Co‐doping Strategy for Developing Perovskite Oxides as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction

Xu, Xiaomin; Su, Chao; Zhou, Wei; Zhu, Yinlong; Chen, Yubo; Shao, Zongping

doi:10.1002/advs.201500187

Cited by 250 publications

(169 citation statements)

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“…The OER performance of the ultrafine PBSCF-III nanofiber was superior to that of the recently reported advanced perovskite catalysts with novel compositions11121314, nanostructures1115 and atmosphere-treated surfaces1718 in terms of iR -corrected η ( i is the current, R is the ohmic resistance), Tafel slope and catalyst mass loading in 0.1 M KOH (Fig. 2d, for example, η =0.358 V, Tafel slope of 52 mV dec −1 , 0.202 mg oxide cm −2 disk for PBSCF-III are lower than η =∼0.55 V, Tafel slope of 129 mV dec −1 , 0.64 mg oxide cm −2 disk for surface-modified BSCF (calcined at 950 °C under O 2 )18 and η =0.49 V, Tafel slope of 69 mV dec −1 , 0.25 mg oxide cm −2 disk for ∼80 nm LaCoO 3 (ref.…”

Section: Resultsmentioning

confidence: 72%

“…We further demonstrate the controlled synthesis of PBSCF nanofibers with diameters from ∼196 to 20 nm to enhance the OER mass activity and understand the nanosize effect. Importantly, PBSCF nanofibers of ∼20 nm in diameter show markedly enhanced OER activities compared to that of the PBSCF powders, superior to the commercial IrO 2 catalyst and those of recently reported advanced perovskite catalysts11121314151718. An enhancement in intrinsic activity of the same PBSCF material with decreasing the diameter to ∼20 nm (ultrafine nanofiber versus micron-sized powder) is observed, which is explained by favourable e g electron filling of ultrafine nanofiber, stronger adsorption of oxygen-containing adsorbates, possible surface reduction and heterostructure.…”

mentioning

confidence: 85%

“…( d ) OER activity comparison in 0.1 M KOH. iR -corrected overpotential ( η ) at 10 mA cm −2 disk , Tafel slope and catalyst mass loading of PBSCF-0, III and IrO 2 in this work are compared with recently reported advanced perovskite catalysts with novel compositions11121314, nanostructures1115 and atmosphere-treated surfaces1718; all η derived from literatures are iR -corrected, mass loading of Ca 0.9 Yb 0.1 MnO 3− δ is missing17 and is assumed to be the same to the lowest number in the figure; BSCF is Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3− δ ; iR -correction is very important for reliable comparison of results from different test devices (Supplementary Fig. 13; Supplementary Table 3; Supplementary Note 6).…”

Section: Figurementioning

confidence: 99%

“…Unfortunately, the surface amorphization with formation of structural motifs with local order of edge-sharing octahedra was found for BSCF during the OER910. Strategies such as A/B cation substitution (or doping)11121314, nanostructure engineering111516 and surface treatment1718 have been successfully applied to enhance activity and/or stability. Double perovskites (AA′B 2 O 5+ δ ) were found to have stable structure during the OER due to proper O p -band centre position relative to the Fermi level19; in particular, PrBaCo 2 O 5+ δ (PBC) was identified with optimal intrinsic OER activity, comparable with that of BSCF catalyst19.…”

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confidence: 99%

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A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

Zhao¹,

Zhang²,

Zhen³

et al. 2017

Nat Commun

341

259

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Rechargeable metal–air batteries and water splitting are highly competitive options for a sustainable energy future, but their commercialization is hindered by the absence of cost-effective, highly efficient and stable catalysts for the oxygen evolution reaction. Here we report the rational design and synthesis of a double perovskite PrBa0.5Sr0.5Co1.5Fe0.5O5+δ nanofiber as a highly efficient and robust catalyst for the oxygen evolution reaction. Co-doping of strontium and iron into PrBaCo2O5+δ is found to be very effective in enhancing intrinsic activity (normalized by the geometrical surface area, ∼4.7 times), as validated by electrochemical measurements and first-principles calculations. Further, the nanofiber morphology enhances its mass activity remarkably (by ∼20 times) as the diameter is reduced to ∼20 nm, attributed to the increased surface area and an unexpected intrinsic activity enhancement due possibly to a favourable eg electron filling associated with partial surface reduction, as unravelled from chemical titration and electron energy-loss spectroscopy.

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Section: Resultsmentioning

confidence: 72%

mentioning

confidence: 85%

Section: Figurementioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

Zhao¹,

Zhang²,

Zhen³

et al. 2017

Nat Commun

341

259

View full text Add to dashboard Cite

show abstract

“…As exhibited in Figure a, the wavenumber at ∼3430 cm −1 approximately corresponds to the stretching vibration of OH − . SCFP, SCPF and S(CF)P exhibit a better OH − adsorption than SCF, indicating that P doping could enhance the hydrophilic character of perovskite oxides, thereby improving the OER performance . The electrochemical surface area (ECSA) is another factor may affect the OER performance, which reflects the effective specific surface area involved in the electrochemical reaction ,.…”

Section: Resultsmentioning

confidence: 99%

Selective Partial Substitution of B‐Site with Phosphorus in Perovskite Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

et al. 2018

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Perovskite oxides are promising electrocatalysts for the oxygen evolution reaction (OER). However, the activity and stability of perovskite oxides still needs to be improved to efficiently utilize renewable and clean energy resources. Herein, we selectively introduced phosphorus (P) into SrCo0.8Fe0.2O3‐δ (SCF) to form modified perovskite oxides, i. e., SrCo0.8Fe0.15P0.05O3‐δ, SrCo0.75Fe0.2P0.05O3‐δ and Sr(Co0.8Fe0.2)0.95P0.05O3‐δ. An improved OER activity and stability compared to un‐doped SCF was clearly observed. Meanwhile, the specific surface area, oxygen vacancy content and electronic conductivity increased due to the P doping. Moreover, a lower valence state of B‐site cations induced by the high‐valence P5+ was detected, which may contribute to the better activity and stability. Among them, the dual‐site substitution to form Sr(Co0.8Fe0.2)0.95P0.05O3‐δ stands out when evaluating the activity and stability in alkaline solution. The results suggest that the P doping could be an effective strategy to develop perovskite electrocatalysts with high electrocatalytic activity and stability.

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Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

Zhu

Zhou

Sunarso

et al. 2016

Adv Funct Materials

Self Cite

286

216

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1 wileyonlinelibrary.com evolution reaction (OER) is currently the limiting factor on the water splitting due to its sluggish kinetics involving the complex four-electron oxidation process. [3] To this end, the presence of an efficient OER electrocatalyst is essential to obtain an accelerated reaction rate. At present, precious metal-based iridium and ruthenium oxides (i.e., IrO 2 and RuO 2 ) are regarded as the OER catalysts benchmarks, [4] but their scarcity and high cost have hindered their wide-scale applications. IrO 2 and RuO 2 catalysts additionally show poor stability during long-term operation in alkaline solutions. [5] As such, tremendous efforts have been devoted to develop low-cost and earth-abundant alternative OER catalysts with high activity and good stability.Over the past few decades, due to their compositional and structural flexibility, precious metal-free perovskitetype oxides with a general formula of ABO 3 (A = alkaline-earth or rare-earth metals and B = transition metals) have attracted interests in various applications, e.g., solid oxide fuel cells (SOFCs), oxygen permeation membranes, metalair batteries, and supercapacitors. [6] Most recently, they were reported to also exhibit high OER activity in an alkaline solution. [7] Rossmeisl group and Koper group theoretically calculated that SrCoO 3 parent oxide would deliver the highest OER activity among LaMO 3 and SrMO 3 (M = transition metals) parent oxides via density functional theory calculations. [8] Shao-Horn and co-workers reported that one of the Developing cost-effective and efficient electrocatalysts for oxygen evolution reaction (OER) is of paramount importance for the storage of renewable energies. Perovskite oxides serve as attractive candidates given their structural and compositional flexibility in addition to high intrinsic catalytic activity. In a departure from the conventional doping approach utilizing metal elements only, here it is shown that non-metal element doping provides an another attractive avenue to optimize the structure stability and OER performance of perovskite oxides. This is exemplified by a novel tetragonal perovskite developed in this work, i.e., SrCo 0.95 P 0.05 O 3-δ (SCP) which features higher electrical conductivity and larger amount of O 2 2− /O − species relative to the non-doped parent SrCoO 3-δ (SC), and thus shows improved OER activity. Also, the performance of SCP compares favorably to that of well-developed perovskite oxides reported. More importantly, an unusual activation process with enhanced activity during accelerated durability test (ADT) is observed for SCP, whereas SC delivers deactivation for the OER. Such an activation phenomenon for SCP may be primarily attributed to the in situ formation of active A-site-deficient structure on the surface and the increased electrochemical surface area during ADT. The concept presented here bolsters the prospect to develop a viable alternative to precious metal-based catalysts.

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Co‐doping Strategy for Developing Perovskite Oxides as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction

Cited by 250 publications

References 52 publications

A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

Selective Partial Substitution of B‐Site with Phosphorus in Perovskite Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

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