Evaluation of Perovskites as Electrocatalysts for the Oxygen Evolution Reaction

Rincón, Rosalba A.; Ventosa, Edgar; Tietz, Frank; Masa, Justus; Seisel, Sabine; Kuznetsov, Volodymyr; Schuhmann, Wolfgang

doi:10.1002/cphc.201402137

Cited by 79 publications

(80 citation statements)

References 32 publications

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“…Compared to the dramatic increase for the BSCF perovskite oxide with the addition of carbon, these results therefore indicate only a fair interaction between LSCF and AB f occurred as recently described. 38 PBCO and PBCO/AB f .- Figure 4a and 4b) finally illustrate the ohmic-drop corrected anodic CV scans for the OER activity with a close up for each in the capacitive region given in Figure 4c and 4d for PBCO and PBCO/AB f electrodes, respectively. Figure 4e and 4f) show the capacity-and ohmic-drop-corrected Tafel plots of the pure PBCO electrode and PBCO/AB f composite electrodes in the OER potential regime (1.0-1.7 V vs. RHE).…”

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confidence: 85%

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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confidence: 85%

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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“…[6][7][8][9][10][11][12][13][14][15] In contrast, several perovskites used as single material electrodes, both in the form of powders or thin fi lms, have shown relatively modest performance compared to the respective perovskite/carbon composite electrodes. [10][11][12][13][14][15][16][17] It is generally argued that carbon is needed in the perovskite-based electrodes to improve the electrical connection between particles and agglomerates, even though several recent literature reports have shown that carbon may play a more complex role as just a simple conductive support. [ 11,12,14,15,17 ] Therefore, understanding why carbon can act as activity booster for the electrochemical activity of some perovskite oxides is crucial, both from a fundamental point of view and for the rational design of better perovskite-based electrocatalysts.…”

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confidence: 92%

Superior Bifunctional Electrocatalytic Activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ/Carbon Composite Electrodes: Insight into the Local Electronic Structure

Fabbri

Nachtegaal

Cheng

et al. 2015

Advanced Energy Materials

115

102

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By using X-ray absorption near edge structure spectroscopy (XANES), changes in the local electronic structure of the perovskite have been observed when a composite perovskite/ carbon electrode is developed. This fi nding provides a novel understanding of perovskite/carbon composite electrodes and thus opens new perspectives for the optimization of the composite electrodes or for tailoring new perovskite compositions. Furthermore, our results also indicate that the electrode preparation process can deeply change the perovskite electronic structure. This should be always carefully taken into account in order to develop a proper electronic structure/catalytic activity correlation for this class of compounds.The selected perovskite composition for this study is Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ (BSCF) since this perovskite has already been shown to be a promising bifunctional catalyst (i.e., high ORR and OER activity) in combination with carbon but not as a single perovskite catalyst. [ 6,7,[14][15][16]20 ] BSCF was prepared by a sol-gel combustion method, and after calcination at 1000 °C for 2 h, phase formation was confi rmed by X-ray diffraction analysis (Supporting Information, Figure S1). Acetylene black carbon was treated in nitric acid at 80 °C overnight in order to create surface oxygen-containing functional groups that were shown to improve and stabilize the AB catalytic activity in alkaline environment. [ 14 ] The electrodes were prepared by ultrasonicating BSCF or BSCF and acetylene black (AB; 5:1 weight ratio) in isopropanol and Na + -modifi ed Nafi on as a binder; then optimized thin porous fi lms were deposited on glassy carbon substrates that allow investigating electrochemical activity of the material by the thin fi lm rotating disk electrode (RDE) technique. [ 21 ] The ORR and OER currents for the BSCF and the BSCF/AB electrodes are shown in Figure 1 . For both reactions, the composite BSCF/AB electrode shows a signifi cant lower overpotential compared to the BSCF electrode. Regarding the ORR, the BSCF/AB composite electrode shows a decrease in the overpotential (130 ± 10 mV at −0.025 mAcm geo −2 ) and an increase in the reduction current over the whole ORR potential range compared to the BSCF electrode. As found previously by rotating ring disk electrode (RRDE) measurements, adding carbon to BSFC electrodes can also signifi cantly infl uence the reaction pathway transitioning from mainly hydroperoxide as product (two-electron reduction) on the BSCF and the carbon single material electrodes, to almost complete O 2 reduction to water on the BSCF/AB composites. [ 14 ] Also in case of the OER, the BSCF/AB composite electrode displays a signifi cant higher activity compared to the BSCF electrode. At the value of 10 Ag metal −1 the BSCF/AB composite electrodes display a quasi steady-state potential of 1.55 ± 0.012 V (RHE), about 100 mV lower than the BSCF single material Perovskite oxides have been investigated for a wide range of applications, and recently they have gained attention as oxygen electrocata...

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“…[1][2][3][4][5][6][7] Next to scarce noble metal oxides, several first-row transition metal oxides and, in particular, perovskite-based systems with the general formula ABO 3 perform well as OER catalysts. [6][7][8][9][10] Theoretical studies suggest that the catalytic activity of the four-electron transfer reaction forming molecular O 2 depends on strength and flexibility of the metal-oxygen bond, which can shift the redox activity from metal to lattice oxygen surface sites due to ligand hole formation. [7,28,34,39,40] Thus, an understanding of the underlying microscopic mechanisms, the nature of active sites, and catalyst stability is necessary to rationalize the search for active and stable catalysts.…”

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confidence: 99%

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

Mierwaldt

Roddatis

Risch

et al. 2017

Advanced Sustainable Systems

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The sluggish kinetics of the oxygen evolution reaction (OER) is a grand challenge for energy storage technologies. Several perovskites and other oxides of earth‐abundant elements are found to exhibit improved catalytic OER activity. However, less attention is paid to the electrochemical stability, an important factor for large‐scale application. The ongoing search for stable catalysts calls for characterizing active catalyst surfaces and identifying mechanisms of deactivation, activation, or repair. In situ techniques are indispensable for these tasks. This study uses environmental transmission electron microscopy on the highly correlated perovskite Pr1–xCaxMnO3 and the Ruddlesden–Popper Pr0.5Ca1.5MnO4 as model electrodes to elucidate the underlying mechanisms of the stability trends identified on rotating ring disk electrodes. An electron beam at fluxes well below those that would cause radiation damage is used to induce positive local electrode potentials due to secondary electron emission, driving electrochemical reactions in H2O vapor. The stability of the model systems increases with increasing ionic character of the MnO bond, while more covalent bonds are prone to corrosion, which is triggered by formation of point defects in the oxygen sublattice.

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Evaluation of Perovskites as Electrocatalysts for the Oxygen Evolution Reaction

Cited by 79 publications

References 32 publications

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

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

Superior Bifunctional Electrocatalytic Activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ/Carbon Composite Electrodes: Insight into the Local Electronic Structure

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

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Evaluation of Perovskites as Electrocatalysts for the Oxygen Evolution Reaction

Cited by 79 publications

References 32 publications

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

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

Superior Bifunctional Electrocatalytic Activity of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ/Carbon Composite Electrodes: Insight into the Local Electronic Structure

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

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Superior Bifunctional Electrocatalytic Activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ/Carbon Composite Electrodes: Insight into the Local Electronic Structure