Oxygen Defect Engineering: Improving the Activity for Oxygen Evolution Reaction by Tailoring Oxygen Defects in Double Perovskite Oxides (Adv. Funct. Mater. 34/2019)

Zhu, Yunmin; Zhang, Lei; Zhao, Bote; Chen, Huijun; Liu, Xi; Zhao, Ran; Wang, Xinwei; Liu, Jiang; Chen, Yan; Liu, Meilin

doi:10.1002/adfm.201970236

Cited by 40 publications

(47 citation statements)

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“…In situ high‐resolution synchrotron‐based XRD measurements can help to clarify the real‐time structural changes of the catalyst, expected to occur only in the outer ≈14 nm of the catalyst surface . Figure S3 a shows synchrotron‐based XRD of the as‐prepared SP/DP sample, immersed in KOH aqueous solution, and at various potentials (vs. RHE).…”

Section: Resultsmentioning

confidence: 99%

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Sun

Guan

et al. 2020

ChemSusChem

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Perovskite‐based oxides have emerged as promising oxygen evolution reaction (OER) electrocatalysts. The performance is closely related to the lattice, electronic, and defect structure of the oxides, which determine surface and bulk properties and consequent catalytic activity and durability. Further, interfacial interactions between phases in a nanocomposite may affect bulk transportation and surface adsorption properties in a similar manner to phase doping except without solubility limits. Herein, we report the development of a single/double perovskite nanohybrid with limited surface self‐reconstruction capability as an OER electrocatalyst. Such superior performance arises from a structure that maintains high crystallinity post OER catalysis, in addition to forming an amorphous layer following the self‐reconstruction of a single perovskite structure during the OER process. In situ X‐ray absorption near edge structure spectroscopy and high‐resolution synchrotron‐based X‐ray diffraction reveal an amorphization process in the hybrid single/double perovskite oxide system that is limited in comparison to single perovskite amorphization, ensuring high catalytic activity.

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Section: Resultsmentioning

confidence: 99%

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Sun

Guan

et al. 2020

ChemSusChem

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“…[ 53–58 ] However, the binding energies in the O2s XPS spectrum of R‐NiFe‐CPs are shifted slightly to higher values and a new peak located at 531.57 eV appears, which can be assigned to oxygen deficiencies. [ 33a,b,56–60 ] The negative shift for Ni and Fe 2p and the positive shift for O 2s are due to strong electronic interactions with electron transfer from anions to cations. [ 29a,b,32,61 ] Overall, the charge regulation by structural deficiencies and distortions in R‐NiFe‐CPs caused electron redistributions, which enhance the electron transfer properties and further improve the OER performance, as will be discussed in the following sections.…”

Section: Resultsmentioning

confidence: 99%

Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance

Zhao

Wan

Chen

et al. 2020

Advanced Energy Materials

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fuel shortage and climate change. [1] Noble metal-based materials (e.g., Pt and its alloys) have been well investigated and are among the most promising electrocatalysts for water splitting to generate clean hydrogen. [2,3] However, Pt group-based catalysts are still constrained by their scarcity and high cost for scalable and commercial electrocatalysis. Hence, the development of noble-metal-free catalysts with comparable catalytic activity and robust durability is an urgent task to realize technical applications of water electrolysis. [4,5] Coordination polymer assemblies (CPAs), which are composed of a metal center linked to organic or inorganic ligands combine tunable porous structures, well-dispersed metal sites, high surface areas, and good chemical stability. This renders them excellent materials for drug delivery, [6] gas storage and separation, [7] batteries, [8,9] and catalysis. [10-13] Thanks to their unique structural properties, transition metal-based CPAs keep attracting broad interest in the field of heterogeneous electrocatalysts. [9a,b-14] However, their intrinsic poor conductivity, low mass permeability, and confined active metal centers need to be systematically improved for their application as efficient electrocatalysts. Moreover, instability issues of the ligands such as self-oxidation or degradation at high oxidation potentials need to be resolved for directly using CPAs as long-term electrocatalysts. [14-17] Several strategies, for example, morphological modulation, electronic tuning, and surface modification, have been confirmed as promising approaches to improve the electrocatalytic performance of CPAs and CPs. [14,16-21] In a representative study, ultra-thin NiCo bimetallic CPA nanosheets with enhanced OER activity compared to bulk NiCo bimetallic CPAs, were synthesized through an ultrasonication exfoliation method. [14] Zhang et al. [16] demonstrated that monolayered heterogenous nanosheets of hybrid CoFeO x /CPAs were promising OER electrocatalysts. Some of us recently [20] proposed that the high and durable electrocatalytic activity of a new 1D cobalt coordination polymer (Co-dppeO 2) is due to its highly disordered structure, giving rise to exceptional resilience. Further theoretical calculations and in situ characterizations proved that the key architecture behind the high OER activity was arising from the {H 2 O-Co 2 (OH) 2-OH 2 } edge-site motifs. This study demonstrated the high potential of low-cost Engineering low-crystalline and ultra-thin nanostructures into coordination polymer assemblies is a promising strategy to design efficient electrocatalysts for energy conversion and storage. However, the rational utilization of coordination polymers (CPs) or their derivatives as electrocatalysts has been hindered by a lack of insight into their underlying catalytic mechanisms. Herein, a convenient approach is presented where a series of Ni 10-x Fe x-CPs (0 ≤ x ≤ 5) is first synthesized, followed by the introduction of abundant structural deficiencies using a facile reductive method ...

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“…Furthermore, as presented in Figure S11 in the Supporting Information, the Faraday capacitance of the NiCo 2.148 O 4 PNSs significantly increased after 10 CV cycles, which indicated the enhanced surface reconstruction. [ 39 ] The changes in the O 1s XPS profile [ 40 ] (Figure S12a, Supporting Information) and supplementary peak at ≈680 cm −1 in the Raman spectra [ 41 ] (Figure S12b, Supporting Information) of the NiCo 2.148 O 4 PNSs after the OER further confirmed the surface reconstruction.…”

Section: Figurementioning

confidence: 86%

NiCo₂O₄‐Based Nanosheets with Uniform 4 nm Mesopores for Excellent Zn–Air Battery Performance

et al. 2020

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evolution and oxygen reduction reaction (OER and ORR) performance of the air cathode limits the efficiency of Zn-air batteries owing to the sluggish kinetics and multistep proton-coupled electron transfer process on the catalyst surface. [4-6] Anode passivation typically reduces the performance of Zn-air batteries in hard alkaline electrolytes. Moreover, aqueous electrolytes limit the temperature range of the Zn-air battery applications. [7,8] Several strategies, such as the preparation of superior catalysts with remarkable OER and ORR activity and excellent stability, [9-12] the design of new Zn-air battery systems in facile media (such as natural conditions), [13-15] and tailoring the electrolyte properties to achieve a wide temperature range for Zn-air battery applications, [7,8,16-18] have been developed to address these problems and enhance the performance of Zn-air batteries. Although many efforts have been dedicated to increasing the use of Zn-air battery in different fields, the current performance of the Zn-air batteries is still unsatisfactory utilizations in many fields, particularly under low temperature condition. The performance of Zn-air batteries depends on the bifunctional catalytic activity of the air-cathode electrode. Typically, noble Herein, a strategy is reported for the fabrication of NiCo 2 O 4-based mesoporous nanosheets (PNSs) with tunable cobalt valence states and oxygen vacancies. The optimized NiCo 2.148 O 4 PNSs with an average Co valence state of 2.3 and uniform 4 nm nanopores present excellent catalytic performance with an ultralow overpotential of 190 mV at a current density of 10 mA cm −2 and long-term stability (700 h) for the oxygen evolution reaction (OER) in alkaline media. Furthermore, Zn-air batteries built using the NiCo 2.148 O 4 PNSs present a high power and energy density of 83 mW cm −2 and 910 Wh kg −1 , respectively. Moreover, a portable battery box with NiCo 2.148 O 4 PNSs as the air cathode presents long-term stability for 120 h under low temperatures in the range of 0 to −35 °C. Density functional theory calculations reveal that the prominent electron exchange and transfer activity of the electrocatalyst is attributed to the surface lower-coordinated Co-sites in the porous region presenting a merging 3d-e g-t 2g band, which overlaps with the Fermi level of the Zn-air battery system. This favors the adsorption of the *OH, and stabilized *O radicals are reached, toward competitively lower overpotential, demonstrating a generalized key for optimally boosting overall OER performance. Zn-air batteries, as a promising alternative to fossil fuel, have received much attention owing to their safety, cleanliness, and efficiency. [1-3] However, Zn-air batteries still present shortcomings for large-scale applications, as follows. The oxygen The ORCID identification number(s) for the author(s) of this article can be found under

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Oxygen Defect Engineering: Improving the Activity for Oxygen Evolution Reaction by Tailoring Oxygen Defects in Double Perovskite Oxides (Adv. Funct. Mater. 34/2019)

Cited by 40 publications

References 0 publications

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance

NiCo₂O₄‐Based Nanosheets with Uniform 4 nm Mesopores for Excellent Zn–Air Battery Performance

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Oxygen Defect Engineering: Improving the Activity for Oxygen Evolution Reaction by Tailoring Oxygen Defects in Double Perovskite Oxides (Adv. Funct. Mater. 34/2019)

Cited by 40 publications

References 0 publications

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Bulk and Surface Properties Regulation of Single/Double Perovskites to Realize Enhanced Oxygen Evolution Reactivity

Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance

NiCo2O4‐Based Nanosheets with Uniform 4 nm Mesopores for Excellent Zn–Air Battery Performance

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Product

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NiCo₂O₄‐Based Nanosheets with Uniform 4 nm Mesopores for Excellent Zn–Air Battery Performance