Acidic Oxygen Evolution Reaction Research Articles

Synergistic Engineering of Dopant and Support of Ru Oxide Catalyst Enables Ultrahigh Performance for Acidic Oxygen Evolution

AbstractActive and robust electrocatalysts for acidic oxygen evolution reaction (OER) are of crucial importance for efficient proton exchange membrane water electrolyzer (PEM‐WE). Ruthenium (Ru) oxide has attracted considerable attention due to its high activity. However, the unsatisfying stability of Ru oxide in acidic OER environments hinders the application. Here, Ce‐doped RuO2 nanoparticles are designed and supported on Co─N─C material (Ce@RuO2/CoNC) for acidic OER. It is demonstrated that Ce@RuO2/CoNC delivers a super low overpotential of 150 mV and an excellent stability of 1000 h at 10 mA cm−2, outperforming most previously reported Ru‐based catalysts. The mass activity is estimated as 2365.5 AgRu−1 at 1.5 V (vs RHE), representing ≈2× advance compared to the best prior study. Furthermore, applied in a single‐cell PEM‐WE device, it can steadily operate for 1000 h at 200 mA cm−2. The studies show that Ce‐doping and Co─N─C support synergistically enhance the activity and stability of Ru oxide by optimizing the free energies of OER intermediates and suppressing the dissolution of Ru.

Ruthenium Single-Atom Modulated Protonated Iridium Oxide for Acidic Water Oxidation in Proton Exchange Membrane Electrolysers.

Proton exchange membrane water electrolysers promise to usher in a new era of clean energy, but they remain a formidable obstacle in designing active and durable electrocatalysts for the acidic oxygen evolution reaction (OER). In this study, a protonated iridium oxide embedded with single-atom dispersed ruthenium atoms (H3.8Ir1- xRuxO4) that demonstrates exceptional activity and stability in acidic water oxidation is introduced. The single Ru dopants favorably induce localized oxygen vacancies in the Ir─O lattice, synergistically strengthening the adsorption of OOH* intermediates and enhancing the intrinsic OER activity. In addition, the preferential oxidation of Ru and the electronegativity of the oxygen vacancies significantly stabilize the Ir─O active sites, improving the OER stability. Consequently, the H3.8Ir1─ xRuxO4 catalyst shows an overpotential of 255mV at 10mA cm-2 and displays exceptional catalytic endurance in acidic electrolytes, surpassing 1100 h, representing a remarkable one-order-of-magnitude increase in stability compared to that of pristine H3.8IrO4. A proton exchange membrane electrolyser utilizing the H3.8Ir1- xRuxO4 catalyst as an anode exhibits stable performance for more than 1280 h under a high current density of 2 A cm-2.

Efficient and durable OER electrocatalysts through vacancy engineering and core-shell structure design in acidic environment

The electrocatalytic conversion of water into green hydrogen energy through overall water splitting advances sustainable energy goals. However, it is limited by the slow kinetics of the oxygen evolution reaction (OER) and durability challenges at high potentials. Here, we rationally develop a series of Mn-doped RuO2-coated Ru (Mn-Ru@RuO2) catalysts involving unique core-shell structures and abundant lattice distortions induced by oxygen defects. The optimal Mn-Ru@RuO2 sample demonstrated robust activity, achieving a low overpotential of 220 mV at 10 mA cm−2. Notably, this sample exhibited minimal degradation after 220 h and a 25.5-fold increase in mass activity (1.37 A mgRu−1) compared to commercial RuO2 at an overpotential of 300 mV. These results suggest that regulated oxygen deficiencies and optimal Ru3+/Ru4+ ratios facilitate the lattice oxygen oxidation (LOM) mechanism and the formation of a high concentration of ∗OH radicals, enhancing acidic OER performance. Additionally, the unique core-shell structures effectively prevent over-oxidation of the RuO2 shell, ensuring superior durability. This research not only breaks the trade-off of electrochemical activity and durability, but also provides valuable insights into the design of highly efficient and stable electrocatalysts.

Monitoring the Structural Changes in Iridium Nanoparticles during Oxygen Evolution Electrocatalysis with Operando X-ray Total Scattering.

Understanding the structure of nanoparticles under (electro)catalytic operating conditions is crucial for uncovering structure-property relationships. By combining operando X-ray total scattering and pair distribution function analysis with operando small-angle X-ray scattering (SAXS), we obtained comprehensive structural information on ultrasmall (<3 nm) iridium nanoparticles and tracked their changes during oxygen evolution reaction (OER) in acid. When subjected to electrochemical conditions at reducing potentials, the metallic Ir nanoparticles are found to be decahedral. The iridium oxide formed in the electrochemical oxidation contains small rutile-like clusters composed of edge- and corner-connected [IrO6] octahedra of a very confined range. These rutile domains are smaller than 1 nm. Combined with complementary SAXS data analysis to extract the particle size, we find that the OER-active iridium oxide phase lacks crystalline order. Additionally, we observe an iridium oxide contraction under OER conditions, which is confirmed by operando X-ray absorption spectroscopy. Our results highlight the need for multitechnique operando studies for a complete understanding of the electrochemically formed Ir oxide active in OER.

Iridium Single-Atom-Ensembles Stabilized on Mn-Substituted Spinel Oxide for Durable Acidic Water Electrolysis.

Exploring single-atom-catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost-effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single-atom-catalysts and Ir/Ru-based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal-leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short-range Ir single-atom-ensembles (IrSAE) stabilized on the surface of Mn-substituted spinel Co3O4 (IrSAE-CMO), which exhibits excellent mass activity and significantly improved durability (degradation-rate: ≈2mVh-1), outperforming benchmark IrO2 (≈44mVh-1) and conventional Irsingle-atoms on pristine-Co3O4 for acidic OER. First-principle calculations reveal that Mn-substitution in the octahedral sites of Co3O4 substantially reduces the migration energy barrier for Irsingle-atoms on the CMO surface compared to pristine-Co3O4, facilitating the migration of Irsingle-atoms to form strongly correlated IrSAE during pyrolysis. Extensive ex situ characterization, operando X-ray absorption and Raman spectroscopies, pH-dependence activity tests, and theoretical calculations indicate that the rigid IrSAE with appropriate Ir-Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir-dissolution and structural collapse, boosting the stability in an acidic environment.

Scalable Solid-State Synthesis of Carbon-Supported Ir Electrocatalysts for Acidic Oxygen Evolution Reaction: Exploring the Structure-Activity Relationship.

Enhancing iridium (Ir)-based electrocatalysts to achieve high activity and robust durability for the oxygen evolution reaction (OER) in acidic environments has been an ongoing mission in the commercialization of proton exchange membrane (PEM) electrolyzers. In this study, we present the synthesis of carbon-supported Ir nanoparticles (NPs) using a modified impregnation method followed by solid-state reduction, with Ir loadings of 20 and 40 wt % on carbon. Among the catalysts, the sample with an Ir loading of 20 wt % synthesized at 1000 °C with a heating rate of 300 °C/h demonstrated the highest mass-normalized OER performance of 1209 A gIr-1 and an OER current retention of 80% after 1000 cycles of cyclic voltammetry (CV). High-resolution STEM images confirmed the uniform dispersion of NPs, with diameters of 1.6 ± 0.4 nm across the support. XPS analysis revealed that the C-O and C═O peaks shifted slightly toward higher binding energies for the best-performing catalyst. In comparison, the metallic Ir state shifted toward lower binding energies compared to other samples. This suggests electron transfer from the carbon support to the Ir NPs, indicating a potential interaction between the catalyst and the support. This work underscores the strong potential of the solid-state method for the scalable synthesis of supported Ir catalysts.

Breaking the Bottleneck of Activity and Stability of RuO2-Based Electrocatalysts for Acidic Oxygen Evolution.

Electrochemical acidic oxygen evolution reaction (OER) is an important part for water electrolysis utilizing a proton exchange membrane (PEM) apparatus for industrial H2 production. RuO2 has garnered considerable attention as a potential acidic OER electrocatalyst. However, the overoxidation of Ru active sites under high potential conditions is usually harmful for activity and stability, thereby posing a challenge for large-scale commercialization, which needs effective strategies to circumvent the leaching of Ru and further activate Ru sites. Herein, a Mini-Review is presented to summarize the recent developments regarding the activation and stabilization of the Ru active sites and lattice oxygen through the modulation of the d-band center, coordination environment, bridged heteroatoms, and vacancy engineering, as well as structural protection strategies and reaction pathway optimization to promote the acidic OER activity and stability of RuO2-based electrocatalysts. This Mini-Review offers a profound understanding of the design of RuO2-based electrocatalysts with greatly enhanced acidic OER performances.

Designing neighboring-site activation of single atom via tunnel ions for boosting acidic oxygen evolution

Realizing an efficient turnover frequency in the acidic oxygen evolution reaction by modifying the reaction configuration is crucial in designing high-performance single-atom catalysts. Here, we report a “single atom–double site” concept, which involves an activatable inert manganese atom redox chemistry in a single-atom Ru-Mn dual-site platform with tunnel Ni ions as the trigger. In contrast to conventional single-atom catalysts, the proposed configuration allows direct intramolecular oxygen coupling driven by the Ni ions intercalation effect, bypassing the secondary deprotonation step instead of the kinetically sluggish adsorbate evolution mechanism. The strong bonding of Ni ions activates the inert manganese terminal groups and inhibits the cross-site disproportionation process inherent in the Mn scaffolding, which is crucial to ensure the dual-site platform. As a result, the single-atom Ru-Ni-Mn octahedral molecular sieves catalyst delivers a low overpotential, adequate mass activity and good stability.

Highly valent cobalt-manganese spinel nanowires induced by fluorine-doping for durable acid oxygen evolution reaction

The increase in the fraction of high-valent metal cations is of significant importance for enhancing the stability of noble-metal-free catalysts in the acid oxygen evolution reaction (OER). Herein, we report the preparation of a cobalt-manganese oxide spinel nanowire catalyst, where the incorporation and stabilization of high-valent cation fractions are induced by electron-withdrawing anionic fluorine groups. By the XPS, the strongly electronegative F atoms improve the ratio of Co3+/Co2+ and Mn4+/Mn3+, thereby enhancing OER activity and stability. The hydrophilicity F-MCO nanowires have a large specific surface area and great conductivity, which expose more catalytically active sites and continuously promotes oxygen evolution. The proposed F-MCO catalyst requires only an overpotential of 210 mV at the current density of 10 mA cm−2 and can maintain stable operation for more than 100 h. And a photovoltaic-electrolysis device with the F-MCO electrocatalyst delivers a solar-to-hydrogen efficiency of 15.1 %.

Formation of Core‐Shell Ir@TiO2 Nanoparticles through Hydrogen Treatment as Acidic Oxygen Evolution Reaction Catalysts

Formation of Core‐Shell Ir@TiO₂ Nanoparticles through Hydrogen Treatment as Acidic Oxygen Evolution Reaction Catalysts

Deciphering the work function induced local charge regulation towards activating an octamolybdate cluster-based solid for acidic water oxidation.

The advancement of highly robust and efficient electrocatalysts for the oxygen evolution reaction (OER) under acidic conditions is imperative for the sustainable production of green hydrogen. In accomplishing sustainable and sturdy electrocatalysts for oxygen evolution at low pH, the challenge is tough for non-iridium/ruthenium-based electrocatalysts. This study elaborates on the intrinsic alterations in electronic arrangements and structural disorder upon the precise activation of an octamolybdate cluster-based solid [{Cu(pz)4}2Mo8O26]·2H2O through room temperature grinding with rGO (reduced graphene oxide), resulting in enhanced conductivity, stability, and activity of the electrocatalyst towards the acidic OER without employing any benchmark metal ion (Ru or Ir). Additionally, the work function of the composites was found to be low compared to that of pristine polyoxometalates (POMs), indicative of the improved conducive behavior, which is lacking in the POM structure. The catalyst displays a notably reduced overpotential of 185 mV to achieve a current density of 10 mA cm-2, coupled with significant stability lasting 24 hours at a higher current density of 100 mA cm-2. These findings propose the manipulation of crystalline POMs with highly conductive non-metallic elements to facilitate superior water oxidation at lower pH levels which can help in the production of green hydrogen.

Regulating Strain and Electronic Structure of Indium Tin Oxide Supported IrOx Electrocatalysts for Highly Efficient Oxygen Evolution Reaction in Acid.

The development of proton exchange membrane water electrolysis is a promising technology for hydrogen production, which has always been restricted by the slow kinetics of the oxygen evolution reaction (OER). Although IrOx is one of the benchmark acidic OER electrocatalysts, there are still challenges in designing highly active and stable Ir-based electrocatalysts for commercial application. Herein, a Ru-doped IrOx electrocatalyst with abundant twin boundaries (TB-Ru0.3Ir0.7Ox@ITO) is reported, employing indium tin oxide with high conductivity as the support material. Combing the TB-Ru0.3Ir0.7Ox nanoparticles with ITO support could expose more active sites and accelerate the electron transfer. The TB-Ru0.3Ir0.7Ox@ITO exhibits a low overpotential of 203 mV to achieve 10 mA cm-2 and a high mass activity of 854.45 A g-1noblemetal at 1.53 V vs RHE toward acidic OER, which exceeds most reported Ir-based OER catalysts. Moreover, improved long-term stability could be obtained, maintaining the reaction for over 110 h at 10 mA cm-2 with negligible deactivation. DFT calculations further reveal the activity enhancement mechanism, demonstrating the synergistic effects of Ru doping and strains on the optimization of the d-band center (εd) position and the adsorption free energy of oxygen intermediates. This work provides ideas to realize the trade-off between high catalytic activity and good stability for acidic OER electrocatalysts.

Rationalizing Acidic Oxygen Evolution Reaction over IrO2: Essential Role of Hydronium Cation

Rationalizing Acidic Oxygen Evolution Reaction over IrO₂: Essential Role of Hydronium Cation

Synergistic Sr Activation and Cr Buffering Effect on RuO2 Electronic Structures for Enhancing the Acidic Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) performance of ruthenium-based oxides strongly correlates with the electronic structures of Ru. However, the widely adopted monometal doping method unidirectionally regulates only the electronic structures, often failing to balance the activity and stability. Here, we propose an "elastic electron transfer" strategy to achieve bidirectional optimization of the electronic structures of Sr, Cr codoped RuO2 catalysts for acidic OER. The introduction of electron-withdrawing Sr intrinsically activates the Ru sites by increasing the oxidation state of Ru. Simultaneously, Cr acts as an electron buffer, donating electrons to Ru in the presence of Sr in the as-prepared catalysts and absorbing excess electrons from Sr leaching during the OER. Such a bidirectional regulation feature of Cr prevents overoxidation of Ru and maintains its high oxidation state during the OER. The optimal Ru3Cr1Sr0.175 catalyst exhibits a low overpotential (214 mV @ 10 mA cm-2) and excellent stability (over 300 h).

Modulating Carrier Oxygen Vacancies to Enhance Strong Oxide‐Support Interaction in IrO2/Nb2O5‐x Catalysts for Promoting Acidic Oxygen Evolution Reaction

AbstractGiven the pronounced dissolution of electrocatalysts in acidic environments, the quest for effective oxygen evolution reaction (OER) electrocatalysts suitable for proton exchange membrane (PEM) water electrolyzers persists as a formidable challenge. In this investigation, catalysts are synthesized by creating oxygen vacancies within various metal oxides (Nb2O5‐x, Ta2O5‐x, ZrO2‐x, TiO2‐x) through plasma‐assisted method, thereby facilitating the immobilization of IrO2 onto these defect‐rich surfaces. The findings unveil that IrO2/Nb2O5‐x manifests reduced overpotentials during acidic OER, achieving an overpotential down to 225 mV@10 mA cm−2, coupled with outstanding durability at multicurrent densities exceeding 200 h, attributed to strong oxide‐support interaction (SOSI) between the IrO2 catalyst and Nb2O5‐x substrate. Density functional theory (DFT) computations uncover intensified binding affinities between IrO2 and Nb2O5‐x, thus modulating the central energy levels of Ir's d orbitals toward favorable OER conditions, consequently bolstering the electrocatalytic activity and stability of the composite catalyst. Furthermore, employing IrO2/Nb2O5‐x as a PEM electrolyzer anode enables consistent operation at 1000 mA cm−2 for 200 h, with an Ir content of only 0.2852 mg cm−2 and an energy consumption of 4.34 kWh Nm−3 H2. This achievement substantially lowers the cost of hydrogen production to US$ 0.96 per kilogram, underscoring its potential for practical applications.

Half-metallization Atom-Fingerprints Achieved at Ultrafast Oxygen-Evaporated Pyrochlores for Acidic Water Oxidation.

The stability and catalytic activity of acidic oxygen evolution reaction (OER) are strongly determined by the coordination states and spatial symmetry among metal sites at catalysts. Herein, an ultrafast oxygen evaporation technology to rapidly soften the intrinsic covalent bonds using ultrahigh electrical pulses is suggested, in which prospective charged excited states at this extreme avalanche condition can generate a strong electron-phonon coupling to rapidly evaporate some coordinated oxygen (O) atoms, finally leading to a controllable half-metallization feature. Simultaneously, the relative metal (M) site arrays can be orderly locked to delineate some intriguing atom-fingerprints at pyrochlore catalysts, where the coexistence of metallic bonds (M─M) and covalent bonds (M─O) at this symmetry-breaking configuration can partially restrain crystal field effect to generate a particular high-spin occupied state. This half-metallization catalyst can effectively optimize the spin-related reaction kinetics in acidic OER, giving rise to 10.3 times (at 188mV overpotential) reactive activity than pristine pyrochlores. This work provides a new understanding of half-metallization atom-fingerprints at catalyst surfaces to accelerate acidic water oxidation.

Supported IrO2 Nanocatalyst with Multilayered Structure for Proton Exchange Membrane Water Electrolysis.

The design of a low-iridium-loading anode catalyst layer with high activity and durability is a key challenge for a proton exchange membrane water electrolyzer (PEMWE). Here, the synthesis of a novel supported IrO2 nanocatalyst with a tri-layered structure, dubbed IrO2@TaOx@TaB that is composed of ultrasmall IrO2 nanoparticles anchored on amorphous TaOx overlayer of TaB nanorods is reported. The composite electrocatalyst shows great activity and stability toward the oxygen evolution reaction (OER) in acid, thanks to its dual-interface structural feature. The electronic interaction in IrO2/TaOx interface can regulate the coverage of surface hydroxyl groups, the Ir3+/ Ir4+ ratio, and the redox peak potential of IrO2 for enhancing OER activity, while the dense TaOx overlayer can prevent further oxidation of TaB substrate and stabilize the IrO2 catalytic layers for improving structural stability during OER. The IrO2@TaOx@TaB can be used to fabricate an anode catalyst layer of PEMWE with an iridium-loading as low as 0.26mgcm-2. The low-iridium-loading PEMWE delivers high current densities at low cell voltages (e.g., 3.9Acm-2@2.0 V), and gives excellent activity retention for more than 1500h at 2.0Acm-2 current density.

Cerium-doped construction of oxygen vacancies in IrO2 to promote acidic OER reaction

Proton exchange membrane electrolysis of water is currently recognized in the world as an up-and-coming method for the preparation of green hydrogen energy. Due to its sustainability and low pollution, it has attracted much attention from practitioners recently. The most advanced iridium oxide (IrO2) is the most promising catalyst.However, developing a highly efficient and stable IrO2 catalyst that can adapt to industrial conditions remains a terrific challenge. One of the main problems to be solved is that the slow oxygen evolution reaction(OER) at the anode limits the production of hydrogen. We propose a straightforward method for synthesizing Ce metal-doped IrO2 with a high oxygen vacancy concentration while simultaneously improving the IrO2 catalytic activity and stability.The Ce-doped IrO2 (Ce-IrO2) exhibits a microscopic nanoparticle morphology and a high density of oxygen vacancies, enabling a rapid oxygen evolution reaction (OER) process with a low overpotential of 240 mV at 10 mA·cm-2 and a remarkable stability of over 50 h under acidic conditions.A growing body of research shows a synergistic effect of oxygen vacancies and mental dopants on the adsorption and evolution of active intermediates in the active center so that the oxygen evolution reaction activity of the Ir-based catalyst can be improved. We hope that ourwork will provide a sample method for acquiring catalysts capable of adapting to a wide range of conditions via metal doping.

Non-Noble-Metal-Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives.

The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO2 reduction, nitrogen fixation, and metal-air batteries. Among various water electrolysis techniques, proton exchange membrane (PEM)-based water electrolysis devices offer numerous advantages, including high current densities, exceptional chemical stability, excellent proton conductivity, and high-purity H2. Nevertheless, the prohibitive cost associated with Ir/Ru-based OER electrocatalysts poses a significant barrier to the broad-scale application of PEM-based water splitting. Consequently, it is crucial to advance the development of non-noble metal OER catalysis substance with high acid-activity and stability, thereby fostering their widespread integration into PEM water electrolyzers (PEMWEs). In this review, a comprehensive analysis of the acidic OER mechanism, encompassing the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM) and oxide path mechanism (OPM) is offered. Subsequently, a systematic summary of recently reported noble-metal-free catalysts including transition metal-based, carbon-based and other types of catalysts is provided. Additionally, a comprehensive compilation of in situ/operando characterization techniques is provided, serving as invaluable tools for furnishing experimental evidence to comprehend the catalytic mechanism. Finally, the present challenges and future research directions concerning precious-metal-free acidic OER are comprehensively summarized and discussed in this review.

Surface‐Segregated IrCo Nanoparticles on CoO Nanosheets with Ultralow Ir Loading for Efficient Acidic Water Splitting

AbstractIrO2 is the benchmark catalyst for acidic oxygen evolution reaction (OER), however, the high cost and low earth abundance hinder its large‐scale application. Herein, surface‐segregated IrCo nanoparticles on CoO nanosheets with a strong electronic interaction are synthesized through the ion exchange‐pyrolysis method. The resulting IrCo−CoO heterostructures, containing an ultra‐low Ir content of 4.73 wt %, demonstrate exceptional performance in the acidic OER. The catalyst exhibits a low overpotential of 270 mV at a current density of 10 mA cm−2 and remarkable stability, with noticeable activity decay observed only after 140 hours of continuous operation. These results surpass most reported Ir‐based electrocatalysts. Specifically, the mass activity at the overpotential of 300 mV for the IrCo−CoO catalyst reaches 124.52 mA mgIr−1, which is 20 times higher than that of commercial IrO2. Furthermore, we constructed a home‐made overall water splitting cell utilizing IrCo−CoO heterostructures as both anode and cathode electrodes, achieving a current density of 10 mA cm‐−2 at a voltage of 1.51 V. Our findings present a promising strategy for designing high‐efficient catalysts with significantly reduced noble metals loading.