cm² with efficiencies often exceeding 70% based on higher heating value.^[28] The system's compact design and rapid response make it suitable for fluctuating renewable energy inputs.^[29] Anion exchange membrane (AEM) electrolysis represents an emerging hybrid approach, combining the benefits of alkaline conditions with a solid anion-conducting polymer membrane.^[30] It allows the use of non-precious metal catalysts, such as nickel or cobalt-based materials, potentially reducing costs while operating in alkaline media.^[30] Current research focuses on improving membrane durability and ion conductivity to approach the performance of established technologies.^[31] On an industrial scale, water electrolysis systems have scaled to megawatt capacities, with examples including 1 MW PEM stacks from manufacturers like Nel Hydrogen, used for on-site green hydrogen production.^[32] These stacks integrate multiple cells to achieve outputs of several kilograms of hydrogen per hour, supporting applications in energy storage and industrial processes.^[32]

Chemical Oxygen Production

Chemical oxygen production encompasses non-electrochemical methods that generate molecular oxygen (O₂) through thermal or catalytic decomposition of chemical precursors, offering portable and reliable alternatives for confined environments where electrical power is unavailable or impractical. These processes typically involve exothermic reactions initiated by heat or catalysts, producing oxygen for breathing or propulsion without relying on external energy inputs like voltage. Unlike electrolytic methods, which require sustained electricity and achieve efficiencies around 50-70% based on overpotential losses, chemical approaches prioritize simplicity and storability, though they are often single-use and limited by reactant mass. One prominent method is the thermal decomposition of sodium chlorate (NaClO₃), commonly employed in chlorate candles for emergency oxygen supply. The reaction proceeds as 2 NaClO₃ → 2 NaCl + 3 O₂, occurring at temperatures of 400-500°C, where the chlorate decomposes exothermically to yield approximately 0.42 kg of O₂ per kg of NaClO₃ (practical yield).^[3] These devices incorporate iron powder as a catalyst and binder materials like barium peroxide to initiate and sustain the reaction, ensuring steady oxygen release over 20-60 minutes depending on candle size. Chlorate candles are integral to life-support systems in submarines, spacecraft, and aircraft, providing high-purity oxygen (>98%) in sealed, self-contained units that activate via a percussion igniter.^[33]^[34] Another established technique involves the catalytic decomposition of hydrogen peroxide (H₂O₂), represented by 2 H₂O₂ → 2 H₂O + O₂, which liberates 0.47 kg of O₂ per kg of pure H₂O₂ and is highly exothermic (ΔH = -98 kJ/mol).^[35] This process is accelerated by catalysts such as manganese dioxide (MnO₂) for industrial-scale generation or enzymes like catalase for controlled, low-temperature applications. In medical contexts, stabilized H₂O₂ solutions decompose via catalase to supply supplemental oxygen in portable concentrators or wound treatments, ensuring biocompatibility and rapid response. For propulsion, high-test peroxide (HTP, >85% concentration) decomposes in monopropellant thrusters, generating steam and oxygen for attitude control in rockets and torpedoes, as demonstrated in historical systems like the German V-2 engine.^[36]^[37]^[38] Metal oxide thermolysis represents an advanced chemical route, particularly in two-step cycles for solar-driven oxygen production. For instance, copper(II) oxide (CuO) undergoes thermal reduction at elevated temperatures (>800°C): 4 CuO → 2 Cu₂O + O₂, releasing oxygen while forming the reduced oxide, which can later react with water or hydrogen in a regeneration step (e.g., Cu₂O + H₂ → 2 Cu + H₂O) to close the cycle without net consumption of the oxide.^[39] This method is harnessed in solar thermochemical water-splitting prototypes, where concentrated solar heat drives the decomposition, offering a pathway for renewable oxygen and hydrogen co-production with efficiencies up to 5-8% in lab-scale reactors. Copper-based systems are favored for their reversible redox behavior and moderate operating temperatures compared to ferrites or ceria.^[40]^[41] Safety is paramount in these processes due to their exothermic nature and potential for runaway reactions. Sodium chlorate decomposition generates intense heat (up to 600°C), necessitating robust containment to prevent fires or explosions from molten residues, while impurities like chlorides can trigger premature ignition if moisture levels exceed 0.1%.^[3] Hydrogen peroxide handling requires stabilization against contaminants (e.g., metals) that catalyze uncontrolled decomposition, leading to pressure buildup in storage vessels; concentrations above 50% demand inert materials and temperature control below 30°C to mitigate decomposition rates exceeding 1% per year.^[42] Metal oxide cycles involve high temperatures, requiring inert atmospheres to avoid side reactions with air, and impurity control in oxide synthesis to maintain cycle stability over thousands of redox loops. Overall, rigorous quality control and personal protective equipment, including gloves and eye shields, are essential to manage corrosivity and oxidation risks.^[43]^[44] Historically, chemical oxygen production gained prominence during World War II, when Japanese forces developed sodium chlorate-based generators for high-altitude pilots to combat hypoxia in aircraft operating above 10,000 feet, marking an early shift from gaseous oxygen bottles to compact, heat-activated systems.^[3] These innovations laid the groundwork for postwar applications in naval and aerospace contexts, emphasizing reliability in oxygen-scarce scenarios.

Photoelectrochemical Processes

Photoelectrochemical processes for oxygen evolution involve the use of semiconductor materials to harness solar energy for driving the water oxidation reaction, producing oxygen and protons. In a typical setup, an n-type semiconductor photoanode, such as titanium dioxide (TiO₂) or bismuth vanadate (BiVO₄), is immersed in an aqueous electrolyte and illuminated with light. Upon absorption, photons excite electrons from the valence band to the conduction band, generating electron-hole pairs; the photogenerated holes migrate to the photoanode surface to oxidize water molecules into O₂, while electrons flow to a counter electrode to reduce protons or another species. This configuration enables bias-free or low-bias operation under sunlight, distinguishing it from purely electrochemical methods by directly coupling light absorption to charge separation and catalysis.^[45]^[46] For efficient oxygen evolution, the semiconductor's band edges must straddle the water redox potentials: the valence band edge should be more positive than +1.23 V versus the reversible hydrogen electrode (RHE) to provide sufficient overpotential for the oxygen evolution reaction (OER), while the conduction band edge needs to be more negative than 0 V versus RHE to support hydrogen evolution at the cathode. Materials like TiO₂ (band gap ~3.2 eV) are thermodynamically suitable but limited to ultraviolet light absorption due to their wide band gap, whereas BiVO₄ (band gap 2.4–2.6 eV) better utilizes visible light while meeting these alignment criteria. Charge carrier dynamics, including separation and transport, are critical, as recombination losses at surfaces or bulk defects can severely limit photocurrent densities, often requiring protective layers or co-catalysts like IrO₂ or CoOₓ to enhance OER kinetics.^[45]^[46]^[47] To overcome voltage limitations in single photoanode systems, tandem cell architectures integrate photovoltaic absorbers with photoelectrochemical components, reducing or eliminating external bias. For instance, perovskite-silicon tandem configurations combine a wide-band-gap perovskite top cell with a silicon bottom cell, providing a photovoltage exceeding 2 V to drive both OER and hydrogen evolution reaction (HER) unassisted; recent implementations have achieved solar-to-hydrogen (STH) efficiencies up to 20.8% in monolithic stacked designs. Z-scheme configurations further enhance efficiency by employing two distinct semiconductors—one optimized for OER (e.g., BiVO₄ modified with CoOₓ) and another for HER (e.g., Sm₂Ti₂O₅S₂ with Pt)—connected via a solid-state electron mediator like reduced graphene oxide, allowing independent optimization of each half-reaction and achieving an apparent quantum yield of 7.0% at 420 nm for overall water splitting. These approaches mimic aspects of natural photosynthesis by spatially separating oxidative and reductive processes but rely on inorganic materials for scalability.^[48]^[49] Recent advances up to 2025 emphasize doping strategies to extend visible light absorption and improve charge transport in photoanodes. In BiVO₄, molybdenum (Mo) or tungsten (W) doping introduces donor states that enhance electron mobility and photocurrent densities up to 2.5 mA/cm² at 1.23 V versus RHE, while lithium (Li) doping at 5 at.% increases water oxidation performance by 20% through reduced recombination. For TiO₂, nitrogen (N) or hydrogen (H) doping narrows the band gap, enabling visible-light response without compromising OER overpotential. These modifications, often combined with nanostructuring, have pushed STH efficiencies toward practical thresholds, though stability under operational conditions remains a key challenge.^[45]^[46]^[47]

Mechanisms and Catalysts

Reaction Pathways

The oxygen evolution reaction (OER) proceeds through distinct mechanistic pathways, primarily the adsorbate evolution mechanism (AEM) and the lattice oxygen mechanism (LOM), each involving sequential proton-coupled electron transfers (PCET) to form O₂ from water.^[50] In the AEM, oxygen-containing adsorbates form stepwise on active metal sites of the catalyst surface, starting with the adsorption of *OH from water oxidation, followed by its dehydrogenation to *O, and subsequent nucleophilic attack by water or hydroxide to yield *OOH, culminating in O₂ release.^[50] The O-O bond formation in AEM can occur via a peroxide-like path (*O + H₂O → *OOH) or an oxyl path (*OH + *O → *OOH), with the transition from *O to *OOH often serving as the rate-determining step due to its high energy barrier.^[51] The LOM, in contrast, incorporates oxygen atoms from the catalyst's oxide lattice into the O₂ product, enabling a more direct coupling pathway that activates lattice O to form *O or *OO species, often accompanied by surface amorphization or reconstruction to replenish the lattice. This mechanism enhances activity by circumventing some AEM limitations but can reduce selectivity in acidic media due to potential metal dissolution from lattice participation. While AEM relies predominantly on stepwise PCET events where proton transfer precedes or follows electron transfer, concerted PCET—simultaneous proton and electron movement—has been implicated in certain O-O coupling steps, particularly in LOM variants.^[51] pH significantly influences pathway dominance, with AEM prevailing in alkaline conditions where abundant OH⁻ facilitates adsorbate formation, whereas LOM becomes more prominent in acidic environments, leveraging lattice oxygen to mitigate proton scarcity effects on kinetics. Spectroscopic techniques provide direct evidence for these intermediates; for instance, in situ X-ray absorption spectroscopy (XAS) and Raman spectroscopy on IrO₂ reveal dynamic *O and *OOH species, supporting Walden-type mechanisms involving concerted PCET and configuration-specific rate limits during OER. Theoretical frameworks further elucidate pathway-activity links through scaling relations, where volcano plots correlate OER overpotential with the binding energies of key intermediates like *O and *OH, predicting optimal catalysts near the plot apex for AEM-dominated processes. These relations, derived from density functional theory, highlight a universal ~1.6 eV scaling slope between *OH and *OOH energies, constraining AEM efficiency and motivating LOM exploration to decouple such limitations.^[52]

Catalyst Materials

The oxygen-evolving complex (OEC) in photosystem II (PSII) features the Mn₄CaO₅ cluster as a natural benchmark for efficient water oxidation, operating at low overpotentials under physiological conditions.^[53] This cubane-like structure, with four manganese ions bridged by oxygen atoms and stabilized by a calcium ion, cycles through S-states to facilitate four-electron oxygen evolution while minimizing oxidative damage.^[54] The Ca²⁺ ion plays a critical role in self-repair mechanisms, enabling rapid reconstitution of the cluster by coordinating water molecules and preventing photodamage during turnover.^[55] Synthetic catalysts aim to replicate or surpass this efficiency, with noble metal oxides like IrO₂ and RuO₂ serving as state-of-the-art benchmarks for acidic oxygen evolution reaction (OER). These rutile-structured materials exhibit high intrinsic activity due to favorable adsorption energies for OER intermediates, achieving overpotentials as low as ~250 mV at 10 mA/cm² in acid for optimized nanostructures.^[56] However, their scarcity and high cost—iridium being rarer than gold—limit scalability for industrial applications.^[57] Recent advances in 2025 have focused on single-atom Ir catalysts, which maximize atomic efficiency by anchoring isolated Ir sites on supports like metal oxides or carbons, reducing loading while maintaining or enhancing activity through optimized coordination environments.^[58] Non-precious alternatives dominate alkaline OER, where NiFe (oxy)hydroxides emerge as leading catalysts, often forming layered structures that deliver overpotentials below 300 mV at 10 mA/cm².^[59] The synergy between Ni and Fe sites promotes deprotonation steps, with Fe incorporation tuning the electronic structure for faster kinetics.^[60] Spinel Co₃O₄ catalysts offer robust performance primarily in alkaline media, leveraging octahedral Co³⁺ sites as primary active centers for O-O bond formation, though modifications are needed for acidic conditions.^[61] Perovskite structures, such as Ba₀.₅Sr₀.₅Co₀.₈Fe₀.₂O₃₋δ (BSCF), provide high activity through mixed-valence Co/Fe sites and flexible lattice oxygen participation, achieving superior turnover frequencies compared to pure oxides.^[62] As of 2025, transition metal phosphides (TMPs) and sulfides have gained traction for anion exchange membrane (AEM) electrolyzers, where their precursors reconstruct in situ to form active (oxy)hydroxide layers under alkaline conditions.^[63] Surface reconstruction in TMPs, such as NiFeP or CoP, enhances activity by exposing high-valence metal sites and creating defective interfaces that lower energy barriers for water oxidation.^[63] These materials offer cost-effective scalability, with overpotentials around 250-300 mV in AEM setups, bridging the gap toward practical hydrogen production.^[64] Emerging trends in 2025 include high-entropy TMPs and AI-optimized designs for further improving stability and activity.^[64] Design principles for OER catalysts emphasize electronic structure optimization, including d-band center tuning to balance intermediate binding strengths. Shifting the d-band center downward relative to the Fermi level weakens oxygen adsorption, reducing overpotentials in transition metal oxides like perovskites and spinels.^[65] Oxygen vacancy engineering further refines performance by increasing active site density and conductivity; for instance, vacancy-rich surfaces in Co₃O₄ or perovskites facilitate lattice oxygen involvement, boosting turnover rates by up to an order of a magnitude.^[66] These strategies, informed by density functional theory, guide the development of durable, earth-abundant catalysts.^[67]

Applications and Challenges

Role in Renewable Energy

Oxygen evolution reaction (OER) plays a pivotal role in green hydrogen production through water splitting, where it is coupled with the hydrogen evolution reaction (HER) to generate hydrogen gas that can power fuel cells for clean energy applications.^[68] This process electrolyzes water into hydrogen and oxygen using renewable electricity, enabling the production of carbon-free fuels essential for decarbonizing sectors like transportation and industry.^[69] For instance, the European Union's REPowerEU plan targets 10 million tons of domestic green hydrogen production annually by 2030 to support energy security and net-zero goals.^[70] Integration of OER with renewable energy sources enhances the viability of carbon-neutral fuel production, such as through solar-driven photoelectrochemical (PEC) systems that directly harness sunlight to drive water splitting.^[47] In PEC setups, OER occurs at photoanodes, converting solar energy into chemical fuels like hydrogen without intermediate electricity conversion, thereby improving overall efficiency.^[69] Similarly, wind-powered electrolysis utilizes offshore or onshore wind farms to supply electricity for OER and HER, producing hydrogen that can be stored and used to balance grid intermittency while generating synthetic fuels.^[71] These integrations are crucial for scaling up renewable hydrogen to replace fossil-based energy carriers. Beyond terrestrial applications, OER enables oxygen generation in closed-loop life support systems, such as NASA's Oxygen Generation Assembly (OGA) on the International Space Station (ISS), which electrolyzes water to produce breathable oxygen for astronauts.^[72] The OGA has operated reliably since 2006, recovering up to 90% of water from crew metabolic byproducts to sustain long-duration missions.^[73] Economically, advancements in OER catalysts are key to reducing green hydrogen production costs, which stood at approximately $5 per kilogram in 2020 and are projected to fall below $2 per kilogram by 2030 through lower overpotentials and scalable electrolysis.^[74] Efficient OER electrocatalysts minimize energy losses, directly contributing to these cost declines by enhancing electrolysis efficiency.^[75] In 2025, pilot projects like the Hydrogen Offshore Production (HOP2) initiative demonstrate progress with proton exchange membrane (PEM) electrolyzers integrated into offshore wind farms, aiming for gigawatt-scale deployment to produce cost-competitive green hydrogen at sea.^[76] Additionally, efforts such as the H2SHIFT project are advancing AEM technologies for offshore wind-powered electrolysis, further optimizing renewable integration.^[77]

Stability and Efficiency Issues

One persistent challenge in oxygen evolution reaction (OER) catalysis is the inherent overpotential required, with even benchmark catalysts like IrO₂ exhibiting a minimum of approximately 300 mV at a current density of 10 mA cm⁻², reflecting the sluggish four-electron transfer kinetics.^[12] This overpotential scales unfavorably with increasing current density, often exceeding 400 mV at industrially relevant levels above 500 mA cm⁻², due to mass transport limitations and ohmic losses that hinder scalability for large-scale electrolyzers.^[78] Catalyst degradation further exacerbates efficiency losses, particularly through dissolution in acidic media where iridium-based catalysts suffer significant Ir loss, reducing active site density over time.^[79] In alkaline environments, catalysts undergo surface reconstruction, such as Ni oxides transforming into oxyhydroxides, which can initially boost activity but leads to structural instability.^[80] Additionally, the lattice oxygen mechanism (LOM) promotes amorphization by mobilizing lattice oxygen, resulting in vacancy formation and accelerated corrosion, as observed in various transition metal oxides.^[81] As of 2025, key challenges include ensuring durability under intermittent operation driven by renewable energy fluctuations, where rapid cycling accelerates degradation in NiCoOₓ catalysts, as demonstrated in simulated solar-driven electrolysis tests showing accelerated voltage rise.^[82] Impurity poisoning, such as Fe contaminants in alkaline electrolytes, further compromises stability by altering active sites on Ni-based catalysts, necessitating purification strategies for real-world deployment.^[80] Efficiency is quantified through metrics like Faradaic efficiency, which must exceed 95% to minimize side reactions and ensure practical viability, often verified via gas chromatography during OER operation.^[83] Turnover frequency (TOF) targets above 1000 h⁻¹ per active site are essential for high-throughput applications, though many catalysts fall short due to deactivation.^[80] Mitigation strategies focus on alloying, such as Ru-Ir oxides, which balance activity and dissolution resistance by tuning oxophilicity and electronic structure.^[80] Protective layers, including Ni foam supports for non-precious metal catalysts, enhance mechanical integrity and prevent detachment under high current densities, as seen in NiFe systems maintaining performance over extended cycles.^[84]

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Seven mechanisms of oxygen evolution reaction proposed recently
Apr 1, 2024 · However, due to its multi-step and multi-electron transfer process, the kinetics of OER are extremely slow, limiting the development of these ...
[14]
Predicting aqueous stability of solid with computed Pourbaix ...
Oct 21, 2020 · Pourbaix) diagram maps the most stable species in an aqueous environment and has become an invaluable tool in evaluating aqueous stability.
[15]
potential-dependent switching of the mechanism at the volcano apex
Mar 17, 2023 · The anodic four-electron oxygen evolution reaction (OER) corresponds to the limiting process in acidic or alkaline electrolyzers to produce ...
[16]
Why the optimum thermodynamic free-energy landscape of the ...
Why the optimum thermodynamic free-energy landscape of the oxygen evolution reaction reveals an asymmetric shape ... 1.23 V vs. RHE(5)H2O + M → M−OH + H+ ...
[17]
Light harvesting in oxygenic photosynthesis: Structural biology ...
Aug 21, 2020 · The trapping in the RCs of PSI and PSII in vivo occurs within 20 to 300 ps, and the maximal quantum efficiency is close to 1.0 for PSI and 0.9 ...
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May 18, 2023 · It has been shown that dynamic photosynthesis is more sensitive to environmental and non-environmental factors than steady photosynthesis. Hence ...2.1. Growth Light... · 2.4. Carbon Dioxide... · 3.4. Stomatal Behavior
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Highlights in photosynthesis research - Nobel Prize
1771, Joseph Priestley, England, discovers that plants can “purify” air that has been “burned out” by a candle. 1779, Jan Ingenhousz, The Netherlands ...
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Joseph Priestley, Discoverer of Oxygen National Historic Chemical ...
Putting a green plant in the jar and exposing it to sunlight would "refresh" the air, permitting a flame to burn and a mouse to breathe.About Joseph Priestley · Understanding the... · Oxygen and Other Discoveries...
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Photosynthesis: basics, history and modelling - PMC - NIH
The role of CO2 in photosynthesis was shown by Jean Senebier (1782), whereas the synthesis of starch was shown by Julius von Sachs (1862, 1864). However ...
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https://photobiology.info/History_Timelines/Hist-Photosyn.html
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Heavy Oxygen (O18) as a Tracer in the Study of Photosynthesis
'Photosystem II: the water splitting enzyme of photosynthesis and the origin of oxygen in our atmosphere'. ... Water Binding Sites from 18O Isotope Exchange ...
[24]
PHOTOSYSTEM II AND THE OXYGEN-EVOL VING COMPLEX
In the intact oxygen-evolving complex, it seems likely that the 23-kDa protein binds to the 33-kDa species, and the 17-kDa species in tum binds to the 23 kDa ...<|control11|><|separator|>
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Hydrogen Production: Electrolysis | Department of Energy
Electrolysis is the process of using electricity to split water into hydrogen and oxygen. The reaction takes place in a unit called an electrolyzer.
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Anion-Exchange-Membrane Electrolysis with Alkali-Free Water Feed
Aug 1, 2025 · Water is a notoriously stable molecule and the water-splitting reaction (eq 1) has a Gibbs free energy which defines a theoretical cell voltage ...
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High-current density alkaline electrolyzers: The role of Nafion binder ...
Nafion is also chemically stable under the harsh operating environment of AELs, e.g., 25–40% KOH electrolyte and temperature between 60–80°C, under which ...
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Recent advances and perspectives of Ir-based anode catalysts in ...
Nov 16, 2023 · The high current density of 2.4 A cm−2 at 80 °C with a cell voltage of 1.98 V was achieved in the PEM electrolyzer constructed by npIrx-NS with ...
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PEM Water Electrolysis for Hydrogen Production
Green hydrogen is generated in electrolysis systems using water and electricity from renewable sources, such as solar or wind energy, with water as the raw ...
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Recent Advances in Green Hydrogen Production by Electrolyzing ...
May 13, 2025 · AEM electrolyzers operate in alkaline environments with nonprecious metal catalysts and cheaper metal bipolar plates while enabling differential ...
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Review of AEM Electrolysis Research from the Perspective of ... - MDPI
Oct 10, 2024 · This review thoroughly examines recent progress, challenges, and future prospects in the field of alkaline exchange membrane (AEM) electrolysis.
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Water electrolysers / hydrogen generators | Nel Hydrogen
PEM Electrolyser – PSM Series. MW-class PEM Stack Module (PSM) for on-site hydrogen generation utilizing a modular containerized design for ease of installation ...
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Mechanism of combustion in low-exothermic mixtures of sodium ...
In oxygen generators based on sodium chlorate, the metal fuel provides combustion temperatures of 400−800 °C (decomposition of NaClO3 is exothermic and ...
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[PDF] Sodium chlorate - Nouryon
Above this tempera- ture chlorate decomposes slowly and steadily forming salt (sodium chloride) and oxygen. Sodium chlorate in its pure form is not flamma- ble ...Missing: thermal spacecraft
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[PDF] Decomposition of hydrogen peroxide - kinetics and review of chosen ...
Diluted solutions of H2O2 can be safely decomposed in the presence of proper enzymes known as catalase peroxidases, which are possessed by all aerobes.
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About Hydrogen Peroxide for Propulsion Applications
Hydrogen peroxide (HTP) is used as a liquid oxidizer/propellant, decomposing into water and oxygen with heat. It has a low Isp performance and is constrained ...
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Hydrogen peroxide – A promising oxidizer for rocket propulsion and ...
Hydrogen peroxide, especially HTP, is proposed as an oxidizer for solid rocket propulsion, with potential for bipropellant, hybrid, and monopropellant systems.
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[PDF] Hydrogen Peroxide: Potential for Repurposing into an Oxygen ...
Feb 11, 2025 · It has been reported that the rate of decomposition of hydrogen peroxide by catalase depends on the concentration of catalase and hydrogen.
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High-Temperature Thermochemical Heat Storage via the CuO/Cu2O ...
Nov 26, 2020 · A thermochemical redox cycle based on the CuO/Cu 2 O pair is considered for high-temperature heat storage in concentrated solar energy applications.Missing: decomposition | Show results with:decomposition
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High heating rate decomposition dynamics of copper oxide by ...
Dec 1, 2017 · CuO decomposes in two steps at both slower and higher heating rates, releasing oxygen. At 10^5 K/s, the decomposition occurs in two steps.
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The interaction between CuO and Al 2 O 3 and the reactivity of ...
Nov 22, 2016 · The reversible decomposition of CuO into Cu2O and oxygen at high temperature, typically between 850 and 1000 °C, provides a means of ...
[42]
[PDF] Hydrogen Peroxide - Hazardous Substance Fact Sheet
This Fact Sheet is a summary of available information regarding the health hazards that may result from exposure. Duration of exposure, concentration of the ...
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Hydrogen Peroxide | Safety and Handling - Evonik Active Oxygens
Hydrogen peroxide safety and potential risks It is highly corrosive to the skin and eyes. It is a strong oxidizing chemical and, therefore, tends to react ...
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[PDF] Control of the Hazards Associated with Reactive Chemicals - ioMosaic
40) Runaway Reaction means a reaction that is out of control because the rate of heat generation by exothermic chemical reaction exceeds the rate of heat.
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Jun 18, 2024 · This review summarizes the rational design and recent progress of photoanode materials for solar fuel production via the photoelectrochemical (PEC) approach.1 Introduction · 3 Materials Design And... · 4.1 Band Gap And Defect...
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Advancing photoelectrochemical systems for sustainable energy ...
Jun 25, 2025 · Photoelectrochemical (PEC) systems offer a promising approach to harness solar energy for producing essential chemicals and sustainable fuels.Pec Water Splitting For... · Pec Chlorine Generation · Pec Nitrogen Fixation
[47]
Advanced oxygen evolution reaction catalysts for solar-driven ...
The recent developments in OER catalyst decoration on semiconductor photoanodes for promoting PEC water splitting have been described and discussed.
[48]
Integrated halide perovskite photoelectrochemical cells with solar ...
Jun 26, 2023 · The second was formed using a monolithic stacked silicon-perovskite tandem, with a peak STH efficiency of 20.8% and 102 h of continuous ...
[49]
Efficient and stable visible-light-driven Z-scheme overall water ...
Jan 9, 2024 · This system is able to split water into hydrogen and oxygen for more than 100 hours with a solar-to-hydrogen energy conversion efficiency of 0.22%.
[50]
https://doi.org/10.1039/C9CS00607A
[51]
Potential-dependent transition of reaction mechanisms for oxygen ...
Jul 15, 2023 · We consider all the three distinctive types of OER mechanisms on Ni(M)OOH under alkaline conditions, i.e., AEM, IMOC, and LOM, each of which is ...
[52]
https://doi.org/10.1016/j.chemphys.2005.05.038
[53]
and protein scaffolding in the formation of natureTs water oxidizing ...
Nov 10, 2020 · Photosynthetic O2 evolution is catalyzed by the Mn4CaO5 cluster of the water oxidation complex of the photosystem II (PSII) com-.
[54]
Current analysis of cations substitution in the oxygen-evolving ...
Apr 30, 2024 · The catalytic center of water oxidation consists of four manganese cations and one calcium cation interconnected by oxygen bridges—Mn4CaO5. The ...
[55]
Probing the functional role of Ca2+ in the oxygen-evolving complex ...
Mar 20, 2007 · In this study, we probe the role of Ca2+ in oxygen evolution by monitoring the S1 to S2 state transition in PSII membranes and PSII core complexes.
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Synthesis and Activities of Rutile IrO 2 and RuO 2 Nanoparticles for ...
Here we report a synthesis of r-IrO 2 and r-RuO 2 nanoparticles (NPs) of ∼6 nm, and examine their OER activities in acid and alkaline solutions.Experimental Section · Supporting Information · Author Information · References
[57]
Oxygen and hydrogen evolution reactions on Ru, RuO2, Ir, and IrO2 ...
Mar 15, 2016 · It is found that independent of the electrolyte, OER activity decreases as Ru > Ir ≈ RuO2 > IrO2, while dissolution increases as IrO2 ≪ RuO2 < ...
[58]
Advances in Single‐Atom Catalysts for Acidic and Alkaline Oxygen ...
Sep 9, 2025 · This review systematically summarizes the latest applications of noble-metal and non-noble-metal single-atom catalysts over the past five ...
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Characterization of NiFe oxyhydroxide electrocatalysts by integrated ...
Mar 6, 2017 · NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for ...
[60]
(PDF) NiFe‐Based Electrocatalysts for Alkaline Oxygen Evolution
Oct 7, 2024 · In this contribution, a comprehensive overview of NiFe‐based OER electrocatalysts is provided, starting with fundamental mechanisms, evaluation ...
[61]
Clarifying the controversial catalytic active sites of Co3O4 for the ...
Spinel cobalt oxide (Co3O4), with both tetrahedral (Co2+) and octahedral (Co3+) sites, has been widely studied as an efficient non-precious OER catalyst.
[62]
Oxygen Evolution Reaction in Ba0.5Sr0.5Co0.8Fe0.2O3-δ Aided by ...
Aug 18, 2020 · Among the perovskites used to catalyze the oxygen evolution reaction (OER), Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) exhibits excellent activity ...Introduction · Experimental Section · Results and Discussion · Conclusion
[63]
Transition metal-based electrocatalysts for alkaline oxygen evolution ...
Currently, three types of OER routes are recognized, namely: 1) adsorbate evolution mechanism (AEM), 2) lattice oxygen-mediated mechanism, and 3) oxide path ...
[64]
Basics, developments, and strategies of transition metal phosphides ...
Sep 25, 2024 · The surface reconstruction effects of TMPs during OER have been widely studied. The surface P atoms ensure the metal atoms are positively ...
[65]
Overcoming Stability Hurdles of Transition Metal Phosphides for H2 ...
Sep 11, 2025 · This process led to surface reconstruction and the exposure of Co sites, which, over time, led to continued phosphorus loss, resulting in ...
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Modulating the D‐Band Center of Electrocatalysts for Enhanced ...
Sep 13, 2024 · Modulating the d-band center of transition metal electrocatalysts is an effective approach to regulate the adsorption energy of intermediates, ...Abstract · Introduction · Theoretical Basics · Modulation Strategies Based...
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Oxygen vacancy-originated highly active electrocatalysts for the ...
We report a new oxygen evolution reaction mechanism originating from oxygen vacancies, which remarkably enhances the OER activity of oxygen deficient ...
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Continuous strain tuning of oxygen evolution catalysts with ...
Feb 28, 2024 · Compressive strain, downshifting the d-band center of transition metal oxides, is an effective way to accelerate the sluggish kinetics of oxygen ...
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Hydrogen production from water electrolysis: role of catalysts
Feb 11, 2021 · Highly effective catalysts are required to minimize the overpotentials for OER and HER towards efficient H2 and O2 production. The design of ...
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Solar Hydrogen Production: Advances, Challenges, Future
Feb 26, 2022 · Solar H 2 production is considered as a potentially promising way to utilize solar energy and tackle climate change stemming from the combustion of fossil ...
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The case for global H2 trade: a factual response to T&E
Feb 20, 2024 · The REPower EU targets for green hydrogen by 2030 include 10 million tons (Mt) of domestic production and 10Mt imported internationally from multiple global ...
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Integration of renewable energy sources in tandem with electrolysis
Mar 10, 2025 · This review systematically examines the latest advancements in electrolysis technologies—alkaline, proton exchange membrane electrolysis cell ( ...
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[PDF] Status of the Advanced Oxygen Generation Assembly
Jul 20, 2023 · Future Exploration missions will require an Oxygen Generation Assembly (OGA) to electrolyze water to supply oxygen for crew metabolic ...
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Advanced Oxygen Generation - NASA
Feb 11, 2022 · On the space station, the Oxygen Generation System, or Oxygen Generation Assembly called the OGA, has been doing a fantastic job for 14 years.
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[PDF] Green hydrogen cost reduction: Scaling up electrolysers to ... - IRENA
Industry investors plan at least 25 gigawatts (GW) of electrolyser capacity for green hydrogen by 2026. Still, far steeper growth is needed – in renewable power ...
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Reducing Energy Costs during Hydrogen Production from Water ...
Jul 1, 2024 · Hence, there is an urgent need to develop electrocatalysts with high activity and selectivity to reduce electrolysis potential and suppress ...
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[PDF] Hydrogen Offshore Production - Net Zero Technology Centre
Phase 2 of the HOP2 project is ongoing, with a public report due to be published in Q3 2025 outlining the key findings. The initial concept was developed for ...
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H2SHIFT: Supporting innovation in hydrogen production
Sep 18, 2025 · Alternative electrolysis, including high temperature and anion exchange membrane (AEM) electrolysis ... Hydrogen production from offshore wind ...Missing: electrolyzers | Show results with:electrolyzers
[79]
Enhancing Oxygen Evolution Reaction at High Current Densities on ...
Dec 20, 2016 · Note that, the O-NFS-ECT achieves a large current density up to 500 mA cm−2 under an extremely low overpotential of 300 mV, which can meet the ...
[80]
Tackling activity-stability paradox of reconstructed NiIrO x ... - Nature
Dec 4, 2024 · Typically, these catalysts tend to undergo a reconstruction into an amorphous IrOxHy phase during the OER, as documented in prior studies. Acid ...
[81]
Activity–Stability Relationships in Oxygen Evolution Reaction
A review. The oxygen evolution reaction (OER) is one of the key kinetically limiting half reactions in electrochem. energy conversion. Model epitaxial catalysts ...
[82]
Amorphous electrocatalysts for oxygen and hydrogen evolution ...
The drawback is possible catalyst degradation due to lattice oxygen loss, dissolution, or surface reconstruction. The catalyst types include noble metals ...
[83]
Accelerated Durability Assessment and a Proposed Degradation ...
Oct 29, 2025 · Accelerated Durability Assessment and a Proposed Degradation Mechanism of NiCoOx OER Catalysts under Simulated Intermittent Renewable Power: ...Missing: poisoning impurities
[84]
Recommended electrochemical measurement protocol for oxygen ...
Faradaic efficiency. The Faradaic efficiency in OER measurements (FEOxygen) represents the ratio between the measured O2 production and the expected one, the ...
[85]
Exceptional electrocatalytic oxygen evolution efficiency and stability ...
Mar 10, 2019 · In this paper, an efficient OER electrocatalyst based on NiFe was prepared via one-step electrodeposition using NF as substrate. To obtain NiFe ...Missing: mitigation | Show results with:mitigation