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1.
Cobalt‐containing spinel oxides are promising electrocatalysts for the oxygen evolution reaction (OER) owing to their remarkable activity and durability. However, the activity still needs further improvement and related fundamentals remain untouched. The fact that spinel oxides tend to form cation deficiencies can differentiate their electrocatalysis from other oxide materials, for example, the most studied oxygen‐deficient perovskites. Here, a systematic study of spinel ZnFexCo2?xO4 oxides (x = 0–2.0) toward the OER is presented and a highly active catalyst superior to benchmark IrO2 is developed. The distinctive OER activity is found to be dominated by the metal–oxygen covalency and an enlarged Co?O covalency by 10–30 at% Fe substitution is responsible for the activity enhancement. While the pH‐dependent OER activity of ZnFe0.4Co1.6O4 (the optimal one) indicates decoupled proton–electron transfers during the OER, the involvement of lattice oxygen is not considered as a favorable route because of the downshifted O p‐band center relative to Fermi level governed by the spinel's cation deficient nature.  相似文献   

2.
Three CoFe-bimetallic oxides with different compositions (termed as CoFeOx-A/N/H) are prepared by thermally treating metal-organic-framework (MOF) precursors under different atmospheres (air, N2, and NaBH4/N2), respectively. With the aid of vast oxygen vacancies (Ov), cobalt at tetrahedral sites (Co2+(Th)) in spinel Co3O4 is diffused into interstitial octahedral sites (Oh) to form rocksalt CoO and ternary oxide CoFe2O4 has been induced to give the unique defective CoO/CoFe2O4 heterostructure. The resultant CoFeOx-H exhibits superb electrocatalytic activity toward water oxidation: overpotential at 10 mA cm−2 is 192 mV, which is 122 mV smaller than that of CoFeOx-A. The smaller Tafel slope (42.53 mV dec−1) and higher turnover frequency (785.5 h−1) suggest fast reaction kinetics. X-ray absorption spectroscopy, ex situ characterizations, and theoretical calculations reveal that defect engineering effectively tunes the electronic configuration to a more active state, resulting in the greatly decreased binding energy of oxo intermediates, and consequently much lower catalytic overpotential. Moreover, the construction of hetero-interface in CoFeOx-H can provide rich active sites and promote efficient electron transfer. This work may shed light on a comprehensive understanding of the modulation of electron configuration of bimetallic oxides and inspire the smart design of high-performance electrocatalysts.  相似文献   

3.
Cobalt‐containing spinel oxides are promising electrocatalysts for the oxygen evolution reaction (OER) owing to their remarkable activity and durability. However, the activity still needs further improvement and related fundamentals remain untouched. The fact that spinel oxides tend to form cation deficiencies can differentiate their electrocatalysis from other oxide materials, for example, the most studied oxygen‐deficient perovskites. Here, a systematic study of spinel ZnFexCo2?xO4 oxides (x = 0–2.0) toward the OER is presented and a highly active catalyst superior to benchmark IrO2 is developed. The distinctive OER activity is found to be dominated by the metal–oxygen covalency and an enlarged Co? O covalency by 10–30 at% Fe substitution is responsible for the activity enhancement. While the pH‐dependent OER activity of ZnFe0.4Co1.6O4 (the optimal one) indicates decoupled proton–electron transfers during the OER, the involvement of lattice oxygen is not considered as a favorable route because of the downshifted O p‐band center relative to Fermi level governed by the spinel's cation deficient nature.  相似文献   

4.
The progress of effective and durable electrocatalysts for oxygen evolution reaction (OER) is urgent, which is essential to promote the overall efficiency of green hydrogen production. To improve the performance of spinel cobalt-based oxides, which serve as promising water oxidation electrocatalysts in alkaline electrolytes, most researches have been concentrated on cations modification. Here, an anionic regulation mechanism is employed to adopt sulfur(S) anion substitution to supplant NiCo2O4 by NiCo2S4, which contributed to an impressive OER performance in alkali. It is revealed that the substitution of S constructs a sub-stable spinel structure that facilitates its reconstruction into active amorphous oxysulfide under OER conditions. More importantly, as the active phase in the actual reaction process, the hetero-anionic amorphous oxysulfide has an appropriately tuned electronic structure and efficient OER electrocatalytic activity. This work demonstrates a promising approach for achieving anion conditioning-based tunable structure reconstruction for robust and easy preparation spinel oxide OER electrocatalysts.  相似文献   

5.
Tuning energy levels plays a crucial role in developing cost‐effective, earth‐abundant, and highly active oxygen evolution catalysts. However, to date, little attention has been paid to the effect of using heteroatom‐occupied lattice sites on the energy level to engineer electrocatalytic activity. In order to explore heteroatom‐engineered energy levels of spinel Co3O4 for highly‐effective oxygen electrocatalysts, herein Al atoms are directly introduced into the crystal lattice by occupying the Co2+ ions in the tetrahedral sites and Co3+ ions in the octahedral sites (denoted as Co2+Td and Co3+Oh, respectively). Experimental and theoretical simulations demonstrate that Al3+ ions substituting Co2+Td and Co3+Oh active sites, especially Al3+ ions occupying the Co2+Td sites, optimizes the adsorption, activation, and desorption features of intermediate species during oxygen evolution reaction (OER) processes. As a result, the optimized Co1.75Al1.25O4 nanosheet exhibit unprecedented OER activity with an ultralow overpotential of 248 mV to deliver a current of 10 mA cm–2, among the best Co‐based OER electrocatalysts. This work should not only provide fundamental understanding of the effect of Al‐occupied different Co sites in Co3–xAlxO4 composites on OER performance, but also inspire the design of low‐cost, earth‐abundant, and high‐active electrocatalysts toward water oxidation.  相似文献   

6.
Sluggish kinetics of the multielectron transfer process is still a bottleneck for efficient oxygen evolution reaction (OER) activity, and the reduction of reaction overpotential is crucial to boost reaction kinetics. Herein, a correlation between the OER overpotential and the cobalt‐based electrode composition in a “Microparticles‐in‐Spider Web” (MSW) superstructure electrode is revealed. The overpotential is dramatically decreased first and then slightly increased with the continuous increase ratio of Co/Co3O4 in the cobalt‐based composite electrode, corresponding to the dynamic change of electrochemically active surface area and charge‐transfer resistance with the electrode composition. As a proof‐of‐concept, the optimized electrode displays a low overpotential of 260 mV at 10.0 mA cm?2 in alkaline conditions with a long‐time stability. This electrochemical performance is comparable and even superior to the most currently reported Co‐based OER electrocatalysts. The remarkable electrocatalytic activity is attributed to the optimization of the electrochemically active sites and electron transfer in the MSW superstructure. Theoretical calculations identify that the metallic Co and Co3O4 surface catalytic sites play a vital role in improving electron transport and reaction Gibbs free energies for reducing overpotential, respectively. A general way of boosting OER kinetics via optimizing the electrode configurations to mitigate reaction overpotential is offered in this study.  相似文献   

7.
The design of high‐efficiency non‐noble bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting technologies and associated renewable energy systems. Spinel‐structured oxides with rich redox properties can serve as alternative low‐cost OER electrocatalysts but with poor HER performance. Here, zirconium regulation in 3D CoFe2O4 (CoFeZr oxides) nanosheets on nickel foam, as a novel strategy inducing bifunctionality toward OER and HER for overall water splitting, is reported. It is found that the incorporation of Zr into CoFe2O4 can tune the nanosheet morphology and electronic structure around the Co and Fe sites for optimizing adsorption energies, thus effectively enhancing the intrinsic activity of active sites. The as‐synthesized 3D CoFeZr oxide nanosheet exhibits high OER activity with small overpotential, low Tafel slope, and good stability. Moreover, it shows unprecedented HER activity with a small overpotential of 104 mV at 10 mA cm?2 in alkaline media, which is better than ever reported counterparts. When employing the CoFeZr oxides nanosheets as both anode and cathode catalysts for overall water splitting, a current density of 10 mA cm?2 is achieved at the cell voltage of 1.63 V in 1.0 m KOH.  相似文献   

8.
Cobalt pnictides show good catalytic activity and stability on oxygen evolution reaction (OER) behaviors in a strong alkaline solution. Identifying the intrinsic composition/structure‐property relationship of the oxide layer on the cobalt pnictides is critical to design better and cheaper electrocatalysts for the commercial viability of OER technologies. In this work, the restructured oxide layer on the cobalt pnictides and its effect on the activity and mechanism for OER is systematically analyzed. In‐situ electrochemical impedance spectroscopy (EIS) and near edge x‐ray absorption fine structure (NEXAFS) spectra indicate that a higher OER performance of cobalt pnictides than Co3O4 is attributed to the more structural disorder and oxygen defect sites in the cobalt oxide layer evolved from cobalt pnictides. Using angle resolved x‐ray photoelectron spectroscopy (AR‐XPS) further demonstrates that the oxygen defect sites mainly concentrate on the subsurface of cobalt oxide layer. The current study demonstrated promising opportunities for further enhancing the OER performance of cobalt‐based electrocatalysts by controlling the subsurface defects of the restructured active layer.  相似文献   

9.
10.
The rational design of atomic‐scale interfaces in multiphase nanohybrids is an alluring and challenging approach to develop advanced electrocatalysts. Herein, through the selection of two different metal oxides with particular intrinsic features, advanced Co3O4/CeO2 nanohybrids (NHs) with CeO2 nanocubes anchored on Co3O4 nanosheets are developed, which show not only high oxygen vacancy concentration but also remarkable 2D electron gas (2DEG) behavior with ≈0.79 ± 0.1 excess e?/u.c. on the Ce3+ sites at the Co3O4–CeO2 interface. Such a 2DEG transport channel leads to a high carrier density of 3.8 × 1014 cm?2 and good conductivity. Consequently, the Co3O4/CeO2 NHs demonstrate dramatically enhanced oxygen evolution reaction (OER) performances with a low overpotential of 270 mV at 10 mA cm?2 and a high turnover frequency of 0.25 s?1 when compared to those of pure Co3O4 and CeO2 counterparts, outperforming commercial IrO2 and some recently reported representative OER catalysts. These results demonstrate the validity of tailoring the electrocatalytic properties of metal oxides by 2DEG engineering, offering a step forward in the design of advanced hybrid nanostructures.  相似文献   

11.
The oxygen evolution reaction (OER) is pivotal in multiple gas‐involved energy conversion technologies, such as water splitting, rechargeable metal–air batteries, and CO2/N2 electrolysis. Emerging anion‐redox chemistry provides exciting opportunities for boosting catalytic activity, and thus mastering lattice‐oxygen activation of metal oxides and identifying the origins are crucial for the development of advanced catalysts. Here, a strategy to activate surface lattice‐oxygen sites for OER catalysis via constructing a Ruddlesden–Popper/perovskite hybrid, which is prepared by a facile one‐pot self‐assembly method, is developed. As a proof‐of‐concept, the unique hybrid catalyst (RP/P‐LSCF) consists of a dominated Ruddlesden–Popper phase LaSr3Co1.5Fe1.5O10‐δ (RP‐LSCF) and second perovskite phase La0.25Sr0.75Co0.5Fe0.5O3‐δ (P‐LSCF), displaying exceptional OER activity. The RP/P‐LSCF achieves 10 mA cm?2 at a low overpotential of only 324 mV in 0.1 m KOH, surpassing the benchmark RuO2 and various state‐of‐the‐art metal oxides ever reported for OER, while showing significantly higher activity and stability than single RP‐LSCF oxide. The high catalytic performance for RP/P‐LSCF is attributed to the strong metal–oxygen covalency and high oxygen‐ion diffusion rate resulting from the phase mixture, which likely triggers the surface lattice‐oxygen activation to participate in OER. The success of Ruddlesden–Popper/perovskite hybrid construction creates a new direction to design advanced catalysts for various energy applications.  相似文献   

12.
Transition metal oxides have recently received great attention for application in advanced lithium‐ion batteries (LIBs) and oxygen evolution reaction (OER). Herein, the ethylenediaminetetraacetic cobalt complex as a precursor to synthesize ultrafine Co3O4 nanoparticles encapsulated into a nitrogen‐doped carbon matrix (NC) composites is presented. The as‐prepared Co3O4/NC‐350 obtained by pyrolysis at 350 °C demonstrates superior rate performance (372 mAh g?1 at 5.0 A g?1) and high cycling stability (92% capacity retention after 300 cycles at 1.0 A g?1) as anode for LIBs. When evaluated as an electrocatalyst for OER, the Co3O4/NC‐350 achieves an overpotential of 298 mV at a current density of 10 mA cm?2. The NC‐encapsualted porous hierarchical structure assures fast and continuous electron transportation, high activity sites, and strong structural integrity. This works offers novel complex precursors for synthesizing transition metal–based electrodes for boosting electrochemical energy conversion and storage.  相似文献   

13.
Developing highly active electrocatalysts for oxygen evolution reaction (OER) is critical for the effectiveness of water splitting. Low‐cost spinel oxides have attracted increasing interest as alternatives to noble metal–based OER catalysts. A rational design of spinel catalysts can be guided by studying the structural/elemental properties that determine the reaction mechanism and activity. Here, using density functional theory (DFT) calculations, it is found that the relative position of O p‐band and MOh (Co and Ni in octahedron) d‐band center in ZnCo2?xNixO4 (x = 0–2) correlates with its stability as well as the possibility for lattice oxygen to participate in OER. Therefore, it is testified by synthesizing ZnCo2?xNixO4 spinel oxides, investigating their OER performance and surface evolution. Stable ZnCo2?xNixO4 (x = 0–0.4) follows adsorbate evolving mechanism under OER conditions. Lattice oxygen participates in the OER of metastable ZnCo2?xNixO4 (x = 0.6, 0.8) which gives rise to continuously formed oxyhydroxide as surface‐active species and consequently enhances activity. ZnCo1.2Ni0.8O4 exhibits performance superior to the benchmarked IrO2. This work illuminates the design of highly active metastable spinel electrocatalysts through the prediction of the reaction mechanism and OER activity by determining the relative positions of the O p‐band and the MOh d‐band center.  相似文献   

14.
The widely used route of high‐temperature pyrolysis for transformation of Prussian blue analogs (PBAs) to functional nanomaterials leads to the fast removal of CN? ligands, and thus the formation of large metal aggregates and the loss of porous structures inside PBAs. Here, a controllable pyrolysis route at low temperature is reported for retaining the confined effect of CN? ligands to metal cations during the whole pyrolysis process, thereby preparing high‐surface‐area cubes comprising disordered bimetallic oxides (i.e., Co3O4 and Fe2O3) nanoparticles. The disordered structure of Co3O4 enables the exposure of abundant oxygen vacancies. Notably, for the first time, it is found that the in situ generated CoOOH during the oxygen evolution reaction (OER) can inherit the oxygen vacancies of pristine Co3O4 (i.e., before OER), and such CoOOH with abundant oxygen vacancies adsorbs two ?OH in the following Co3+ to Co4+ for markedly promoting OER. However, during the similar step, the ordered Co3O4 with less oxygen vacancies only involves one ?OH, resulting in the additional overpotentials for adsorbing ?OH. Consequently, with high surface area and disordered Co3O4, the as‐synthesized electrocatalysts have a low potential of 237 mV at 10 mA cm?2, surpassing most of reported electrocatalysts.  相似文献   

15.
The increase of reaction temperature of electrocatalysts is regarded as an efficient method to improve the oxygen evolution reaction (OER) activity. Herein, it is reported that the electrocatalytic performance of dual functional (i.e., electrocatalytic and photothermal functions) Co3O4 can be dramatically improved via its photothermal effect. The operating temperature of the Co3O4 electrode is elevated in situ under near infrared (NIR) light irradiation, resulting in enhanced oxygen evolution activity due to its accelerated electrical conductivity, reaction kinetics, and desorption rate of O2 bubbles from the electrode. In addition, photothermal effect can also enhance the electrocatalytic reaction rates of metal‐doped Co3O4 electrodes, indicating that it is able to significantly improve the OER activities of electrodes together with other modification strategies. With the assistance of the photothermal effect, the obtained Ni‐doped Co3O4 catalyst requires an extremely low overpotential of 208 mV to achieve a benchmark of 10 mA cm?2 with a small Tafel slope, superior to most reported Co‐based catalysts. Significantly, the electrocatalytic performance of other electrodes with photothermal effect, such as CoN, CoP, and CoS, are also boosted under NIR light irradiation, indicating opportunities for implementing photothermal enhancement in electrocatalytic water splitting.  相似文献   

16.
ZnO–Bi2O3–B2O3-based varistors doped with each kind of cobalt oxides were prepared by conventional ceramic processing. The effects of CoO, Co2O3 and Co3O4 on the microstructure and the electrical characteristics of varistor samples sintered at 880 °C were investigated separately. Analysis of microstructure indicated the cobalt cations were distributed both in grain regions and grain boundary regions and no crystalline phases containing cobalt were detected in XRD patterns for the samples with various cobalt oxides. All these cobalt oxides could effectively enhance the varistor performance by effectively increasing the nonlinear coefficient and lowing the leakage current, while the breakdown voltage fields increased slightly. Capacitance–voltage characteristics showed the potential barriers of varistor samples increased with the addition of each cobalt oxide. It was found that the addition of same amount of cobalt cations in various cobalt oxides had a different effect on the varistor samples. Best electrical properties were obtained for the varistor sample containing Co3O4, in which the nonlinearity coefficient is 28.5, the leakage current density is 3.4 μA and the breakdown voltage field is as low as 260 V/mm.  相似文献   

17.
Microporous tricobalt tetraoxide, Co3O4, nanoparticles (NPs) clusters have been successfully fabricated using a simple but efficient controlled solution combustion route. Such a synthesis involves combustion reaction of cobalt nitrate with cetyl trimethylammonium bromide (CTAB). The combustion process has been analyzed by simultaneous thermal analysis. The resultant powders were characterized by means of X-ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and nitrogen adsorption at −196 °C. The morphology and specific surface area of the obtained Co3O4 nanoparticles clusters have proved to be strongly dependent on the fuel (F)/oxidizer (O) molar ratio and the calcination temperature. It was found that both the crystallite size and the lattice parameter nanocrystalline Co3O4 increase with increasing the F/O molar ratio as well as the calcination temperature. X-ray diffraction confirmed the formation of CoO phase together with spinel Co3O4 using F/O ratio of 1. The concentration of such phase increases with increasing the F/O ratio. Moreover, when the calcination is applied at 900–1000 °C traces of CoO was obtained together with Co3O4 as a major phase.  相似文献   

18.
Developing efficient and low-cost electrocatalysts for the oxygen evolution reaction (OER) is of paramount importance to many chemical and energy transformation technologies. The diversity and flexibility of metal oxides offer numerous degrees of freedom for enhancing catalytic activity by tailoring their physicochemical properties, but the active site of current metal oxides for OER is still limited to either metal ions or lattice oxygen. Here, a new complex oxide with unique hexagonal structure consisting of one honeycomb-like network, Ba4Sr4(Co0.8Fe0.2)4O15 (hex-BSCF), is reported, demonstrating ultrahigh OER activity because both the tetrahedral Co ions and the octahedral oxygen ions on the surface are active, as confirmed by combined X-ray absorption spectroscopy analysis and theoretical calculations. The bulk hex-BSCF material synthesized by the facile and scalable sol–gel method achieves 10 mA cm−2 at a low overpotential of only 340 mV (and small Tafel slope of 47 mV dec−1) in 0.1 m KOH, surpassing most metal oxides ever reported for OER, while maintaining excellent durability. This study opens up a new avenue to dramatically enhancing catalytic activity of metal oxides for other applications through rational design of structures with multiple active sites.  相似文献   

19.
Exploring highly active and durable electrocatalysts for oxygen evolution reaction (OER) is significant to achieve efficient anion exchange membrane (AEM) water electrolysis. Herein, hollow Co-based N-doped porous carbon spheres decorated with ultrafine Ru nanoclusters (HS-RuCo/NC) are reported as efficient OER electrocatalysts via the pyrolysis of carboxylate-terminated polystyrene-templated bimetallic zeolite imidazolate frameworks accommodating Ru (III) ions. The unique hollow structure with hierarchically porous characteristics contributes to the electrolyte penetration for fast mass transport and the exposure of more metal sites. Theoretical and experimental studies reveal the synergistic effect between the in situ formed RuO2 and Co3O4 as another critical factor for the high OER performance, where the coupling of RuO2 with Co3O4 can optimize the electronic configuration of RuO2/Co3O4 heterostructure and decrease the energy barrier during OER. Meanwhile, the presence of Co3O4 can efficiently suppress the over-oxidation of RuO2, endowing the catalysts with high stability. As expected, when the resultant HS-RuCo/NC was integrated into an AEM water electrolyzer, the obtained electrolyzer exhibits a cell voltage of 2.07 V to launch the current density of 1 A cm−2 and excellent long-term stability at 500 mA cm−2 under room temperature in alkaline solution, outperforming the commercial RuO2-based AEM water electrolyzer (2.19 V).  相似文献   

20.
Transition‐metal oxides are extensively investigated as efficient electrocatalysts for the oxygen evolution reaction (OER). However, large‐scale applications remain challenging due to their moderate catalytic activity. Optimized regulation of surface states can lead to improvement of catalytic properties. Here, the design of Mn@Cox Mn3?x O4 nanoparticles with abundant edge sites via a simple seed‐mediated growth strategy is described. The unsaturated coordination generated on the edge sites of Cox Mn3?x O4 shells makes a positive contribution to the surface‐structure tailoring. Density functional theory calculations indicate that the edge sites with unsaturated coordination exhibit intense affinity for OH? in the alkaline electrolyte, which greatly enhances the electrochemical OER performance of the catalysts. The resulting Mn@Cox Mn3?x O4 catalysts yield a current density of 10 mA cm?2 at an overpotential of 246 mV and a relatively low Tafel slope of 46 mV dec?1. The successful synthesis of these metal oxides nanoparticles with edge sites may pave a new path for rationally fabricating efficient OER catalysts.  相似文献   

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