Plasma‐Engraved Co<sub>3</sub>O<sub>4</sub> Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Xu, Lei; Jiang, Qianqian; Xiao, Zhaohui; Li, Xingyue; Huo, Jia; Wang, Shuangyin; Dai, Liming

doi:10.1002/ange.201600687

Cited by 537 publications

(266 citation statements)

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“…. 3 were rich in oxygen vacancies, which was in accordance with our EPR findings [40]. The Fe and Ni 2p spectra were also examined to get better understanding of the RNiFe LDH electrode, as shown in Fig.…”

Section: Results and Disscussionsupporting

confidence: 84%

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

et al. 2018

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Exploring efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER) is critical to water splitting. While nickel-iron layered double hydroxide (NiFe LDH) has been long recognized as a promising nonprecious electrocatalyst for OER, its intrinsic activity needs further improvement. Herein, we design a highly-efficient oxygen evolution electrode based on defective NiFe LDH nanoarray. By combing the merits of the modulated electronic structure, more exposed active sites, and the conductive electrode, the defective NiFe LDH electrocatalysts show a low onset potential of 1.40 V (vs. RHE). An overpotential of only 200 mV is required for 10 mA cm −2 , which is 48 mV lower than that of pristine NiFe-LDH. Density functional theory plus U (DFT+U) calculations are further employed for the origin of this OER activity enhancement. We find the introduction of oxygen vacancies leads to a lower valance state of Fe and the narrowed bandgap, which means the electrons tend to be easily excited into the conduction band, resulting in the lowered reaction overpotential and enhanced OER performance.

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Section: Results and Disscussionsupporting

confidence: 84%

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

et al. 2018

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“…It is worth to notice that BP nanosheets in 1 m KOH exhibit improved current density and lower onset potential (about 1.45 eV) than the previous reported 1.48 eV for bulk BP. [1,32,[53][54][55][56][57][58] Although pristine BP shows an inferior behavior when considering the overpotential to deliver 10 mA cm −2 to the graphene-based electrocatalysts or other state-of-the-art composited materials, [59][60][61][62][63] which might be attributed to the limited conductive and surface area of BP nanosheets, the OER performance of BP nanosheets has been improved significantly when compared to that of BP bulk. Considering that bulk BP is hard to cast on glassy carbon electrode, we simply grinded bulk BP into small fractions and investigated the OER performance under the same conditions.…”

Section: Resultsmentioning

confidence: 99%

Few‐Layer Black Phosphorus Nanosheets as Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

Ren

Zhou

et al. 2017

Advanced Energy Materials

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Black phosphorus (BP) is a new rediscovered layered material, which has attracted enormous interests in the field of electrocatalysis. Recent investigations reveal that bulk BP is a promising electrocatalyst for oxygen evolution reactions (OER), whereas its bulk crystal structure restricts sufficient active sites for achieving highly efficient OER catalytic performances. Toward this end, few‐layer BP nanosheets prepared by facile liquid exfoliation are applied as electrocatalysts and exhibit preferable electrocatalytic OER activity in association with structural robustness; subsequently, the dependence of current density and applied bias potential on the concentration of OH− has also been uncovered. Most importantly, we are aware that reduction in the thickness of BP nanosheets would generate extra active sites from the ultrathin planar structure and complimenting to the electrocatalytic activities. It is further anticipated that the current work might provide further implementation about the OER performance of BP nanosheets, thereby, offering extendable availabilities for BP‐based electrocatalysts in constructing high‐performance OER devices.

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“…[27][28][29] The two major peaks of Co 2p 3/2 at ab inding energy (BE) of 779.6 and 781.4 eV correspond to the Co 3+ + and Co 2+ + oxidations tates,r espectively.T he other two peaks at BE = 784.3 and 788.2 eV are associated with the shake-up satellites of Co 3+ + and Co 2+ + ,r espectively.T he surfaceC o 3+ + /Co 2+ + atomic ratios are given in Ta The O1sc urves are asymmetrica nd complicated because of the presence of more than one peak that arises from the overlapping contributions of different chemical oxygen species (Figure 7b). [27,30] The peaks observedf or the Co 3 O 4 sample at BE = 529.6 and5 31.3 eV can be attributed to surface lattice oxygen (O latt )a nd surface oxygen defect species( O ads ;w hichi ncludes low-coordinate oxygen species and chemisorbed water), respectively.T he O ads /O latt ratio calculated by integrating the peak areas of the O1ss pectra is showni nT able 1. [27,30] The peaks observedf or the Co 3 O 4 sample at BE = 529.6 and5 31.3 eV can be attributed to surface lattice oxygen (O latt )a nd surface oxygen defect species( O ads ;w hichi ncludes low-coordinate oxygen species and chemisorbed water), respectively.T he O ads /O latt ratio calculated by integrating the peak areas of the O1ss pectra is showni nT able 1.…”

Section: Surfaceelementalc Omposition (Xps)mentioning

confidence: 99%

Integrated Cobalt Oxide Based Nanoarray Catalysts with Hierarchical Architectures: In Situ Raman Spectroscopy Investigation on the Carbon Monoxide Reaction Mechanism

Zhang

et al. 2018

ChemCatChem

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Herein, a facile strategy for the in situ growth of a Co3O4‐based precursor with unique hierarchical architectures oriented diagonal or perpendicular to Ni surfaces is reported. This strategy to prepare grafted ZIF‐67@Co3O4 and MOF‐199@Co3O4 precursor structures is based on a simple hydrothermal synthesis method to obtain the Co3O4 precursor and the subsequent in situ growth of ZIF‐67 and MOF‐199, respectively. The morphologies of the Co3O4 products can be tailored by controlling the solvent polarity and concentration of precipitants. CO is chosen as a probe molecule to evaluate the catalytic performance of the as‐synthesized Co3O4‐based oxide catalysts, and the structure–activity relationships are confirmed by using TEM, H2 temperature‐programmed reduction, X‐ray photoelectron spectroscopy, Raman spectroscopy and in situ Raman spectroscopy, and extended X‐ray absorption fine structure analysis. These analysis results demonstrate that irislike Co3O4 exhibits a high catalytic activity for CO oxidation and contains an abundance of surface defect sites (Co3+ species) to result in an excellent low‐temperature reducibility, oxygen vacancies and unsaturated chemical bonds on the surface. Moreover, we used in situ Raman spectroscopy to record the structural transformation of Co3O4 directly during the reaction, which confirmed that CO oxidation on the surface of Co3O4 can proceed through the Langmuir–Hinshelwood mechanism (<200 °C) and the Mars–van Krevelen mechanism (>200 °C).

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Plasma‐Engraved Co₃O₄ Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Cited by 537 publications

References 25 publications

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

Few‐Layer Black Phosphorus Nanosheets as Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

Integrated Cobalt Oxide Based Nanoarray Catalysts with Hierarchical Architectures: In Situ Raman Spectroscopy Investigation on the Carbon Monoxide Reaction Mechanism

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Plasma‐Engraved Co3O4 Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction

Cited by 537 publications

References 25 publications

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

A highly-efficient oxygen evolution electrode based on defective nickel-iron layered double hydroxide

Few‐Layer Black Phosphorus Nanosheets as Electrocatalysts for Highly Efficient Oxygen Evolution Reaction

Integrated Cobalt Oxide Based Nanoarray Catalysts with Hierarchical Architectures: In Situ Raman Spectroscopy Investigation on the Carbon Monoxide Reaction Mechanism

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Plasma‐Engraved Co₃O₄ Nanosheets with Oxygen Vacancies and High Surface Area for the Oxygen Evolution Reaction