Oxide Oxygen Evolution Reaction Research Articles

Mesoporous RE0.5Ce0.5O2-x Fluorite Electrocatalysts for the Oxygen Evolution Reaction.

Developing highly active and stable electrocatalysts for the oxygen evolution reaction (OER) is key to improving the efficiency and practical application of various sustainable energy technologies including water electrolysis, CO2 reduction, and metal air batteries. Here, we use evaporation-induced self-assembly (EISA) to synthesize highly porous fluorite nanocatalysts with a high surface area. In this study, we demonstrate that a 50% rare-earth cation substitution for Ce in the CeO2 fluorite lattice improves the OER activity and stability by introducing oxygen vacancies into the host lattice, which results in a decrease in the adsorption energy of the OH* intermediate in the OER. Among the binary fluorite compositions investigated, Nd2Ce2O7 is shown to display the lowest OER overpotential of 243 mV, achieved at a current density of 10 mA cm-2, and excellent cycling stability in an alkaline medium. Importantly, we demonstrate that rare-earth oxide OER electrocatalysts with high activity and stability can be achieved using the EISA synthesis route without the incorporation of transition and noble metals.

In situ formation of robust nanostructured cobalt oxyhydroxide/cobalt oxide oxygen evolution reaction electrocatalysts

The conversion of mixed metal sulfide precursors into active and robust metal oxide/hydroxide oxygen evolution reaction electrocatalysts is reported.

Understanding the Origin of Reconstruction in Transition Metal Oxide Oxygen Evolution Reaction Electrocatalysts.

Electrochemical water splitting to generate hydrogen energy fills a gap in the intermittency issues for wind and sunlight power. Transition metal (TM) oxides have attracted significant interest in water oxidation due to their availability and excellent activity. Typically, the transitional metal oxyhydroxides species derived from these metal oxides are often acknowledged as the real catalytic species, due to the irreversible structural reconstruction. Hence, in order to innovatively design new catalyst, it is necessary to provide a comprehensive understanding for the origin of surface reconstruction. In this review, the most recent developments in the reconstruction of transition metal-based oxygen evolution reaction electrocatalysts were introduced, and various chemical driving forces behind the reconstruction mechanism were discussed. At the same time, specific strategies for modulating pre-catalysts to achieve controllable reconfiguration, such as metal substituting, increase of structural defect sites, were summarized. At last, the issues for the further understanding and optimization of transition metal oxides compositions based on structural reconstruction were provided.

Multiple synergies on cobalt-based spinel oxide nanowires for electrocatalytic oxygen evolution

Cobalt-based spinel oxides have excellent oxygen evolution reaction (OER) activities and are cheap to produce; however, they have limited commercial applications due to their poor electrical conductivities and weak stabilities. Herein, we soaked Co3-xNixO4 nanowires in NaBH4 solutions, which endowed Co3-xNixO4 with significant oxygen vacancy content and decorated BOx motifs outside the Co3-xNixO4 nanowires. X-ray photoelectron spectroscopy and in situ Raman data suggest that these evolutions improved the conductivity, hydrophilicity, and increased active sites of the spinel oxides, which synergistically boosted their overall OER performances. This improved performance made the optimized BOx-covered Co2.1Ni0.9O4 nanowires generate a current density of 10 mA cm−2 when used for the OER at an overpotential of only 307 mV, maintaining excellent stability at 50 mA cm−2 for 24 h. This study provides a facile method for designing cobalt-based spinel oxide OER catalysts.

Ex Situ Reconstruction-Shaped Ir/CoO/Perovskite Heterojunction for Boosted Water Oxidation Reaction.

The oxygen evolution reaction (OER) is the performance-limiting step in the process of water splitting. In situ electrochemical conditioning could induce surface reconstruction of various OER electrocatalysts, forming reactive sites dynamically but at the expense of fast cation leaching. Therefore, achieving simultaneous improvement in catalytic activity and stability remains a significant challenge. Herein, we used a scalable cation deficiency-driven exsolution approach to ex situ reconstruct a homogeneous-doped cobaltate precursor into an Ir/CoO/perovskite heterojunction (SCI-350), which served as an active and stable OER electrode. The SCI-350 catalyst exhibited a low overpotential of 240 mV at 10 mA cm-2 in 1 M KOH and superior durability in practical electrolysis for over 150 h. The outstanding activity is preliminarily attributed to the exponentially enlarged electrochemical surface area for charge accumulation, increasing from 3.3 to 175.5 mF cm-2. Moreover, density functional theory calculations combined with advanced spectroscopy and 18O isotope-labeling experiments evidenced the tripled oxygen exchange kinetics, strengthened metal-oxygen hybridization, and engaged lattice oxygen oxidation for O-O coupling on SCI-350. This work presents a promising and feasible strategy for constructing highly active oxide OER electrocatalysts without sacrificing durability.

Amorphous Oxysulfide Reconstructed from Spinel NiCo2S4 for Efficient Water Oxidation

The progress of effective and durable electrocatalysts for oxygen evolution reaction (OER) is urgent, which is essential to promote the overall efficiency of green hydrogen production. To improve the performance of spinel cobalt-based oxides, which serve as promising water oxidation electrocatalysts in alkaline electrolytes, most researches have been concentrated on cations modification. Here, an anionic regulation mechanism is employed to adopt sulfur(S)anion substitution to supplant NiCo2 O4 by NiCo2 S4 , which contributed to an impressive OER performance in alkali. It is revealed that the substitution of S constructs a sub-stable spinel structure that facilitates its reconstruction into active amorphous oxysulfide under OER conditions. More importantly, as the active phase in the actual reaction process, the hetero-anionic amorphous oxysulfide has an appropriately tuned electronic structure and efficient OER electrocatalytic activity. This work demonstrates a promising approach for achieving anion conditioning-based tunable structure reconstruction for robust and easy preparation spinel oxide OER electrocatalysts.

Efficient Ternary Mn-Based Spinel Oxide with Multiple Active Sites for Oxygen Evolution Reaction Discovered via High-Throughput Screening Methods.

The discovery of more efficient and stable catalysts for oxygen evolution reaction (OER) is vital in improving the efficiency of renewable energy generation devices. Given the large numbers of possible binary and ternary metal oxide OER catalysts, high-throughput methods are necessary to accelerate the rate of discovery. Herein, Mn-based spinel oxide, Fe10 Co40 Mn50 O, is identified for the first time using high-throughput methods demonstrating remarkable catalytic activity (overpotential of 310mV on fluorine-doped tin oxide (FTO) substrate and 237mV on Ni foam at 10mA cm-2 ). Using a combination of soft X-ray absorption spectroscopy and electrochemical measurements, the high catalytic activity is attributed to 1) the formation of multiple active sites in different geometric sites, tetrahedral and octahedral sites; and 2) the formation of active oxyhydroxide phase due to the strong interaction of Co2+ and Fe3+ . Structural and surface characterizations after OER show preservation of Fe10 Co40 Mn50 O surface structure highlighting its durability against irreversible redox damage on the catalytic surface. This work demonstrates the use of a high-throughput approach for the rapid identification of a new catalyst, provides a deeper understanding of catalyst design, and addresses the urgent need for a better and stable catalyst to target greener fuel.

Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis.

The oxygen evolution reaction (OER) is one of the key kinetically limiting half reactions in electrochemical energy conversion. Model epitaxial catalysts have emerged as a platform to identify structure-function-relationships at the atomic level, a prerequisite to establish advanced catalyst design rules. Previous work identified an inverse relationship between activity and the stability of noble metal and oxide OER catalysts in both acidic and alkaline environments: The most active catalysts for the anodic OER are chemically unstable under reaction conditions leading to fast catalyst dissolution or amorphization, while the most stable catalysts lack sufficient activity. In this perspective, we discuss the role that epitaxial catalysts play in identifying this activity-stability-dilemma and introduce examples of how they can help overcome it. After a brief review of previously observed activity-stability-relationships, we will investigate the dependence of both activity and stability as a function of crystal facet. Our experiments reveal that the inverse relationship is not universal and does not hold for all perovskite oxides in the same manner. In fact, we find that facet-controlled epitaxial La0.6Sr0.4CoO3-δ catalysts follow the inverse relationship, while for LaNiO3-δ, the (111) facet is both the most active and the most stable. In addition, we show that both activity and stability can be enhanced simultaneously by moving from La-rich to Ni-rich termination layers. These examples show that the previously observed inverse activity-stability-relationship can be overcome for select materials and through careful control of the atomic arrangement at the solid-liquid interface. This realization re-opens the search for active and stable catalysts for water electrolysis that are made from earth-abundant elements. At the same time, these results showcase that additional stabilization via material design strategies will be required to induce a general departure from inverse stability-activity relationships among the transition metal oxide catalysts to ultimately grant access to the full range of available oxides for OER catalysis.

Bimetallic Intersection in PdFe@FeOx‐C Nanomaterial for Enhanced Water Splitting Electrocatalysis

AbstractSupported Fe‐doped Pd‐nanoparticles (NPs) are prepared via soft transformation of a PdFe‐metal oraganic framework (MOF). The thus synthesized bimetallic PdFe‐NPs are supported on FeOx@C layers, which are essential for developing well‐defined and distributed small NPs, 2.3 nm with 35% metal loading. They are used as bifunctional nanocatalysts for the electrocatalytic water splitting process. They display superior mass activity for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), both in alkaline and acid media, compared with those obtained for benchmarking platinum HER catalyst, and ruthenium, and iridium oxide OER catalysts. PdFe‐NPs also exhibit outstanding stability against sintering that can be explained by the protecting role of graphitic carbon layers provided by the organic linker of the MOF. Additionally, the superior electrocatalytic performance of the bimetallic PdFe‐NPs compared with those of monometallic Pd/C NPs and FeOx points to a synergetic effect induced by Fe–Pd interactions that facilitates the water splitting reaction. This is supported by additional characterization of the PdFe‐NPs prior and post electrolysis by TEM, XRD, X‐ray photoelectron spectroscopy, and Raman revealing that dispersed PdFe NPs on FeOx@C promote interactions between Pd and Fe, most likely to be Pd–O–Fe active centers.

Highly Active Ni–Fe Based Oxide Oxygen Evolution Reaction Electrocatalysts for Alkaline Anion Exchange Membrane Electrolyser

Oxygen evolution reaction (OER) electrocatalysts are pivotal for sustainable hydrogen production through anion exchange membrane electrolysis. Cost-effective transition metals such as nickel and iron-based oxides (Ni–Fe–Ox) have been recognized as viable catalysts for the oxygen evolution process in alkaline media. In this work, we study the electrochemical characterization and stability of the Ni–Fe–Ox to find the suitability for AEM electrolysis. The results indicate that Ni–Fe–Ox has 5 times higher activity than pure Ni. The Ni–Fe–Ox electrodes exhibit an exceptionally high catalytic activity of 22 mA cm−2 at 1.55 V vs. RHE, and a Tafel value as low as 97 dec−1, for OER to occur. These findings imply that OER occurs at similar places along the Ni–Fe–Ox interface and that the Ni—Fe2O3 contact plays a significant role as the OER active site. Furthermore, it is also worth noting that the presence of metallic Ni allows for fast electron transit within the interface, which is necessary for successful electrocatalysis. Aside from the excellent OER performance, the exfoliated Ni–Fe–Ox demonstrated great stability with almost constant potential after 10 h of electrolysis at a current density of 10 mA cm−2. This work confirms Ni–Fe–Ox is a promising, highly efficient and cost-effective OER catalyst for AEM electrolysis.

Electrochemical conversion of chromium from tannery effluents for potential reuse in industrial applications.

Electrochemical oxidation of trivalent chromium from leather tanning mud waste leachates (containing ca 6g.L-1 Cr(III)) to its hexavalent form was carried out using a PbOx/Pb anode electrode in a prototype small (0.4 L) cylindrical batch electrochemical reactor. The PbOx/Pb anode was prepared by electrochemical anodization at constant current (75mAcm-2 for 30min) in a sulfuric acid solution and characterized by the cyclic voltammetry technique to investigate the effect of pH on the process. It was found that at pH = 3, Cr(III) oxidation prevails over the competing water oxidation-oxygen evolution reaction (OER), hence increasing the efficiency of the process. A detailed study of pH (0-3), current density (12-24mAcm-2), and cell type (divided-undivided) effects on bulk electrolysis of Cr(III) leachates in the batch prototype reactor resulted in process optimization. At pH = 3, 12mAcm-2 and a cathode inserted in a porous diaphragm envelope, nearly 70% conversion was achieved at a nearly 60% current efficiency, among the highest in the previously reported literature. The method (further optimized with an ion-selective membrane separator) could offer an attractive route for tannery Cr(III) conversion to Cr(VI) for reuse as an etchant or electroplating agent.

Comprehensive Structural Descriptor for Electrocatalytic Oxygen Evolution Activities of Iron Oxides

AbstractTo determine the structural descriptor of the oxygen evolution reaction (OER) in a wide range of Fe‐based oxides, we investigate Fe2O3 polymorphs. Remarkably, the OER activity of the polymorphs strongly depends on the atomic configurations in the crystals, and shorter Fe−O bond lengths are more beneficial for the OER. DFT calculations reveal that the trend of Fe−O bond length on the Fe2O3 polymorphs exhibits a positive correlation with their energy gaps between the occupied oxygen 2p and the unoccupied iron 3d orbitals, i. e., charge‐transfer energy, which promotes the OER activities of metal oxides. Surprisingly, the relationship between the Fe−O bond length and the OER activity can also be applied to a wide range of previously reported Fe‐based multimetal oxide OER catalysts, regardless of their chemical compositions and categories of crystal structures, including perovskite, spinel, brownmillerite, and other types of oxides. The discovered descriptor is an important guideline for the rational design of Fe‐based oxides with excellent catalytic properties for the OER and contributes to the establishment of a hydrogen society.

Boron-doped amorphous iridium oxide with ultrahigh mass activity for acidic oxygen evolution reaction

Oxygen evolution reaction (OER), as the primary anodic reaction, plays a critical role in many electrochemical energy conversion processes. As the state-of-the-art OER catalysts, iridium-based materials are largely hindered from practical applications mainly due to the extreme scarcity of iridium. Here we demonstrate the successful fabrication of boron-doped amorphous iridium oxide (IrOx-B) via a facile boric acid-assisted method, which realizes an ultrahigh OER mass activity of 2779 A g Ir −1 at 300 mV overpotential, representing one of the best acidic OER catalysts reported so far. It is found that boric acid can not only facilitate the exposure of Ir, but also dope the amorphous IrOx with a form of metaborate, which could further modify the electronic and local ligand structure of Ir for the improved intrinsic activity. Interestingly, the reported strategy is universal that can be applied to improve other metal oxide OER catalysts, highlighting a versatile strategy for creating high-performance electro-catalysts with ultrahigh mass activity for OER and beyond.

A‐Site Management Prompts the Dynamic Reconstructed Active Phase of Perovskite Oxide OER Catalysts

AbstractPerovskites (ABX3) are promising oxygen evolution reaction (OER) catalysts for their highly intrinsic activity. The in‐depth understanding and the adjustment of dynamic reconstruction of active phases for perovskites in OER are still a daunting challenge. Here, a refined A‐site management strategy is proposed for perovskite oxides, which facilitates the surface reconstruction of the B‐site element based active phase to enhance the OER performance. Electrocatalyst LaNiO3 displays a dynamic reconstruction feature during OER with the growth of a self‐assembled NiOOH active layer, based on the in situ electrochemical Raman technology. Precise A‐site Ce doping lowers the reconstruction potential for the active phase and the dynamic structure–activity correlation is well established. Theoretical calculations demonstrate that A‐site Ce substitution upshifts the O 2p level for greater structural flexibility with optimized oxygen vacancy content, thereby activating the B‐site atom and promoting the active phase reconstruction. These results suggest that A‐site management prompts the B‐site element based active phase dynamic reconstruction via engineered X‐site content as a bridge. Therefore, indicating the strong correlation of each‐site component in perovskite oxides during OER and deepening the understanding of the fundamental processes of the structural transformation and further benefiting the accurate design of high‐efficiency perovskite OER electrocatalysts.

Assembly of a Highly Active Iridium-Based Oxide Oxygen Evolution Reaction Catalyst by Using Metal-Organic Framework Self-Dissolution.

The proton exchange membrane (PEM) electrolyzer for hydrogen production has multiple advantages but is greatly restricted by expensive iridium and sluggish oxygen evolution reaction (OER) kinetics. The most promising way to reduce the precious metal loading is to design and develop highly active Ir-based catalysts. In this study, a versatile approach is reported to prepare a hybrid in the form of a catalyst-support structure (Fe-IrOx@α-Fe2O3, abbreviated Ir@Fe-MF) by utilizing the self-dissolving properties of Fe-MIL-101 under aqueous conditions. The formation of this hybrid is mainly due to the Ir4+ and released Fe3+ ions coprecipitated to assemble into Fe-IrOx nanoparticles, and the Fe3+ released from the inward collapse of the metal-organic framework (MOF) spontaneously forms α-Fe2O3. The prepared Ir@Fe-MF-2 hybrid exhibits enhanced catalytic activity toward OER with a lower onset potential and Tafel slop, and only 260 mV overpotential is required to drive the current density to reach 10 mA cm-2. The performed characterizations clearly indicate that the IrO6 coordination structure is changed significantly by Fe incorporated into the IrO2 lattice. The performed X-ray adsorption spectra (XAS) provides evidence that Ir 5d orbital degeneracy is eliminated because of multiple orbitals being semi-occupied in the presence of Fe, which is mainly responsible for the enhancement of OER activity. These findings open an opportunity for the design and preparation of more efficient OER catalysts of transition metal oxides by utilization of the MOF materials. It should be highlighted that a long-term stability of this catalyst run at a high current density in acidic conditions still faces great challenges.

Hierarchical microspheres of Co2CrO4 nanoplates for electrocatalytic water oxidation

Co2CrO4 microspheres were hydrothermally synthesized as new electrocatalyst for water oxidation/oxygen evolution reaction (OER). SEM and TEM analyses revealed the hierarchical morphology of the microspheres which are assembly of nanoplates formed by the assembly of individual nanoparticles with ca. 17 nm size. BET analyses showed that this new material has very large surface area (125 m2 g−1). Co2CrO4 microspheres were then used to modify glassy carbon electrode for electrocatalytic investigations in alkaline medium. The results revealed that this new material has promising catalytic performance toward OER with an onset potential of 1.52 V vs. RHE and an overpotential of 456 mV at 10 mA cm−2 current density. In addition, the microspheres presented very good stability during long-term constant potential electrolysis. In general, the catalytic performance of Co2CrO4 microspheres is comparable to the one of benchmark RuO2 with an advantage of being more stable and cost-effective.

Enhanced activity of mesoporous SrCo0.8Fe0.1Nb0.1O3-δ perovskite electrocatalyst by H2O2 treatment for oxygen evolution reaction

The development of transition metal oxide oxygen evolution reaction (OER) electrocatalysts provides a new design strategy for renewable energy technologies (water electrolyzers and metal air cells). In the perovskite metal oxide family, we chose SrCo0.8Fe0.1Nb0.1O3-δ (SCFN) OER catalyst with excellent catalytic properties, and in order to further increase its performance. Here, we treat mesoporous SCFN perovskite electrocatalysts with H2O2. After 5 times treatment in H2O2, the specific surface area of SCFN-5 reaches 20.9 m2 g−1, whereas as-prepared SCFN-0 only has 2.3 m2 g−1. SCFN-5 catalyst shows significantly high OER catalytic activity, displaying an overpotential of 0.44 V at 10 mA cm−2 and charge transfer resistance (Rct) value of 59 Ω, which are much lower than those of untreated and ball-milled SCFN samples. Our results indicate that several factors, including the high surface area, good charge transfer abilities, formation of hydrous oxide and the oxidation of Co3+ may contribute to the excellent OER activity.

Elucidation of Structure-Activity Correlations in a Nickel Manganese Oxide Oxygen Evolution Reaction Catalyst by Operando Ni L-Edge X-ray Absorption Spectroscopy and 2p3d Resonant Inelastic X-ray Scattering.

Herein, we report the synthesis and electrochemical oxygen evolution experiments for a graphene-supported Ni3MnO4 catalyst. The changes that occur at the Ni active sites during the electrocatalyic oxygen evolution reaction (OER) were elucidated by a combination of operando Ni L-edge X-ray absorption spectroscopy (XAS) and Ni 2p3d resonant inelastic X-ray scattering (RIXS). These data are compared to reference measurements on NiO, β-Ni(OH)2, β-NiOOH, and γ-NiOOH. Through this comparative analysis, we are able to show that under alkaline conditions (0.1 M KOH), the oxides of the Ni3MnO4 catalyst are converted to hydroxides. At the onset of catalysis (1.47 V), the β-Ni(OH)2-like phase is oxidized and converted to a dominantly γ-NiOOH phase. The present study thus challenges the notion that the β-NiOOH phase is the active phase in OER and provides further evidence that the γ-NiOOH phase is catalytically active. The ability to use Ni L-edge XAS and 2p3d RIXS to provide a rational basis for structure-activity correlations is highlighted.

Highly Active and Durable Perovskite OER Catalyst for Pure Water Anion Exchange Membrane Electrolysis

Anion exchange membrane (AEM) water electrolysis can afford cheaper hydrogen (H2) production compared to the current state-of-the-art of proton exchange membrane (PEM) electrolysis. In AEM electrolysis, i.e., in alkaline environment, platinum group metal (PGM)-free catalysts can be adopted as oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts, contrary to the PEM electrolysis in which PGM-catalysts should be used. Furthermore, expensive titanium flow-field that is indispensable in acidic PEM electrolyzer can be replaced by inexpensive stainless flow-field. These advantages of AEM electrolysis make AEM electrolysis attractive technology to produce H2 in low cost. However currently performance of AEM electrolysis is much lower than that of PEM electrolysis. Therefore to make the AEM electrolysis technology viable, significant advancement in AEM electrolysis technology is needed. Many PGM-free OER catalysts measured in aqueous alkaline electrolytes, such as 0.1 M KOH or NaOH, have demonstrated as high activities as that of PGM IrO2 OER catalysts measured in an aqueous acid electrolytes in an electrochemical cell test. This implies that the low AEM electrolysis performance is possibly caused by some detrimental effect of AEM/anion exchange ionomer (AEI) onto catalysts. In this work we exploited different types of catalysts and AEIs to investigate the effect of catalyst-AEI interaction on AEM electrolysis performance. We observed that catalyst-AEI interaction substantially affects the AEM water electrolysis performance. The higher activity and durability of perovskite oxide OER catalyst than IrO2 OER catalyst in AEM water electrolysis can be explained by this catalyst-AEI interaction. In this talk, we will discuss the causes for low AEM electrolysis and possible pathways to improve AEM water electrolysis performance. Acknowledgements The authors gratefully acknowledge research support from the HydroGEN Advanced Water Splitting Materials Consortium, established as part of the Energy Materials Network under the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office.

Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation

The development of efficient and low-cost electrocatalysts for the oxygen evolution reaction (OER) is critical for improving the efficiency of water electrolysis. Here, we report a strategy using Fe substitution to enable the inactive spinel CoAl2O4 to become highly active and superior to the benchmark IrO2. The Fe substitution is revealed to facilitate surface reconstruction into active Co oxyhydroxides under OER conditions. It also activates deprotonation on the reconstructed oxyhydroxide to induce negatively charged oxygen as an active site, thus significantly enhancing the OER activity of CoAl2O4. Furthermore, it promotes the pre-oxidation of Co and introduces great structural flexibility due to the uplift of the oxygen 2p levels. This results in the accumulation of surface oxygen vacancies along with lattice oxygen oxidation that terminates as Al3+ leaches, preventing further reconstruction. We showcase a promising way to achieve tunable electrochemical reconstruction by optimizing the electronic structure for low-cost and robust spinel oxide OER catalysts.