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1.
Oxygen evolution reaction (OER) is regarded as a limit-efficiency process in electrochemical water splitting generally, which needs to develop the effective and low-cost non-noble metal electrocatalysts. Oxygen vacancies have been verified to be beneficial to enhance the electrocatalytic performance of catalysts. Herein, we report the facile synthesis of reduced CoFe2O4/graphene (r-CFO/rGO) composite with rich oxygen vacancies by a citric acid assisted sol-gel method, heat treatment process and the sodium borohydride (NaBH4) reduction. The introduction of graphene and freezing dry technique prevents the restacking of GO and the aggregation of CFO nanoparticles (NPs) and increases the electronic conductivity of the catalyst. Fast heating rate and low anneal temperature favors to obtain low crystallinity and lattice defects for CFO. NaBH4 reduction treatment further creates the rich oxygen vacancies and electrocatalytic active sites. The obtained r-CFO/rGO with high specific surface area (108 m2 g−1), low crystallinity and rich oxygen vacancies demonstrates a superior electrocatalytic activity with the smaller Tafel slope (68 mV dec−1), lower overpotential (300 mV) at the current density of 10 mA cm−2, and higher durability compared with the commercial RuO2 catalyst. This green, low-cost method can be extended to fabricate similar composites with rich defects for wide applications.  相似文献   

2.
Enhancing the catalytic activity of Co3O4 electrocatalysts featuring abundant oxygen vacancies is required to enable their application in oxygen evolution reaction (OER). However, developing a harmless defect engineering strategy based on mild conditions to realize such an enhancement remains a challenge. Here, ultrathin Co3O4 nanosheets with abundant oxygen vacancies were prepared through a simple two-step method comprising a hydrothermal process and pre-oxidation to study the catalytic activity of the nanosheets toward OER. The ultrathin sheet structure and the Co3O4 nanosheets surface provide abundant active sites. The oxygen vacancy not only improves the catalyst activity, but also improves the electron transfer efficiency. These advantages make ultrathin Co3O4 nanosheets with abundant oxygen vacancies an excellent electrocatalyst for oxygen evolution. In an alkaline medium, ultrathin Co3O4 nanosheets exhibited excellent OER catalytic activity, with a small overpotential (367 mV for 10 mA/cm2) and faster reaction kinetics (65 mV/dec).Moreover, the electrocatalyst still maintained 68% of its original catalytic activity after 24 h operation. This work provides an extensive and reliable method for the preparation of low-cost and highly efficient OER electrocatalysts.  相似文献   

3.
Heterostructured materials with special interfaces and features give a unique character for much electrocatalytic process. In this work, the introduction of exogenous modifier Ni-MOF improved the reaction kinetics and morphology of the NiCo2O4@Ni-MOF/NF catalyst. As-obtained NiCo2O4@Ni-MOF/NF has excellent oxygen evolution reaction (OER) performance and urea oxidation reaction (UOR) performance. The catalyst need overpotential of 340 mV at a current density of 100 mA cm?2 for OER and a potential of 1.31 V at the same current density for UOR. The Tafel slopes of NiCo2O4@Ni-MOF/NF is 38.34 and 15.33 mV dec?1 for OER and UOR respectively, which is more superior than 78.58 and 66.73 mV dec?1 of NiCo2O4/NF. The nanosheets microstructure is beneficial to the adsorption and transport of electrolyte and the presence of a large number of mesoporous channels can also accelerate gas release, and then improves activity of the catalyst. Density functional theory calculation demonstrate that NiCo2O4 plays a role in absorbing water, while the existence of in situ generated NiOOH can promote the electron transfer efficiency. It is synergies of NiCo2O4 and in situ generated NiOOH that enhance the decomposition of water on the surface of the NiCo2O4@Ni-MOF/NF. This investigation provides a new strategy for the application of spinel oxide and MOF materials.  相似文献   

4.
The efficiency of electrochemical water splitting is greatly hindered by the thermodynamic uphill reaction of oxygen evolution reaction (OER). Thus, it is important to synthesize an active OER electrocatalysts with abundant active sites, favorable conductivity and good durability. Herein, a facile reduction method using NaBH4 as readily available reductant has been developed to fabricate the reduced CoFe2O4 nanosheets (NS). The obtained reduced CoFe2O4 NS are rich in oxygen deficient sites, leading to more active sites as well as the enhanced conductivity than the pristine CoFe2O4 hollow nanosphere, which reaches the current density of 10 mA cm?2 at the overpotential of 320 mV in 1 M KOH. Meanwhile, CoFe2O4 samples with three different morphology nanostructures including hollow nanospheres, bulk and nanoparticles have been provided to study the effect of different morphology on NaBH4 reduction efficiency. As expected, after NaBH4 reduction, CoFe2O4 hollow nanosphere with relatively higher surface area exhibits most obvious improvement for OER activity and also its corresponding reduced CoFe2O4 NS showed best OER performance than the reduced CoFe2O4 bulk as well as the reduced CoFe2O4 nanoparticles, implying the hollow nanospheres feature more accessible surface area than bulk and nanoparticles samples, thus greatly facilitate efficiency of NaBH4 reduction treatment.  相似文献   

5.
Oxygen evolution reaction (OER) is an important bottleneck for large-scale acidic water splitting applications due to its sluggish reaction kinetics. Therefore, the development of highly active, stable, and inexpensive electrocatalysts for OER remains a challenge. Herein, we develop the iridium doped Co3O4 (Ir–Co3O4) with low Ir content of 2.88 wt% for efficient acidic OER. Considering systemic characterizations, it is probably concluded that Ir can be uniformly doped into the lattice of Co3O4 and induce a certain distortion. The electrochemical results reveal that Ir–Co3O4 nanoparticles demonstrate significantly enhanced electrocatalytic OER activity and stability in 0.5 M H2SO4 solution compared with pure Co3O4, in which the overpotential at the current density of 10 mA cm−2 decreases from 382 mV to 225 mV and the value of Tafel slope decreases from 101.7 mV dec−1 to 64.1 mV dec−1. Besides, Ir–Co3O4 exhibits excellent electrocatalytic durability for continuous 130 h's test without any activity attenuation. Moreover, this work provides a kind of high-performance acidic OER electrocatalyst for the development of hydrogen energy.  相似文献   

6.
Oxygen evolution reaction (OER) plays a decisive role in electrolytic water splitting. However, it is still challengeable to develop low-cost and efficient OER electrocatalysts. Herein, we present a combination strategy via heteroatom doping, hetero-interface engineering and introducing conductive skeleton to synthesize a hybrid OER catalyst of CNT-interconnected iron-doped NiP2/Ni2P (Fe-(NiP2/Ni2P)@CNT) heterostructural nanoflowers by a simple hydrothermal reaction and subsequent phosphorization process. The optimized Fe-(NiP2/Ni2P)@CNT catalyst delivers an ultralow Tafel slope of 46.1 mV dec?1 and overpotential of 254 mV to obtain 10 mA cm?2, which are even better than those of commercial OER catalyst RuO2. The excellent OER performance is mainly attributed to its unique nanoarchitecture and the synergistic effects: the nanoflowers constructed by a 2D-like nanosheets guarantee large specific area and abundant active sites; the highly conductive CNT skeleton and the electronic modulation by the heterostructural NiP2/Ni2P interface and the hetero-atom doping can improve the catalytic activity; porous nanostructure benefits electrolyte penetration and gas release; most importantly, the rough surface and rich defects caused by phosphorization process can further enhance the OER performance. This work provides a deep insight to boost catalytic performance by heteroatom doping and interface engineering for water splitting.  相似文献   

7.
Spinel CoFe2O4 supported on three dimensional graphene (3DG) is prepared by hydrothermal reaction, which is denoted as CoFe2O4/3DG. The 3DG is prepared by the templated method, where coal tar pitch (CTP) and MgO are used as the carbon source and the template, respectively. The microstructure and composition of the resultant have been investigated by X-ray diffraction as well as X-ray photoelectron spectroscopy indicating the formation of spinel CoFe2O4 and composite of CoFe2O4/3DG. The multilayer structure of 3DG and CoFe2O4/3DG is also examined by the Raman spectra. Electrochemically, CoFe2O4/3DG shows high-performance half-wave potential is 0.80 V vs. RHE in O2-saturated 0.1 M KOH, which is compared to 20 wt% Pt/C. When evaluated for OER activity, CoFe2O4/3DG obtains a low overpotential 1.63 V vs. RHE (at j = 10 mA cm−2), which is 180 mV better than 20 wt% Pt/C. Moreover, it possesses excellent durability superior to 20 wt% Pt/C.  相似文献   

8.
Spinel oxide electrocatalysts supported on carbon nanofibers (CNFs), denoted as and NiMn2O4/CNF and NiCo2O4/CNF, are investigated for the oxygen evolution reaction (OER) in alkaline electrolyte. NiCo2O4/CNF and NiMn2O4/CNF are prepared according to an optimized electrospinning method using polyacrylonitrile (PAN) as carbon nanofibers precursor. After the thermal treatment at 900 °C for 1 h in the presence of helium and the subsequent one at 350 °C for 1 h in air, nanosized metal oxides with a spinel structure supported on carbon nanofibers are obtained. The physico-chemical investigation shows relevant difference in the crystallite size (9 nm for the NiCo2O4/CNF and 20 nm for the NiMn2O4/CNF) and a more homogeneous distribution for NiMn2O4 supported on carbon nanofibers. These characteristics derive from the different catalytic effects of Co and Mn during the thermal treatment as demonstrated by thermal analysis. The OER activity of NiCo2O4/CNF and NiMn2O4/CNF is studied in a single cell based on a zero gap anion-exchange membrane-electrode assembly (MEA). The NiMn2O4/CNF shows a better mass activity than NiCo2O4/CNF at 50 °C (116 A g−1 @ 1.5 V and 362 A g−1 @ 1.8 V vs. 39 A g−1 @ 1.5 V and 253 A g−1 @ 1.8 V) but lower current density at specific potentials. This is the consequence of a lower concentration of the active phase on the support resulting from the need to mitigate the particle growth in NiMn2O4/CNF.  相似文献   

9.
Transition metals sulfide-based nanomaterials have recently received significant attention as a promising cathode electrode for the oxygen evolution reaction (OER) due to their easily tunable electronic, chemical, and physical properties. However, the poor electrical conductivity of metal-sulfide materials impedes their practical application in energy devices. Herein, firstly nano-sized crystals of cobalt-based zeolitic-imidazolate framework (Co-ZIF) arrays were fabricated on nickel-form (NF) as the sacrificial template by a facile solution method to enhance the electrical conductivity of the electrocatalyst. Then, the Co3S4/NiS@NF heterostructured arrays were synthesized by a simple hydrothermal route. The Co-ZIFs derived Co3S4 nanosheets are grown successfully on NiS nanorods during the hydrothermal sulfurization process. The bimetallic sulfide-based Co3S4/NiS@NF-12 electrocatalyst demonstrated a very low overpotential of 119 mV at 10 mA cm?2 for OER, which is much lower than that of mono-metal sulfide NiS@NF (201 mV) and ruthenium-oxide (RuO2) on NF (440 mV) electrocatalysts. Furthermore, the Co3S4/NiS@NF-12 electrocatalyst showed high stability during cyclic voltammetry and chronoamperometry measurements. This research work offers an effective strategy for fabricating high-performance non-precious OER electrocatalysts.  相似文献   

10.
The development of economical, durable, and efficient oxygen evolution reaction (OER) electrocatalysts is essential for large-scale industrial water electrolysis. Here, a straightforward strategy is proposed to synthesize a series of nickel selenide nanosheets supported on nickel foam (NiSe2/NF) materials by directly selenizing nickel foam substrates at different temperatures under an inert atmosphere. When evaluated as electrocatalysts in OER, the optimal self-supported NiSe2/NF-350 shows an excellent performance in 1.0 M KOH medium with an overpotential of 458 mV at 100 mA cm?2, a small Tafel slope of 45.8 mV dec?1, and a long-term stability for 36 h. Furthermore, the structural and compositional preservation for NiSe2/NF-350 after stability test was also verified by various characterizations.  相似文献   

11.
It is an inevitable choice to find efficient and economically-friendly electrocatalysts to reduce the high overpotential of oxygen evolution reaction (OER), which is the key to improve the energy conversion efficiency of water splitting. Herein, we synthesized Cu2S/Ni3S2 catalysts on nickel foam (NF) with different molar ratios of Ni/Cu by a simple two-step hydrothermal method. Cu2S/Ni3S2-0.5@NF (CS/NS-0.5@NF) effectively reduces the overpotential of OER, displaying small overpotentials (237 mV@100 mA cm?2 and 280 mV@500 mA cm?2) in an alkaline solution, along with a low Tafel slope of 44 mV dec?1. CS/NS-0.5@NF also presents an excellent durability at a relatively high current density of 100 mA cm?2 for 100 h. The excellent performance is benefited by the prominent structural advantages and desirable compositions. The nanosheet has a high electrochemical active surface area and the porous structure is conducive to electrolyte penetration and product release. This work provides an economically-friendly Cu-based sulfide catalyst for effective electrosynthesis of OER.  相似文献   

12.
Developing effective and robust electrocatalysts that are applicable for intense conditions is promising for variable industrial oxygen evolution reaction (OER). Herein, we have developed a simple hydrothermal strategy to construct a three dimensional nanoflower-like VOx nanosheets (VOx/NiS/NF) that utilizes S-modified NF as substrate. NiS/NF can provide not only high-surface area for the growth of VOx but also better conductivity and stability derived from NiS. XRD shows the formation of amorphous VOx supported on NiS/NF. XPS confirms the existence and valence state of V, Ni and S. EDX and SEM elemental mapping reveal the composition and great distribution of V, O, Ni and S. SEM and TEM show that the thin VOx nanosheets covered on the surface of NiS/NF uniformly, which implying more exposed active sites. OER measurements display that VOx/NiS/NF has the outstanding catalytic activity with the lower overpotential (330 mV, 50 mA cm−2), smaller tafel slope (121 mV dec−1) and lower value of semicircle of EIS than VOx/NF. The modification of NF may be the key for enhancement performances for OER due to reduced charge transfer resistance. The strong durability of VOx/NiS/NF may be attributed to the tighter integration between VOx and NiS/NF in alkaline electrolytes. The impressive results may provide a new strategy to design suitable substrate with good dispersion and conductivity to prepare effective electrocatalysts for OER.  相似文献   

13.
Low-cost and earth-abundant nickel chalcogenides with versatilities in electrocatalysis, conversion and storage of energy are hindered in practical application due to the low electrical conductivity and small specific surface area. In the present work, we report a simple preparation of 2D nanocomposites of NiSx (5 nm) uniformly embedded in several layered graphite (NiSx@graphite) through the sulfidation of nickel naphtalenedicarboxylic acid framework nanosheets (∼9 nm). The obtained NiSx@graphite nanosheet composites are used for oxygen evolution reaction (OER) catalysis. Electrochemical studies reveal that their OER activities under strongly alkaline conditions are ranked in the order of Ni9S8@graphite > NiS@graphite > NiS2@graphite. The outstanding OER performance offered by Ni9S8@graphite owes to the synergistic effects of large specific surface area and the special structure between nickel sulfide and graphite layer, and the intrinsic large TOFs and the optimal adsorption energy of Ni9S8. Furthermore, Ni9S8@graphite as an anode material used for lithium ion batteries (LIBs) also shows a high specific capacity with competitive rate performance. Such excellent performance and low price render nickel chalcogenides a promising candidate for the future OER catalyst and LIBs application.  相似文献   

14.
Electrochemical water splitting for hydrogen production is a promising solution for the production of renewable and environmentally friendly energy sources, but it is hindered by the sluggish kinetic process of oxygen evolution reaction (OER). Here, a novel hierarchical core-shell nanoarray NiCo/Ni/CuO/CF was synthesized by assembling Ni–Co hydroxide nanosheets directly on the metallic nickel coated CuO nanowires, as a highly efficient electrocatalyst for alkaline OER. This NiCo/Ni/CuO/CF anode exhibited low overpotentials of 246 mV and 286 mV at current densities of 10 mA cm−2 and 100 mA cm−2, respectively, and a small Tafel slope of 37.9 mV dec−1. Moreover, NiCo/Ni/CuO/CF showed robust durability at least 60 h at a current density of 100 mA cm−2. Detailed investigations verified that the unique nanosheets/nanowires architecture with high conductivity metallic nickel layer can expand the exposure of active sites and accelerate the transport of electrons.  相似文献   

15.
Highly efficient bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for the development of renewable energy technologies such as fuel cells and metal-air batteries. Herein, a ceria (CeO2) – modified reduced graphene oxide (CeO2/rGO) nanocomposite was fabricated via a facile yet cost-effective method under a mild condition. The prepared CeO2/rGO nanocomposite showed remarkable catalytic activity, high tolerance to methanol and durability toward ORR in alkaline media. Meanwhile, the catalyst also displayed remarkable activity for the OER with more negative onset potential and higher current compared with commercial Pt/C catalyst. The high oxygen reaction activity of the catalyst could contribute to synergistic effect of the combination of the oxygen vacancies of CeO2 and excellent electronic conductivity of rGO. The results suggested that the CeO2/rGO nanocomposite has potential advantages as a bifunctional electrocatalyst in the practical applications.  相似文献   

16.
Trimetallic NiFeCo selenides (NiFeCoSex) anchored on carbon fiber cloth (CFC) as efficient electrocatalyst for oxygen evolution reaction (OER) in alkaline medium have been synthesized via a facile two-step method. Firstly, trimetallic NiFeCo (oxy) hydroxides have been electrodeposited on CFC support (NiFeCo/CFC). Secondly, a solvothermal selenization process has been used to convert NiFeCo/CFC into NiFeCoSex/CFC using N, N-dimethylformamide (DMF) as solvent. The composition and homogeneous distribution of NiFeCoSex/CFC nanoparticles are determined by XRD, XPS, SEM elemental mapping and EDX images. Furthermore, SEM images reveal that NiFeCoSex/CFC has volcano-shaped morphology with rough surface and homogenously distributed on the surface of CFC, which may provide more active sites for OER. The electrochemical measurements show that trimetallic NiFeCoSex/CFC possesses the better electrocatalytic activity with the lower overpotential (150 mV at 10 mA cm?2), Tafel slope (85 mV dec?1), larger double-layer capacitance (200 mF cm?2) and long-term stability than unary or binary metal selenides. The enhanced activity of NiFeCoSex/CFC may be attributed to the trimetallic NiFeCo selenides and selenides-CFC synergistic interaction. It may offer a promising way to design transition multimetallic selenides supported on conductive support as electrocatalysts for OER.  相似文献   

17.
Efficient non-noble metal catalysts for the oxygen evolution reaction (OER) are particularly important in the practical applications of electrocatalytic water splitting (ECWS). Herein, based on a simple quasi chemical vapor deposition (Q-CVD) method, we fabricate a newly Ni3S2@3-D graphene free-standing electrode for efficient OER applications. The Ni3S2@3-D graphene integrates the advantageous features of 3-D graphene and Ni3S2 towards OER, such as more interfacial catalytic sites, pore-rich structure, N-doped structure and good electrical conductivity. Benefiting from the favorable features, the Ni3S2@3-D graphene (especially 900 °C sample) exhibits excellent OER performances in alkaline medium, which includes a low on-set potential (1.53 V), low overpotential of 305 mV at a current density of 10 mA cm−2, and a smaller Tafel slope (50 mV dec−1). This catalyst also shows ultrahigh stability after chronoamperometry response at 10 mA cm−2 for 48 h with 30% increase in the current density. The present work opens a new approach for the one-pot construction of hybrid materials between metal sulfide and graphene to increase the electrocatalytic activity of non-noble metal OER catalysts.  相似文献   

18.
The oxygen evolution reaction (OER) has been acknowledged as a bottleneck in electrocatalytic water splitting due to its sluggish kinetic, so it is eager to search for non-precious metal catalysts with high activity and stability. Herein, we demonstrate a facile strategy to obtain a nickel-iron-aerogels and graphene oxide composite, grown on nickel foam (NiFe@GO/NF) via a mild sol-gel method. The aerogels with the three-dimensional cross-linked networks are successfully anchored to graphene oxide (GO) nanosheets, which greatly increases the specific surface area of aerogels (242.4 m2 g?1) and effectively avoids the agglomeration of the cross-linked networks. Benefited from the special composite morphology and the synergistic effect of NiFe-bimetal and GO, the NiFe@GO/NF driving a 10 mA cm?2 only requires a low overpotential of 233 mV in 1 M KOH. Surprisingly, the NiFe@GO/NF shows considerable OER performance in industrial operating environments (6 M KOH and 50 °C). Thus, the NiFe@GO/NF could be a very promising electrocatalyst for water oxidation.  相似文献   

19.
Driving oxygen evolution reaction (OER) at extremely low overpotential and the blockage of oxygen gas inside the catalytic material leads to the deactivation of catalytic activity, therefore it is an essential step in electrochemical energy conversion systems, but still very challenging task. The clay minerals including bentonite and kaolinite are rich with plenty of active centers and favorable chemical composition for the catalysis applications but limited by the insulating properties, thus they cannot be used as an electrode material for the water splitting. The unique presence of clay minerals in the form of pencil graphite rod (PGR) and its attractive architecture enabled us to exploit advantageous features and use them as an in situ electrode for growth of metal oxide nanostructures for the electrolysis applications. The naturally inherent presence of SiO2 favors the catalytic properties and durability of the electrode whereas the MgO produces the abundant oxygen vacancies and Co3+ ions for OER process. Herein, we present a facile approach of using PGR as host substrate and co-catalyst for the loading of Co3O4, NiCo2O4 and NiO nanostructures and the modified electrode carried high porosity for easily bubbling of oxygen gas, plenty of intrinsic active centers coming from both clay minerals and metal oxides for excellent OER process. The fabricated electrode is physically well-characterized, and it has a natural ability to sustain a long term stability even at higher current densities and industrial electrolyzer conditions. The NiCo2O4/PGR, Co3O4/PGR, and NiO/PGR electrodes exhibit an overpotential of 234, 242 and 272 mV respectively at a current density of 100 mAcm?2 in 1.0 M KOH electrolytic solution. The presence of large number of oxygen vacancies through SiO2 and MgO, high Ni2+/Ni3+ and Co3+/Co2+ ratios, multi metal centers, large specific surface area, high pore volume, high electrochemical active surface area and fast charge transport within the NiCo2O4/PGR are the main reasons for its superfast OER kinetics. Thus, the proposed method of electrode design will pave a potential way for high performance electrochemical devices like metal air batteries, fuel cell and supercapacitors.  相似文献   

20.
The efficiency and stability of electrocatalysts are the key factors for measuring oxygen evolution reaction. In this work, the MnCo2O4 structure assembled from well-arranged nanowires or nanosheet arrays has been grown vertically on nickel foam by in-situ hydrothermal method. Interestingly, different morphology of MnCo2O4 can be easily regulated by adding NH4F to a mixed solvent to achieve conversion from nanowires to nanosheets. In addition, further synthesis of unique three-dimensional hierarchical core/shell MnCo2O4@CoS nanowires or nanosheets arrays was performed primarily by electrochemical deposition. Both MnCo2O4@CoS-7 cycles nanowires and MnCo2O4@CoS-7 cycles nanosheets exhibit high efficiency and long-lasting stability for the oxygen oxidation reaction. The lower overpotential of only 280 mV and 270 mV at 20 mA cm−2 for the MnCo2O4@CoS-7 cycles nanowires and MnCo2O4@CoS-7 cycles nanosheets were obtained with lower Tafel slopes of 139. 19 mV dec−1 and 131.81 mV dec−1 in 1.0 M potassium hydroxide respectively comparing with our other MnCo2O4@CoS catalysts. The results demonstrate that the crystal morphology of MnCo2O4@CoS does not significantly influence their electrocatalytic activity in water oxidation reactions by comparing nanostructured MnCo2O4@CoS nanowires and MnCo2O4@CoS nanosheets. The high catalytic activity of the MnCo2O4@CoS nanoarrays is attributed to the possession of more active sites, larger specific surface area, abundant oxygen vacancy, and fast electron transport rate. Not only that, the durability of the MnCo2O4@CoS nanoarrays is also excellent after continuous oxygen evolution test of 1000 cycles. The results of XRD, SEM and XPS show that MnCo2O4@CoS-7 cycles nanowires and MnCo2O4@CoS-7 cycles nanosheets materials can be used as a highly efficient and stable catalyst for oxygen evolution reaction.  相似文献   

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