Developments and perspectives of oxide-based catalysts for the oxygen evolution reaction

Fabbri, Emiliana; Habereder, Anja; Waltar, Kay; Kötz, R.; Schmidt, Thomas J.

doi:10.1039/c4cy00669k

Cited by 1,121 publications

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“…The importance of the high-spin Mn(III), through its e 1 g electronic configuration, has been realized in other manganese oxides for OER catalysis (2,9) and also follows the design principle of Suntivich et al (10) that a near-unity eg occupancy may imply good OER catalytic activity. This easy switching of the oxidation state is also a typical behavior for the transition metal cation undergoing back and forth changes between several oxidation states in OER catalysts during the water oxidation cycle (11)(12)(13). OER catalysts like Co-and Ni-doped hematite (12) and cobalt oxides (13), as well as birnessite, operate best in alkaline conditions with a high concentration of OH − , where the following reaction occurs:…”

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confidence: 99%

Redox properties of birnessite from a defect perspective

Peng

McKendry

Ding

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Birnessite, a layered-structure MnO 2 , is an earth-abundant functional material with potential for various energy and environmental applications, such as water oxidation. An important feature of birnessite is the existence of Mn(III) within the MnO 2 layers, accompanied by interlayer charge-neutralizing cations. Using first-principles calculations, we reveal the nature of Mn(III) in birnessite with the concept of the small polaron, a special kind of point defect. Further taking into account the effect of the spatial distribution of Mn(III), we propose a theoretical model to explain the structure-performance dependence of birnessite as an oxygen evolution catalyst. We find an internal potential step which leads to the easy switching of the oxidation state between Mn(III) and Mn(IV) that is critical for enhancing the catalytic activity of birnessite. Finally, we conduct a series of comparative experiments which support our model.birnessite MnO 2 | small polaron | catalysis | water oxidation P hotoelectrochemical (PEC) splitting of water into H2 and O2 (artificial photosynthesis) provides an attractive way to harvest solar energy. The process consists of the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), both of which are facilitated with catalysts in practice. Currently, one of the biggest challenges is to develop a cheap and efficient catalyst for the former reaction with a low overpotential, which is still needed to overcome the kinetic barriers (already lowered by the catalyst) along the path from reactants to products. Birnessite, similar to the oxygen-evolving complex in Photosystem II for photosynthesis in regard to the coexistence of Mn(III) (nominal Mn 3+ ) and Mn(IV) (nominal Mn 4+ ) within its structure (1-3), has already shown a moderate catalytic performance with the overpotentials reported from 0.6 V to 0.8 V (4-8).Birnessite has the general formula Mx MnO2·1.5(H2O), composed of layers of edge-sharing MnO6 octahedra as shown in Fig. 1 for the hexagonal phase, and an interlayer of randomly distributed water molecules and metal (M) cations (like K + , Na + , and Ca 2+ ). With the charge balanced by the interlayer cations, some of the Mn cations within the MnO2 layer are reduced from Mn(IV) to Mn(III). The coexistence of Mn(IV) and Mn(III), and further the "balanced equilibrium" or low energy barrier between them, has been suspected to be a critical factor for its catalytic activity (1). The importance of the high-spin Mn(III), through its e 1 g electronic configuration, has been realized in other manganese oxides for OER catalysis (2, 9) and also follows the design principle of Suntivich et al. (10) that a near-unity eg occupancy may imply good OER catalytic activity. This easy switching of the oxidation state is also a typical behavior for the transition metal cation undergoing back and forth changes between several oxidation states in OER catalysts during the water oxidation cycle (11-13). OER catalysts like Co-and Ni-doped hematite (12) and cobalt oxides (13), as well as ...

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confidence: 99%

Redox properties of birnessite from a defect perspective

Peng

McKendry

Ding

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…The perovskite structure is able to accommodate cation substitution by partial substitution of either the A-and/or B-site cations with another element yielding a plethora of possible A x A 1-x B y B 1-y O 3 compositions and the potential of tuning the material properties such as catalytic activity, electronic and ionic conductivity, chemical stability and thermal properties. 2,10 In addition, according to the condition of charge neutrality, electrons/holes or oxygen vacancies at the oxygen lattice sites would be introduced when A-or B-site cations are partially or fully substituted with other cations. As a result, the defect concentration, electrical properties and oxygen mobility are changed, which has led to their use across a broad range of catalytic applications including oxygen electrocatalysis for high and low temperature applications.…”

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confidence: 99%

“…This reaction, occurring at the anode of the water splitting reaction, is primarily governed by slow kinetics 1 and has therefore been extensively studied to improve the performance of devices such as water electrolyzers. 2,3,4 Significant overpotential losses remain a hurdle which requires the need for rare and expensive noble-metal based electrocatalysts for efficient operation. The development and application of new materials able to compete with expensive state-of-the-art current electrocatalysts for hydrogen generating devices therefore yields a great challenge.…”

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confidence: 99%

Electrocatalysis of Perovskites: The Influence of Carbon on the Oxygen Evolution Activity

Mohamed

Cheng

Fabbri

et al. 2015

J. Electrochem. Soc.

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Single and double perovskite oxides have been reported to be amongst the most active electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolyte. Although a detailed study of the bulk electronic structure-activity relationship towards oxygen evolution on these oxides has been reported, the influence of carbon on the behavior of these oxides as OER catalysts is not yet clearly understood. In the present work we study the influence of functionalized acetylene black (AB f ) carbon in the electrode composition on the OER activity for perovskite oxides using the thin-film rotating disk electrode technique. It was found that the addition of AB f significantly enhances the OER activity of the single perovskite oxides, namely Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ , (BSCF) and La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF). The activity of the double perovskite oxide, (Pr 0.5 Ba 0.5 )CoO 3-δ (PBCO), was relatively unaffected by the addition of AB f in the electrode. Ex situ impedance spectroscopy measurements at room temperature showed that BSCF powder displayed a lower resistivity compared to PBCO with LSCF displaying the highest resistivity of the three materials. These results therefore suggest that the AB f present can more than simply improve the conductive pathway in the perovskite/carbon composite electrodes but can also significantly enhance the electrocatalytic activity of selected perovskites towards the OER. The oxygen evolution reaction (OER), the process of generating molecular oxygen through the electrochemical oxidation of water, is a key reaction in energy storage processes involving hydrogen and central to addressing the impending global energy crisis. This reaction, occurring at the anode of the water splitting reaction, is primarily governed by slow kinetics 1 and has therefore been extensively studied to improve the performance of devices such as water electrolyzers. 2,3,4 Significant overpotential losses remain a hurdle which requires the need for rare and expensive noble-metal based electrocatalysts for efficient operation. The development and application of new materials able to compete with expensive state-of-the-art current electrocatalysts for hydrogen generating devices therefore yields a great challenge.Various electrocatalytic materials have been studied in the past towards improving the OER, where the oxides of Ir and Ru have been conventionally identified as the most active, often in mixtures with other transition metal oxides. 5,6,7 From the numerous metal oxides studied, perovskite oxides emerged as promising electrocatalysts for both the OER and ORR (oxygen reduction reaction) in alkaline media where a number of these oxides have been reported to be sufficiently stable for practical applications. 8,9 The perovskite-type oxide family, has the general formula ABO 3 , where the A-site is occupied by an alkaline earth element, such as Ca, Ba and Sr and rare earth elements (lanthanides) such as La or Pr. The B-site is occupied by a transition metal element in 6-fold coordination to...

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“…Recent studies have focused on reducing the amount of precious metals in OER catalysis, using more Earth-abundant transition metals in their oxide and/or hydroxide form to catalyze the reaction [12][13][14]. However, as reported by recent experimental benchmarking efforts and supported by theoretical calculations, the overpotentials of state-of-the-art catalysts have plateaued close to the theoretical minimum overpotential for the OER, predicted for conventional materials, including those based on precious metals [15,16].…”

Section: Introductionmentioning

confidence: 94%

Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

et al. 2017

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Zirconium phosphate (ZrP), an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER). Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II), Fe(III), Co(II), and Ni(II) cations. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the composite materials and confirm the incorporation of the metal cations either between the layers or on the surface of ZrP. Both types of metal-modified systems were examined for their catalytic activity for the OER in 0.1 M KOH solution. All metal-modified ZrP systems were active for the OER. Trends in activity are discussed as a function of the molar ratio in relation to the two types of catalyst systems, resulting in overpotentials for metal-adsorbed ZrP catalysts that were less than, or equal to, their metal-intercalated counterparts.

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Developments and perspectives of oxide-based catalysts for the oxygen evolution reaction

Abstract: Activity, selectivity and stability of oxygen evolution catalysts for water electrolyzers: an interplay between composition, morphology, preparation and processing.

Cited by 1,121 publications

References 155 publications

Redox properties of birnessite from a defect perspective

Redox properties of birnessite from a defect perspective

Electrocatalysis of Perovskites: The Influence of Carbon on the Oxygen Evolution Activity

Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

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