Oxygen-deficient triple perovskites as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Kim, Nam‐In; Jin, Young; Yoo, Tae Sup; Choi, Sung R.; Afzal, Rana Arslan; Choi, Taekjib; Seo, Young‐Soo; Lee, Kug‐Seung; Hwang, Jun Yeon; Choi, Woo Seok; Joo, Sang Hoon

doi:10.1126/sciadv.aap9360

Cited by 213 publications

(106 citation statements)

References 40 publications

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“…The Fe-LNO exhibits the highest hydroxyl adsorption capacity nearly 1 : 1, and the hydroxyl adsorption capacity of Fe-LNO is even better than that of pure FeOOH, which is much larger than that of LNO (0.2 : 1), indicating that the modification of FeOOH can greatly optimize the adsorption of hydroxyl. To further determine whether the adsorbents are chemisorption of ∗OH or physisorption of hydroxyl, XPS was used to further prove the adsorption state of hydroxyl [ 55 ], as shown in Figure 3(d) . By comparing the area ratio of the hydroxyl peak and water peak of Fe-LNO and LNO, we found that the adsorption of hydroxyl by Fe-LNO was significantly improved in the range of 2.6 : 1 to 5.0 : 1, implying the generation of a high density of extra oxygen vacancies filled by hydroxyl.…”

Section: Resultsmentioning

confidence: 99%

Boosting Lattice Oxygen Oxidation of Perovskite to Efficiently Catalyze Oxygen Evolution Reaction by FeOOH Decoration

et al. 2020

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In the process of oxygen evolution reaction (OER) on perovskite, it is of great significance to accelerate the hindered lattice oxygen oxidation process to promote the slow kinetics of water oxidation. In this paper, a facile surface modification strategy of nanometer-scale iron oxyhydroxide (FeOOH) clusters depositing on the surface of LaNiO3 (LNO) perovskite is reported, and it can obviously promote hydroxyl adsorption and weaken Ni-O bond of LNO. The above relevant evidences are well demonstrated by the experimental results and DFT calculations. The excellent hydroxyl adsorption ability of FeOOH-LaNiO3 (Fe-LNO) can obviously optimize OH- filling barriers to promote lattice oxygen-participated OER (LOER), and the weakened Ni-O bond of LNO perovskite can obviously reduce the reaction barrier of the lattice oxygen participation mechanism (LOM). Based on the above synergistic catalysis effect, the Fe-LNO catalyst exhibits a maximum factor of 5 catalytic activity increases for OER relative to the pristine perovskite and demonstrates the fast reaction kinetics (low Tafel slope of 42 mV dec-1) and superior intrinsic activity (TOFs of ~40 O2 S-1 at 1.60 V vs. RHE).

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Section: Resultsmentioning

confidence: 99%

Boosting Lattice Oxygen Oxidation of Perovskite to Efficiently Catalyze Oxygen Evolution Reaction by FeOOH Decoration

et al. 2020

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“…Among TMOs, perovskite oxides containing more than one metal have been reported for various applications by virtue of their structural and compositional flexibility 22 , 26 – 28 . The multiple ions (including metal and oxygen ions) and variable structures of perovskite oxides can bring about some unique electronic and conductive properties, which then modulate the binding energies of reaction intermediates and electron-transport behavior, and consequently their electrocatalytic activities 16 , 22 , 26 , 29 – 31 . Therefore, designing an ideal perovskite system with multiple catalytic sites, which are tailored for targeting steps in alkaline HER electrocatalysis, may be viable, but still remains a great challenge and yet to be realized.…”

Section: Introductionmentioning

confidence: 99%

Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution

et al. 2020

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The state-of-the-art active HER catalysts in acid media (e.g., Pt) generally lose considerable catalytic performance in alkaline media mainly due to the additional water dissociation step. To address this issue, synergistic hybrid catalysts are always designed by coupling them with metal (hydro)oxides. However, such hybrid systems usually suffer from long reaction path, high cost and complex preparation methods. Here, we discover a single-phase HER catalyst, SrTi0.7Ru0.3O3-δ (STRO) perovskite oxide highlighted with an unusual super-exchange effect, which exhibits excellent HER performance in alkaline media via atomic-scale synergistic active centers. With insights from first-principles calculations, the intrinsically synergistic interplays between multiple active centers in STRO are uncovered to accurately catalyze different elementary steps of alkaline HER; namely, the Ti sites facilitates nearly-barrierless water dissociation, Ru sites function favorably for OH* desorption, and non-metal oxygen sites (i.e., oxygen vacancies/lattice oxygen) promotes optimal H* adsorption and H2 desorption.

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“…Structure-activity relationships and relative design principles derived from ex situ findings are often reported. Many typical perovskite families have been exploited to explore their structure-activity relationships and mechanisms, such as single perovskites ABO 3-δ 10 , single-layer Ruddlesden-Popper (RP) perovskites A 2 BO 4-δ 11 , double perovskites A 2 B 2 O 6-δ 12 , triple perovskites A 3 B 3 O 9-δ 13 , three-layer RP perovskites A 4 B 3 O 10-δ 14 , quadruple perovskites A 4 B 4 O 12-δ 15 , and hexagonal perovskites A 8 B 4 O 15-δ 16 . According to these structure-activity correlations obtained from ex situ characterizations and computations, some activity descriptors are also successfully proposed, including e g orbital occupancy 10 , O 2p band center 12 , and charge-transfer energy 17 .…”

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confidence: 99%

Utilizing ion leaching effects for achieving high oxygen-evolving performance on hybrid nanocomposite with self-optimized behaviors

et al. 2020

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Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl 2 and SrCl 2 into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proofof-concept, self-assembled hybrid Ba 0.35 Sr 0.65 Co 0.8 Fe 0.2 O 3-δ (BSCF) nanocomposite (with BaCl 2 and SrCl 2) exhibits the low overpotential of 260 mV at 10 mA cm-2 in 0.1 M KOH. Multiple operando spectroscopic techniques reveal that the pre-leaching of soluble compounds lowers the difference of interfacial ion concentrations and thus endows the host phase in hybrid BSCF with abundant time and space to form stable edge/face-sharing surface structures. These self-optimized crystalline structures show stable lattice oxygen active sites and short reaction pathways between Co-Co/Fe metal active sites to trigger favorable adsorption of OH − species.

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Oxygen-deficient triple perovskites as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Abstract: Triple perovskite, Nd1.5Ba1.5CoFeMnO9−δ, enriched with oxygen defects shows high activity and durability as a bifunctional oxygen electrocatalyst.

Cited by 213 publications

References 40 publications

Boosting Lattice Oxygen Oxidation of Perovskite to Efficiently Catalyze Oxygen Evolution Reaction by FeOOH Decoration

Boosting Lattice Oxygen Oxidation of Perovskite to Efficiently Catalyze Oxygen Evolution Reaction by FeOOH Decoration

Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution

Utilizing ion leaching effects for achieving high oxygen-evolving performance on hybrid nanocomposite with self-optimized behaviors

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