Engineering phosphorus-doped LaFeO3-δ perovskite oxide as robust bifunctional oxygen electrocatalysts in alkaline solutions

Li, Zhishan; Li, Lin; Wang, Jinsong; Ao, Xiang; Ruan, Yunjun; Zha, Dace; Hong, Guo; Wu, Qi‐Hui; Lan, Yucheng; Wang, Chundong; Jiang, Jianjun; Liu, Meilin

doi:10.1016/j.nanoen.2018.02.051

Cited by 220 publications

(125 citation statements)

References 74 publications

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“…In this work, the OER activity of both cobalt‐doped catalysts (LFC82 and 3DOM‐LFC82) with cubic structure are better than their corresponding Fe‐based catalysts (LF and 3DOM‐LF) with orthorhombic structure, which is consistent with previous studies that the ideal cubic crystal structure can also contribute to the improved activity of OER . The 3DOM architecture and cubic crystal structure in 3DOM‐LFC82 brings about optimized iron oxidation state (e.g., Fe 4+ ), as characterized by XPS Fe 2p spectra (Figure S14, Supporting Information) and corresponding deconvolution results (Figure d and Table S4, Supporting Information) . Fe 4+ species with one electron only in the e g orbital have been reported as active sites for OER .…”

supporting

confidence: 90%

Enabling High and Stable Electrocatalytic Activity of Iron‐Based Perovskite Oxides for Water Splitting by Combined Bulk Doping and Morphology Designing

Dai

Zhu

Zhong

et al. 2018

Adv Materials Inter

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COMMUNICATION (1 of 8)scale is mainly hindered by the large overpotential, originated largely from sluggish kinetics of anodic oxygen evolution reaction (OER) and cathodic hydrogen evolution reaction (HER). For commercial electrolyzers, a much higher operating potential (1.8-2.0 V) is always required than the theoretical value (1.23 V). [5] The iridium/ruthenium oxides (IrO 2 /RuO 2 ) and platinum (Pt) metal are recognized as the state-of-the-art catalysts toward anodic and cathodic reactions, respectively, [6] while their large-scale commercial application is restricted by high cost and resource scarcity. [7] Thus, it is necessary to rationally design high-performance, cost-effective, and abundant catalysts for water splitting. So far, diverse groups of materials including oxides, hydroxides, phosphides, chalcogenides, carbides, and nitrides, have been exploited as potential catalysts for water splitting with different benefits and drawbacks. [8,9] Perovskite oxides with the general formula of ABO 3 , where A is alkaline-and/or rare-earth metal and B is a transition metal (most of which is cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe)), have recently attracted considerable attention in the electrocatalysis field due to their high specific catalytic activity, compositional flexibility, and environmental friendliness. [10,11] From the point of practical applications, iron-based materials are more appealing in the family of perovskite considering that Fe metal is more earth-abundant and cheaper, and less toxic than Co and Ni metals. [12,13] However, Fe-based perovskites always show poor activity and unfavorable durability for OER. [14,15] In particular, the iron-rich perovskites always showed an obvious decrease in activity with time on operation. Refer to the poor activity issue, a few efforts have been devoted to looking for effective strategies (e.g., ion doping, deficiency tuning, and crystal-structure design) to enhance the electrocatalytic activity. [16][17][18][19][20] For example, She et al. reported a systematic study of Sr-doped La 1-x Sr x FeO 3-δ perovskites and found A-site Sr-doping could greatly improve OER activity of parent LaFeO 3 . [16] The OER activity of Fe-based perovskite could also be improved by proper B-site ion doping, e.g., Zr 4+ and Si 4+ . [17,18] Besides the ion doping, Zhu et al. also proposed a strategy for enhancing OER activity by introducing A-site deficiency in LaFeO 3 perovskite. [19] Yagi et al. prepared a quadruple perovskite CaCu 3 Fe 4 O 12 via a high-pressure method, which shows higher OER activity than the simple perovskites. [20] The catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are crucial for water splitting technology, and perovskite oxides have received tremendous attention as promising candidates due to the compositional flexibility and rich properties. Here, reported is the successful deployment of cost-effective iron-based perovskites into efficient water splitting catalysts with both high activity and stability by c...

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confidence: 90%

Enabling High and Stable Electrocatalytic Activity of Iron‐Based Perovskite Oxides for Water Splitting by Combined Bulk Doping and Morphology Designing

Dai

Zhu

Zhong

et al. 2018

Adv Materials Inter

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“…Besides, the O 1s spectra in Figure c and corresponding deconvolution results in Table S3 in the Supporting Information reveal a larger amount of surface highly oxidative oxygen species, namely O 2 2− /O − species of SCR0.1. In previous literatures, O 2 2− /O − species were regarded as active sites for OER catalysis13a,22 and such active O species are closely associated with the surface oxygen vacancies 2a,23. Electron paramagnetic resonance (EPR) measurements were conducted to provide direct evidence to demonstrate the existence of surface oxygen vacancies on the surface of perovskites.…”

mentioning

confidence: 99%

Super‐Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation

Dai

Zhu

Yin

et al. 2019

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Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super‐exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition‐dependent OER activity in SrCo1x Rux O3−δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super‐exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+–O–Ru5+ super‐exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+/Co4+, Ru5+, and O22−/O−, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm−2, which exceeds the benchmark RuO2 and most well‐known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.

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“…Density functional theory (DFT) calculations were carried out to reveal the with reported perovskites, antiperovskite, and other excellent catalysts, in terms of onset potential (at J = À0.1 mA cm À2 )and half-wave potential. [6,30,[34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50]…”

Section: Resultsmentioning

confidence: 99%

Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction

et al. 2019

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Antiperovskite Co 3 InC 0.7 N 0.3 nanomaterials with highly enhanced oxygen reduction reaction (ORR) performance were prepared by tuning nitrogen contents through am etal-organic framework (MOF)-derived strategy.T he nanomaterial surpasses all reported noble-metal-free antiperovskites and even most perovskites in terms of onset potential (0.957 Va tJ = 0.1 mA cm À2 )a nd half-wave potential (0.854 V). The OER and zinc-air battery performance demonstrate its multifunctional oxygen catalytic activities.D FT calculation was performed and for the first time,a4e À dissociative ORR pathway on (200) facets of antiperovskite was revealed. Free energy studies showed that nitrogen substitution could strengthen the OH desorption as well as hydrogenation that accounts for the enhanced ORR performance.T his work expands the scope for material design via tailoring the nitrogen contents for optimal reaction free energy and hence performance of the antiperovskite system.

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Engineering phosphorus-doped LaFeO3-δ perovskite oxide as robust bifunctional oxygen electrocatalysts in alkaline solutions

Cited by 220 publications

References 74 publications

Enabling High and Stable Electrocatalytic Activity of Iron‐Based Perovskite Oxides for Water Splitting by Combined Bulk Doping and Morphology Designing

Enabling High and Stable Electrocatalytic Activity of Iron‐Based Perovskite Oxides for Water Splitting by Combined Bulk Doping and Morphology Designing

Super‐Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation

Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction

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