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1.
Searching for highly efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) using nonnoble metal‐based catalysts is essential for the development of many energy conversion systems, including rechargeable fuel cells and metal–air batteries. Here, Co9–xFexS8/Co,Fe‐N‐C hybrids wrapped by reduced graphene oxide (rGO) (abbreviated as S‐Co9–xFexS8@rGO) are synthesized through a semivulcanization and calcination method using graphene oxide (GO) wrapped bimetallic zeolite imidazolate framework (ZIF) Co,Fe‐ZIF (CoFe‐ZIF@GO) as precursors. Benefiting from the synergistic effect of OER active CoFeS and ORR active Co,Fe‐N‐C in a single component, as well as high dispersity and enhanced conductivity derived from rGO coating and Fe‐doping, the obtained S‐Co9–xFexS8@rGO‐10 catalyst shows an ultrasmall overpotential of ≈0.29 V at 10 mA cm?2 in OER and a half‐wave potential of 0.84 V in ORR, combining a superior oxygen electrode activity of ≈0.68 V in 0.1 m KOH.  相似文献   

2.
Metal–organic frameworks (MOFs) with tunable compositions and morphologies are recognized as efficient self‐sacrificial templates to achieve function‐oriented nanostructured materials. Moreover, it is urgently needed to develop highly efficient noble metal‐free oxygen evolution reaction (OER) electrocatalysts to accelerate the development of overall water splitting green energy conversion systems. Herein, a facile and cost‐efficient strategy to synthesize Co9S8 nanoparticles‐embedded N/S‐codoped carbon nanofibers (Co9S8/NSCNFs) as highly active OER catalyst is developed. The hybrid precursor of core–shell ZIF‐wrapped CdS nanowires is first prepared and then leads to the formation of uniformly dispersed Co9S8/N, S‐codoped carbon nanocomposites through a one‐step calcination reaction. The optimal Co9S8/NSCNFs‐850 is demonstrated to possess excellent electrocatalytic performance for OER in 1.0 m KOH solution, affording a low overpotential of 302 mV to reach the current density of 10 mA cm?2, a small Tafel slope of 54 mV dec?1, and superior long‐term stability for 1000 cyclic voltammetry cycles. The favorable results raise a concept of exploring more MOF‐based nanohybrids as precursors to induce the synthesis of novel porous nanomaterials as non‐noble‐metal electrocatalysts for sustainable energy conversion.  相似文献   

3.
Metal oxides of earth‐abundant elements are promising electrocatalysts to overcome the sluggish oxygen evolution and oxygen reduction reaction (OER/ORR) in many electrochemical energy‐conversion devices. However, it is difficult to control their catalytic activity precisely. Here, a general three‐stage synthesis strategy is described to produce a family of hybrid materials comprising amorphous bimetallic oxide nanoparticles anchored on N‐doped reduced graphene oxide with simultaneous control of nanoparticle elemental composition, size, and crystallinity. Amorphous Fe0.5Co0.5Ox is obtained from Prussian blue analog nanocrystals, showing excellent OER activity with a Tafel slope of 30.1 mV dec?1 and an overpotential of 257 mV for 10 mA cm?2 and superior ORR activity with a large limiting current density of ?5.25 mA cm?2 at 0.6 V. A fabricated Zn–air battery delivers a specific capacity of 756 mA h gZn?1 (corresponding to an energy density of 904 W h kgZn?1), a peak power density of 86 mW cm?2 and can be cycled over 120 h at 10 mA cm?2. Other two amorphous bimetallic, Ni0.4Fe0.6Ox and Ni0.33Co0.67Ox , are also produced to demonstrate the general applicability of this method for synthesizing binary metal oxides with controllable structures as electrocatalysts for energy conversion.  相似文献   

4.
Bifunctional electrocatalysis for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) constitutes the bottleneck of various sustainable energy devices and systems like rechargeable metal–air batteries. Emerging catalyst materials are strongly requested toward superior electrocatalytic activities and practical applications. In this study, transition metal hydroxysulfides are presented as bifunctional OER/ORR electrocatalysts for Zn–air batteries. By simply immersing Co‐based hydroxide precursor into solution with high‐concentration S2?, transition metal hydroxides convert to hydroxysulfides with excellent morphology preservation at room temperature. The as‐obtained Co‐based metal hydroxysulfides are with high intrinsic reactivity and electrical conductivity. The electron structure of the active sites is adjusted by anion modulation. The potential for 10 mA cm?2 OER current density is 1.588 V versus reversible hydrogen electrode (RHE), and the ORR half‐wave potential is 0.721 V versus RHE, with a potential gap of 0.867 V for bifunctional oxygen electrocatalysis. The Co3FeS1.5(OH)6 hydroxysulfides are employed in the air electrode for a rechargeable Zn–air battery with a small overpotential of 0.86 V at 20.0 mA cm?2, a high specific capacity of 898 mAh g?1, and a long cycling life, which is much better than Pt and Ir‐based electrocatalyst in Zn–air batteries.  相似文献   

5.
Development of cost‐effective, active trifunctional catalysts for acidic oxygen reduction (ORR) as well as hydrogen and oxygen evolution reactions (HER and OER, respectively) is highly desirable, albeit challenging. Herein, single‐atomic Ru sites anchored onto Ti3C2Tx MXene nanosheets are first reported to serve as trifunctional electrocatalysts for simultaneously catalyzing acidic HER, OER, and ORR. A half‐wave potential of 0.80 V for ORR and small overpotentials of 290 and 70 mV for OER and HER, respectively, at 10 mA cm?2 are achieved. Hence, a low cell voltage of 1.56 V is required for the acidic overall water splitting. The maximum power density of an H2–O2 fuel cell using the as‐prepared catalyst can reach as high as 941 mW cm?2. Theoretical calculations reveal that isolated Ru–O2 sites can effectively optimize the adsorption of reactants/intermediates and lower the energy barriers for the potential‐determining steps, thereby accelerating the HER, ORR, and OER kinetics.  相似文献   

6.
The development of rechargeable metal–air batteries and water electrolyzers are highly constrained by electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). However, the construction of efficient trifunctional electrocatalysts for ORR/OER/HER are highly desirable yet challenging. Herein, hollow carbon nanotubes integrated single cobalt atoms with Co9S8 nanoparticles (CoSA + Co9S8/HCNT) are fabricated by a straightforward in situ self‐sacrificing strategy. The structure of the CoSA + Co9S8/HCNT are verified by X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy. Theoretical calculations and experimental results embrace the synergistic effects between Co9S8 nanoparticles and single cobalt atoms through optimizing the electronic configuration of the CoN4 active sites to lower the reaction barrier and facilitating the ORR, OER, and HER simultaneously. Consequently, rechargeable liquid and all‐solid‐state flexible Zn–air batteries based on CoSA + Co9S8/HCNT exhibit remarkable stability and excellent power density of 177.33 and 51.85 mW cm?2, respectively, better than Pt/C + RuO2 counterparts. Moreover, the as‐fabricated Zn–air batteries can drive an overall water splitting device assembled with CoSA + Co9S8/HCNT and achieve a current density of 10 mA cm?2 at a low voltage of 1.59 V, also superior to Pt/C + RuO2. Therefore, this work presents a promising approach to an efficient trifunctional electrocatalyst toward practical applications.  相似文献   

7.
Among the bifunctional catalysts for water splitting, recently emerged transition‐metal single‐atom catalysts are theoretically considered to possess high potential, while the experimental activity is not satisfactory yet. Herein, an exceptionally efficient trifunctional metal–nitrogen–carbon (M–N–C) catalyst electrode, composed of a hierarchical carbon matrix embedding isolated nickel atoms with nickel–iron (NiFe) clusters, is presented. 1D microfibers and nanotubes grow sequentially from 2D nanosheets as sacrificial templates via two stages of solution‐ and solid‐phase reactions to form a 1D hierarchy. Exceptionally efficient bifunctional activity with an overpotential of only 13 mV at 10 mA cm?2 toward hydrogen evolution reaction (HER) and an overpotential of 210 mV at 30 mA cm?2 toward oxygen evolution reaction (OER) is obtained, surpassing each monofunctional activity ever reported. More importantly, an overpotential of only 126 and 326 mV is required to drive 500 mA cm?2 toward the HER and OER, respectively. For the first time, industrial‐scale water splitting with two bifunctional catalyst electrodes with a current density of 500 mA cm?2 at a potential of 1.71 V is demonstrated. Lastly, trifunctional catalytic activity including oxygen reduction reaction is also proven with a half‐wave potential at 0.848 V.  相似文献   

8.
Synergistic improvements in the electrical conductivity and catalytic activity for the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) are of paramount importance for rechargeable metal–air batteries. In this study, one‐nanometer‐scale ultrathin cobalt oxide (CoOx) layers are fabricated on a conducting substrate (i.e., a metallic Co/N‐doped graphene substrate) to achieve superior bifunctional activity in both the ORR and OER and ultrahigh output power for flexible Zn–air batteries. Specifically, at the atomic scale, the ultrathin CoOx layers effectively accelerate electron conduction and provide abundant active sites. X‐ray absorption spectroscopy reveals that the metallic Co/N‐doped graphene substrate contributes to electron transfer toward the ultrathin CoOx layer, which is beneficial for the electrocatalytic process. The as‐obtained electrocatalyst exhibits ultrahigh electrochemical activity with a positive half‐wave potential of 0.896 V for ORR and a low overpotential of 370 mV at 10 mA cm?2 for OER. The flexible Zn–air battery built with this catalyst exhibits an ultrahigh specific power of 300 W gcat ?1, which is essential for portable devices. This work provides a new design pathway for electrocatalysts for high‐performance rechargeable metal–air battery systems.  相似文献   

9.
Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N‐doped carbon matrix (Co6W6C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal–organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen‐binding energy. Thus Co6W6C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of ?10 mA cm?2. Besides, Co6W6C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of ?10 mA cm?2. The water splitting device, by applying Co6W6C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm?2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.  相似文献   

10.
The large‐scale commercial application of lithium–oxygen batteries (LOBs) is overwhelmed by the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) associated with insoluble and insulated Li2O2. Herein, an elaborate design on a highly catalytic LOBs cathode constructed by N‐doped carbon nanotubes (CNT) with in situ encapsulated Co2P and Ru nanoparticles is reported. The homogeneously dispersed Co2P and Ru catalysts can effectively modulate the formation and decomposition behavior of Li2O2 during discharge/charge processes, ameliorating the electronically insulating property of Li2O2 and constructing a homogenous low‐impedance Li2O2/catalyst interface. Compared with Co/CNT and Ru/CNT electrodes, the Co2P/Ru/CNT electrode delivers much higher oxygen reduction triggering onset potential and higher ORR and OER peak current and integral areas, showing greatly improved ORR/OER kinetics due to the synergistic effects of Co2P and Ru. Li–O2 cells based on the Ru/Co2P/CNT electrode demonstrate improved ORR/OER overpotential of 0.75 V, excellent rate capability of 12 800 mAh g?1 at 1 A g?1, and superior cycle stability for more than 185 cycles under a restricted capacity of 1000 mAh g?1 at 100 mA g?1. This work paves an exciting avenue for the design and construction of bifunctional catalytic cathodes by coupling metal phosphides with other active components in LOBs.  相似文献   

11.
Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this work, highly monodisperse CoP and Co2P nanocrystals (NCs) are synthesized using a robust solution‐phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal‐rich Co2P NCs show higher OER performance owing to easier formation of plentiful Co2P@COOH heterojunctions. Density functional theory calculation results indicate that the desorption of OH* from cobalt sites is the rate‐limiting step for both CoP and Co2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co2P NC anode can achieve a current density of 10 mA cm?2 at 1.56 V, comparable even to the noble metal‐based Pt/C and RuO2/C pair. Furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm?2 and good stability.  相似文献   

12.
Here, ferrocene(Fc)‐incorporated cobalt sulfide (CoxSy) nanostructures directly grown on carbon nanotube (CNT) or carbon fiber (CF) networks for electrochemical oxygen evolution reaction (OER) using a facile one‐step solvothermal method are reported. The strong synergistic interaction between Fc‐CoxSy nanostructures and electrically conductive CNTs results in the superior electrocatalytic activity with a very small overpotential of ≈304 mV at 10 mA cm?2 and a low Tafel slope of 54.2 mV dec?1 in 1 m KOH electrolyte. Furthermore, the Fc‐incorporated CoxSy (FCoS) nanostructures are directly grown on the acid pretreated carbon fiber (ACF), and the resulting fabricated electrode delivers excellent OER performance with a low overpotential of ≈315 mV at 10 mA cm?2. Such superior OER catalytic activity can be attributed to 3D Fc‐CoxSy nanoarchitectures that consist of a high concentration of vertical nanosheets with uniform distribution of nanoparticles that afford a large number of active surface areas and edge sites. Besides, the tight contact interface between ACF substrate and Fc‐CoxSy nanostructures could effectively facilitate the electron transfer rate in the OER. This study provides valuable insights for the rational design of energy storage and conversion materials by the incorporation of other transition metal into metal sulfide/oxide nanostructures utilizing metallocene.  相似文献   

13.
Herein, the facile preparation of ultrathin (≈3.8 nm in thickness) 2D cobalt phosphate (CoPi) nanoflakes through an oil‐phase method is reported. The obtained nanoflakes are composed of highly ordered mesoporous (≈3.74 nm in diameter) structure and exhibit an amorphous nature. Attractively, when doped with nickel, such 2D mesoporous Ni‐doped CoPi nanoflakes display decent electrocatalytic performances in terms of intrinsic activity, and low kinetic barrier toward the oxygen evolution reaction (OER). Particularly, the optimized 10 at% Ni‐doped CoPi nanoflakes (denoted as Ni10‐CoPi) deliver a low overpotential at 10 mA cm?2 (320 mV), small Tafel slope (44.5 mV dec?1), and high stability for OER in 1.0 m KOH solution, which is comparable to the state‐of‐the‐art RuO2 tested in the same condition (overpotential: 327 mV at 10 mA cm?2, Tafel slope: 73.7 mV dec?1). The robust framework coupled with good OER performance enables the 2D mesoporous Ni10‐CoPi nanoflakes to be a promising material for energy conversion applications.  相似文献   

14.
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   

15.
Iron corrosion causes a great damage to the economy due to the function attenuation of iron‐based devices. However, the corrosion products can be used as active materials for some electrocatalytic reactions, such as oxygen evolution reaction (OER). Herein, the oxygen corrosion on Fe foams (FF) to synthesize effective self‐supporting electrocatalysts for OER, leading to “turning waste into treasure,” is regulated. A dual chloride aqueous system of “NaCl‐NiCl2” is employed to tailor the structures and OER properties of corrosion layers. The corrosion behaviors identify that Cl? anions serve as accelerators for oxygen corrosion, while Ni2+ cations guarantee the uniform growth of corrosion layers owing to the appeared chemical plating. The synergistic effect of “NaCl‐NiCl2” generates one of the highest OER activities that only an overpotential of 212 mV is required to achieve 100 mA cm?2 in 1.0 m KOH solution. The as‐prepared catalyst also exhibits excellent durability over 168 h (one week) at 100 mA cm?2 and promising application for overall water splitting. Specially, a large self‐supporting electrode (9 × 10 cm2) is successfully synthesized via this cost‐effective and easily scale‐up approach. By combining with corrosion science, this work provides a significant stepping stone in exploring high‐performance OER electrocatalysts.  相似文献   

16.
Due to the earth abundance and tunable electronic properties, etc., transition metal oxides (TMOs) show attractive attention in oxygen evolution reaction. O‐vacancies (Vo) play important roles in tailoring the local surface and electronic environment to lower the activation barriers. Herein, an effective strategy is shown to enhance the oxygen evolution reduction (OER) performance on Co3O4 ultrathin nanosheets via combined cation substitution and anion vacancies. The oxygen‐deficient Fe‐Co‐O nanosheets (3–4 nm thickness) display an overpotential of 260 mV@10 mA cm?2 and a Tafel slope of 53 mV dec?1, outperforming those of the benchmark RuO2 in 1.0 m KOH. Further calculations demonstrate that the combined introduction of Fe cation and Vo with appropriate location and content finely tune the intermediate absorption, consequently lowering the rate‐limiting activation energy from 0.82 to as low as 0.15 eV. The feasibility is also proved by oxygen‐deficient Ni‐Co‐O nanosheets. This work not only establishes a clear atomic‐level correlation between cation substitution, anion vacancies, and OER performance, but also provides valuable insights for the rational design of highly efficient catalysts for OER.  相似文献   

17.
Herein, an approach is reported for fabrication of Co‐Nx‐embedded 1D porous carbon nanofibers (CNFs) with graphitic carbon‐encased Co nanoparticles originated from metal–organic frameworks (MOFs), which is further explored as a bifunctional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Electrochemical results reveal that the electrocatalyst prepared by pyrolysis at 1000 °C (CoNC‐CNF‐1000) exhibits excellent catalytic activity toward ORR that favors the four‐electron ORR process and outstanding long‐term stability with 86% current retention after 40 000 s. Meanwhile, it also shows superior electrocatalytic activity toward OER, reaching a lower potential of 1.68 V at 10 mA cm?2 and a potential gap of 0.88 V between the OER potential (at 10 mA cm?2) and the ORR half‐wave potential. The ORR and OER performance of CoNC‐CNF‐1000 have outperformed commercial Pt/C and most nonprecious‐metal catalysts reported to date. The remarkable ORR and OER catalytic performance can be mainly attributable to the unique 1D structure, such as higher graphitization degree beneficial for electronic mobility, hierarchical porosity facilitating the mass transport, and highly dispersed CoNxC active sites functionalized carbon framework. This strategy will shed light on the development of other MOF‐based carbon nanofibers for energy storage and electrochemical devices.  相似文献   

18.

Designing high-efficient and low cost of electrodes with seamless integration of substrate and electrocatalyst particles is of significant concern for electrocatalytic water splitting. In this study, we actualized in situ growth of Co3O4 nanoneedles on titanium (Ti) mesh (denoted as Co3O4@Ti) by a simple combination of hydrothermal approach and subsequently calcination treatment under relatively low temperatures. The as-prepared Co3O4@Ti samples were evaluated as anodes for electrocatalytic oxygen evolution reaction (OER) in alkaline electrolyte. It demonstrates that the optimized Co3O4@Ti electrode displayed good OER activity with a small overpotential of 416 mV at a current density of 20 mA cm?2, which is on a par with commercial RuO2 catalyst (overpotential of 403 mV at 20 mA cm?2). The satisfactory OER performance of Co3O4@Ti electrode is largely attributed to the seamless integration of conductive Ti mesh substrate and the direct growth of Co3O4 nanoneedles on Ti mesh with sufficient active sites. This study suggests the potential application of Co3O4@Ti electrode as preeminent OER catalyst.

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19.
Hydrogen is regarded as the most promising green clean energy in the 21st century. Developing the highly efficient and low‐cost electrocatalysts for oxygen evolution reaction (OER) is of great concern for the hydrogen industry. In the water electrolyzed reaction, the overpotential and the kinetics are the main hurdles for OER. Therefore, an efficient and durable oxygen evolution reaction electrocatalyst is required. In this study, an activated graphene (AG)–black phosphorus (BP) nanosheets hybrid is fabricated for supporting Ni3N particles (Ni3N/BP‐AG) in the application of OER. The Ni3N particles are combined with the BP‐AG heterostructure via facile mechanical ball milling under argon protection. The synthesized Ni3N/BP‐AG shows excellent catalytic performance toward the OER, demanding the overpotential of 233 mV for a current density of 10 mA cm?2 with a Tafel slope of 42 mV dec?1. The Ni3N/BP‐AG catalysts also show remarkable stability with a retention rate of the current density of about 86.4% after measuring for 10 000 s in potentiostatic mode.  相似文献   

20.
Liu  Peng  Cheng  Gao  Liu  Guanliang  Sun  Ming  Fu  Shuchai  Zhou  Zihao  Han  Shengbo  Yu  Lin 《Journal of Materials Science: Materials in Electronics》2021,32(11):14385-14397

Avoiding agglomeration of nanoparticles and regulating the electronic properties are highly essential methods to improve the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of catalysts and enhance the cycle stability of rechargeable metal-air batteries. Herein, orthorhombic CoSe2 nanoparticles anchored in acid-treated Ketjenblack (o-CoSe2/AK) nanoparticles have been synthesized via a hydrothermal reaction and selenization treatment, and exhibit excellent ORR and OER performance (a half-wave potential of 0.84 V for ORR and an overpotential of 380 mV at 10 mA cm?2 for OER). As a catalyst for a rechargeable Zn-air battery, it possesses a largest powder density of 122.0 mW cm?2. Surprisingly, o-CoSe2/AK has demonstrated outstanding stability and durability, especially superior to noble metals. The excellent bifunctional electrocatalytic performance is mainly ascribed to a large specific surface area, and metallic o-CoSe2 nanoparticles with a high dispersion anchored in the AK substrate surface, regulating the electronic structure.

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