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1.
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   

2.
The catalysts are often used in fuel cells and metal-air batteries to speed up electrochemical reactions. In this study, we prepared CoFe2O4 nanoparticles with mainly inverse spinel structure and FeCo2O4 nanoparticles with mainly spinel structure as bifunctional catalysts by hydrothermal method. After annealing at 350 °C, pure CoFe2O4 and FeCo2O4 nanoparticles with uniform size distribution have been obtained. The CoFe2O4 nanoparticles showed high current density of 5.5 mA/cm2 at −0.8 V in the ORR test. It's low Tafel slope of 83.0 mV/dec further confirmed the excellent ORR catalytic properties of CoFe2O4 nanoparticles. Furthermore, the CoFe2O4 nanoparticles also showed good OER properties with satisfied current density of 35.7 mV/cm2 at l.0 V and low OER Tafel slope of 71.0 mV/dec. Both the ORR and OER properties of CoFe2O4 nanoparticles showed good time stability which were compared with FeCo2O4 nanoparticles. These results indicated that CoFe2O4 nanoparticles with mainly inverse spinel structure had better electrocatalytic performance than FeCo2O4 nanoparticles with mainly spinel structure. The CoFe2O4 nanoparticles with mainly inverse spinel structure show a significant potential application in rechargeable battery.  相似文献   

3.
Energy-efficient production of hydrogen through urea electrolysis is still challenging due to the lack of satisfactory catalysts for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in urea containing solution. In this study, Ni–WxC/C (x = 1,2) composite with high activity for urea electrocatalysis was prepared by direct electro-reduction of affordable feedstock of NiO–CaWO4–C in molten CaCl2–NaCl at 873–973 K. The addition of graphite in precursor decreases the particle size of Ni. Introducing WxC into Ni particles can reduce the overpotential for UOR. As a result, the obtained Ni-WxC/graphite composite exhibits high current density for urea oxidation, which is about 11-folds and 52-folds higher than that of Ni/graphite and Ni (@1.53 V vs. RHE), respectively. After changing the carbon source from graphite to CNTs, the anodic current density was further increased by 43%, reaching 50.31 mA cm?2. Moreover, the cathodic catalyst WxC/CNTs obtained by the same preparation process exhibits high performance towards HER, with a low onset potential of 131.5 mV and a Tafel slope of 69.5 mV dec?1. Assembling an electrolyzer using Ni-WxC/CNTs as anode and WxC/CNTs as cathode can yield a current density of 10 mA cm?2 at merely 1.65 V in 1 M KOH/0.33 M urea aqueous solution, with excellent long-term electrochemical durability. The environmental-friendly production process uses affordable feedstocks for the synthesis of efficient catalysts toward urea electrolysis, promising an energy-saving hydrogen production as well as waste treatment.  相似文献   

4.
The urea solution electrolysis has become more attractive than water splitting, because it not only produces clean H2 via the cathodic hydrogen evolution reaction (HER) with lower cell voltage, but also treats sewage containing urea through anodic urea oxidation reaction (UOR). However, lack of efficient electrocatalysts for HER and UOR has limited its development. Herein, hairy sphere -like Ni9S8/CuS/Cu2O composites were synthesized on nickel foam (NF) in situ by a two-step hydrothermal method. The Ni9S8/CuS/Cu2O/NF exhibited good electrocatalytic activity for both HER (?0.146 V vs. RHE to achieve 10 mA cm?2) and UOR (1.357 V vs. RHE to achieve 10 mA cm?2). Based on the bifunctional properties of Ni9S8/CuS/Cu2O/NF, a dual-electrode urea solution electrolytic cell was constructed, which only needed a low voltage of 1.47 V to reach a current density of 10 mA cm?2, and displayed a good stability during a 20-h test. In addition, the reason for the good catalytic activity of Ni9S8/CuS/Cu2O/NF was analyzed and the UOR mechanism was discussed in detail. Our research shows that Ni9S8/CuS/Cu2O/NF is a very promising low-cost dual-function electrocatalyst, which can be used for high-efficiency electrolysis of urea solution to produce hydrogen and treat wastewater.  相似文献   

5.
In recent time direct urea fuel cell (DUFC) emerges as a potential candidate for sustainable urea reach wastewater treatment and power generation. The efficiency of DUFC mainly governed by the anodic urea oxidation reaction (UOR) kinetics. The design and development of efficient electrocatlysts for UOR remains a key factor for practical utilization of DUFC. In current study, we present a single step hydrothermal synthesis of NiWO4 NPs/rGO (h-NiWO4 NPs/rGO) composite for UOR catalysis in alkaline medium. The synthesized NiWO4 NPs/rGO composite offers a 218 mA/cm2 UOR catalytic current density. Moreover, the h-NiWO4 NPs/rGO composite retains its 94% UOR catalytic current after 1000 cyclic voltammetric cycles. Further, h-NiWO4 NPs/rGO composite shows superior UOR catalytic performance than physical mixture of NiWO4 NPs and rGO, NiWO4 NPs, NiO/WO3 physical mixture and only NiO with reference to catalytic current density, onset potential, and durability. The enhanced electrocatalytic activity of the h-NiWO4 NPs/rGO composite attributed to the synergetic coupling of physiochemical properties of NiWO4 NPs and rGO which improves the charge transfer generates larger electroactive surface and reduces catalyst poisoning. An air cathode DUFC with h-NiWO4 NPs/rGO composite modified anode and Pt/C cathode produces a maximum power density of 5.1 mW/cm2 and 927 mV open circuit potential.  相似文献   

6.
Water electrolysis for producing hydrogen is considered to be the most feasible means to develop new green energy. Compared with above, urea electrolysis can improve energy conversion efficiency by introducing urea, and can also be used for purification of wastewater rich in urea. In this paper, a bifunctional electrocatalyst with heterostructure, namely Fe7Se8@Fe2O3 nanosheets supported on nickel foam, were synthesized for the first time through typical hydrothermal and partial oxidation processes. Iron cation promotes electron transfer and adjusts electron structure under the synergistic action of selenium and oxygen anion, thus achieving excellent catalytic activity of urea electrolysis. In an alkaline solution of 1 M KOH with 0.5 M urea, the Fe7Se8@Fe2O3/NF catalyst can drive the current density of 10 mA cm?2 with requiring only potential of 1.313 V and overpotential of 141 mV for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), respectively. What is noteworthy is that Fe7Se8@Fe2O3/NF heterostructure is used as bifunctional electrocatalyst to form urea electrolyzer device, which only needs potential of 1.55 V to drive current density of 10 mA cm?2, which is one of the best catalytic activities reported so far, and the electrode couple showed remarkable stability for 15 h. Density functional theory shows that the Fe7Se8@Fe2O3/NF material exhibits the minimum Gibbs free energy for the adsorption of hydrogen. This work provides a new method for exploring novel and environmentally friendly bifunctional electrocatalysts for urea electrolysis.  相似文献   

7.
The anode oxygen evolution reaction (OER) is a delayed half-reaction of water splitting that requires a relatively high overpotential. Therefore, a more easily oxidized urea oxidation reaction (UOR) has been implemented to replace OER. Co–Mo-based bimetallic oxides have been recognized as interesting candidates for electrocatalytic water splitting due to their unique d electron configurations, but the low conductivity and limited active sites still hinder their development. Herein, we demonstrated that anion-modulation in CoMoO4 nanoplates as coupled hydrogen evolution reaction (HER) and UOR for convenient and efficient urea-assisted hydrogen-production system are demonstrated. The findings of the experiments show that nitrogen doping and phosphorus doping exhibit excellent activity toward alkaline HER and UOR, respectively. As a result, the N–CoMoO4 and P–CoMoO4 electrode exhibit low potentials of ?0.062 V and 1.251 V (vs. RHE) to reach a current of 10 mA cm?2 for HER and UOR. The full urea electrolysis is driven by N–CoMoO4||P–CoMoO4 executes stably for 24 h at a low potential of 1.41 V. This is a unique anion-modulation method in electrocatalysts to combine hydrogen generation and sewage treatment, which could pave the way for the creation of long-term energy conversion systems.  相似文献   

8.
With high energy density and low theoretical potential, the methanol oxidation (MOR) and urea oxidation (UOR) are often used as substitute reactions to the oxygen evolution reaction (OER). As one of the popular non-precious metal catalysts for the MOR/UOR research in recent years, nickel-based layered double hydroxides (LDHs) have abundant active sites and low cost, but suffer from poor catalytic activity and poor stability. In the present study, we prepared NiAl LDH and then grew NiSe2 in situ on its surface at different temperatures, and the catalyst obtained at 450 °C (4NiAlSe-450) exhibited excellent MOR/UOR electrocatalytic performance with potentials of 1.37 V vs. RHE and 1.36 V vs. RHE at a current density of 10 mA cm−2, respectively, which were much higher than those of NiAl LDH (1.42 V vs. RHE and 1.39 vs. RHE). Chronoamperometry curves of 4NiAlSe-450 at 1.5 V potential showed that the methanol/urea oxidation was stable for more than 3 h. The physicochemical properties of 4NiAlSe-450 were analyzed by using X-ray diffraction, X-ray photoelectron spectroscopy and other techniques, and the results showed that the NiSe2 nanoparticles were successfully grown in situ on the calcined layered structure, and therefore the excellent MOR/UOR electrocatalytic performance of 4NiAlSe-450 may be due to the synergistic effect between the NiAl composite oxides and NiSe2.  相似文献   

9.
Designing and optimizing structure is an effective method to enhance electrocatalytic performance of transition metal-based catalysts. In this work, an innovative nanostructured electrode, consisted of peapod-like Ni2P@N-doped carbon nanorods array coating on carbon fiber (CF@p-Ni2P@NC), is devised and synthesized. The N-doped carbon layer is crucial for maintaining the peapod-like nanostructure, which allows for multi-channel electrolyte transport and gas product release. And the carbon layer coating Ni2P nanoparticles also enhance electrical conductivity and stability, thus ensuring fast electron transport from/to active sites and the long-term stability of catalyst during urea oxidation reaction (UOR)/hydrogen evolution reaction (HER). Benefit from the reasonable structure, CF@p-Ni2P@NC present perfect performance with getting 100 mA cm?2 at potential/overpotential of 1.417/0.194 V for UOR/HER in 1.0 M KOH containing 0.5 M urea. In addition, the overall urea-electrolysis system using CF@p-Ni2P@NC bifunctional electrode only requires 1.590 V to obtain 100 mA cm?2.  相似文献   

10.
Electrodeposition provides a simple but effective way to prepare advanced electrode for the application in electrochemical field. In this work, NiMoSe ternary nanospheres were deposited on nickel foam (NiMoSe/NF) by one-step electrodeposition. The morphology, phase and chemical composition of the electrode was characterized by using SEM, TEM, XRD and XPS. The electrode exhibited excellent performance for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). It only required 1.39 V and 81 mV (vs. RHE) to deliver a current density of 10 mA/cm2 for UOR and HER, respectively. The electrolyzer constructed with NiMoSe/NF as both anode and cathode could deliver a current density of 10 mA/cm2 at a driving potential of 1.44 V. The stability test showed that the electrode had good durability as electrode for both UOR and HER. Considering the easiness, simplicity and low cost, the NiMoSe/NF electrode could find wide application in urea electrolysis.  相似文献   

11.
Macaroon-like FeCo2O4 nanomaterial was prepared and used as electrocatalyst in direct glucose alkaline fuel cell (DGAFC), which exhibited high catalytic activity towards glucose oxidation reaction. Maximum power density of 35.91 W m−2 was achieved in the DGAFC equipped with a FeCo2O4 modified activated carbon (AC) anode, which was almost 151% higher than the control. Physical and electrochemical characterizations were performed to provide further understanding of the origin of its high activity. Our results show that the introduction of FeCo2O4 into the AC anode remarkably increase the exchange current density and reduce the charge transfer resistance. It is supposed that there is a synergistic effect between Fe (III) and Co (III), which accelerates electron transfer from glucose to external circuits. This study will promote the development of cost effective and environmentally benign catalysts for electrochemical energy applications.  相似文献   

12.
Defect and interface engineering has been established as efficient methods for altering the electrical structure and improving the activity of electrocatalysts. Here, a rational design architecture consisting of Ni2P nanoparticles embedded in P-doped carbonized wood fibers (Ni2P/PCWF) is synthesized by simultaneous carbonization and phosphorization. A synergistic enhancement effect between electronic structure manipulation and interface regulation is observed in Ni2P/PCWF during the urea oxidation reaction (UOR). First, the P doping of carbon can optimize the electronic structure of Ni2P/PCWF. Second, the charge transport process is aided by the Ni2P nanoparticles embedded in the PCWF. Lastly, electron transfer can be accelerated by the in-situ formed heterogeneous interface between metal phosphides and metal hydroxides (hydroxyl oxides). Due to the synergy of the structural and electrical modulation, Ni2P/PCWF exhibits remarkable electrocatalytic properties toward the UOR under alkaline conditions. It only requires 1.34 V (vs. RHE) to achieve a current density of 50 mA cm?2, and the increase in potential at 10 mA cm?2 for 70 h is insignificant (≈2.9%). This work supports the development of new strategies using sustainable, renewable wood fibers to develop excellent UOR catalysts for energy-saving H2 generation.  相似文献   

13.
Hydrogen evolution reaction (HER) has been identified as a sustainable and environment friendly technology for a wide range of energy conversion and storage applications. The big barrier in realizing this green technology requires a highly efficient, earth-abundant, and low-cost electrocatalyst for HER. Various HER catalysts have been designed and reported, still, their performance is not up to the mark of Pt. Among them, cobalt-based, especially cobalt disulfide (CoS2) has shown significant HER activity and found suitable candidature for HER due to its low cost, simple to prepare, and exhibits good stability. Herein, we synthesized various nanostructured materials including pure CoS2, Co3O4 and their composites by wet chemical methods and found them active for HER. The scanning electron microscopy (SEM) has revealed a morphology of composite as a mixture of nanowires and round shape spherical nanoparticles with several microns in dimension. The X-ray diffraction (XRD) confirmed the cubic phase of CoS2 and cubic phase of Co3O4 in the composite materials. The chemical deposition of CoS2 onto Co3O4 has tailored the HER activity of CoS2@Co3O4 composite material. Two CoS2@Co3O4 composite materials were produced with varying amounts of Co3O4 and labeled as samples 1 and 2. The Co3O4 reduced the adsorption energy for hydrogen, decreased the aggregation of CoS2 and uplifted the stability of CoS2@Co3O4 a composite material in alkaline media. Sample 1 requires an overpotential of 320 mV to reach a current density of 10 mA/cm2 and it exhibits a Tafel slope of 42 mVdec−1which is the key indicator for the fast HER kinetics on sample 1. The sample 1 is highly durable for 50 h and also it has excellent stability. The electrochemical impedance spectroscopy (EIS) revealed a small charge transfer resistance of 28.81 Ohms for the sample 1 with high capacitance double-layer value of 0.81 mF. EIS has supported polarization and Tafel slope results. Based on the partial physical characterization and the electrochemical results, the as-obtained sample 1 (CoS2@Co3O4 composite material) will find potential applications in an extended range of energy conversion and storage devices owing to its low cost, high abundance, and excellent efficiency.  相似文献   

14.
Metal oxides as inexpensive and stable materials in electrochemical processes have been noticed by researchers. In this work, we synthesized a nanocatalyst based on nickel oxide and manganese oxide in the form of binary transition metal oxides (BTMOs), as well as a hybrid of this nanocatalyst with multi-walled carbon nanotubes (MWCNTs) by hydrothermal method. The efficiency of this nanocatalyst was checked for methanol oxidation reaction (MOR). After confirming the successful synthesis of the proposed nanocatalysts with detailed physical characterization and then performing cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrical impedance spectroscopy (EIS) tests, both MnNi2O4 and MnNi2O4- MWCNTs nanocatalysts showed relatively good capabilities in the MOR process. The results showed that adding MWCNTs to the nanocatalyst structure, in addition to increasing electrical conductivity, also increases the active surface of the nanocatalyst. Thus MnNi2O4- MWCNTs nanocatalyst with an exchange current of 3.74 × 10−5 mA/cm2 and 98% cyclic stability compared to MnNi2O4 with an exchange current of 8.61 × 10−8 mA/cm2 and 91% cycle stability, is more efficient in the MOR process. Synthesized nanocatalysts can be cheap, stable, and attractive options for MOR.  相似文献   

15.
Developing highly efficient bifunctional urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) catalysts for urea splitting to hydrogen are one of the strategies to cope with the energy crisis. Here, a series of CrxPy-a/ComPn-b composites were synthesized on Ni foam through hydrothermal and low-temperature phosphorization process for the first time. It is worth noting that CrxPy-1/ComPn-3@NF exhibited excellent UOR performance (1.331 V at 100 mA cm?2) and HER performance (0.299 V at 100 mA cm?2) in an electrolyte of 1 M KOH and 0.5 M urea due to the synergistic effect of Cr–Co. The CrxPy-1/ComPn-3@NF||CrxPy-1/ComPn-3@NF two-electrode system call for only 1.52 V to provide current density of 10 mA cm?2, which is one of the best electrochemistry performances reported up to now. Experimental analysis show that the promoted electrochemistry performances is assigned to faster charge transfer rate, the exposure of more reaction site and better properties of metals. Density Functional theory (DFT) results demonstrate that the presence of the ComPn material accelerates the kinetics of hydrogen production and the CrxPy material improves the properties of metals for the electrode. The work provides a new idea to develop the environmentally friendly and low cost overall urea splitting catalyst with transition metals instead of noble metals.  相似文献   

16.
Electrochemical hydrogen production from water splitting is one of the effective methods for hydrogen production that has recently attracted particular attention. One of the limitations of the electrochemical water splitting method is the slow oxygen evolution reaction (OER), which leads to an increase in overpotential and a decrease in hydrogen production efficiency. Here, Ni–Mo–S ultra-thin nanosheets were synthesized using the pulse reverse electrochemical deposition technique, and then this electrode was used as an electrode material for accelerating hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). Remarkably, the optimized electrode needs only 74 mV to attain the 10 mA cm−2 current density in HER and require only 1.3 V vs RHE potential in the UOR process. Also, results showed that the replacement of the UOR with the OER process resulted in a significant improvement in the electrochemical production of hydrogen in which for delivering the current density of 10 mA cm−2 in overall urea electrolysis, only 1.384 V is needed. In addition, outstanding catalytic stability was obtained, after 50 h electrolysis, the voltage variation was negligible. Such outstanding catalytic activity and stability was due to 3-D ultrathin nanosheets, the synergistic effect between elements, and the superhydrophilic/superaerophobic nature of fabricated electrode.  相似文献   

17.
Replacing dynamics-restricted oxygen evolution reaction (OER) with smart urea oxidation reaction (UOR) is very important for reducing the power consumption for hydrogen production. Here, the Co3Mo3N-400/NF is prepared using a facial way, which exhibits remarkable catalytic performances for UOR, hydrogen evolution reaction (HER) and overall urea electrolysis (OUE) because of the more exposed active sites and high electrical conductivity. At 100 mA/cm2, the Co3Mo3N-400/NF shows a small potential of 1.356 V vs. RHE (reversible hydrogen electrode) for UOR, which is much lower than that for OER. Furthermore, for HER, to reach to 100 mA/cm2, a low overpotential of 299 mV is required, and the urea has negligible influence on the HER process. For OUE, the Co3Mo3N-400/NF||Co3Mo3N-400/NF shows a small cell potential of 1.481 V at 100 mA/cm2 along with a good durability. Our work provides more choice for future OUE to generate hydrogen.  相似文献   

18.
In targeting the most important energy and environmental issues in current society, the development of low-cost, bifunctional electrocatalysts for urea-assisted electrocatalytic hydrogen (H2) production is an urgent and challenging task. In this work, interlaced rosette-like MoS2/Ni3S2/NiFe-layered double hydroxide/nickel foam (LDH/NF) is successfully synthesized by a two-step hydrothermal reaction. Due to its unique interlaced heterostructure, MoS2/Ni3S2/NiFe-LDH/NF exhibits excellent bifunctional catalytic activity towards the urea oxidation reaction (UOR) and the hydrogen evolution reaction (HER) in 1.0 M KOH with 0.5 M urea. In a concurrent two-electrode electrolyser (MoS2/Ni3S2/NiFe-LDH/NF(+,-)), only voltage of 1.343 V is required to reach 50 mA cm−2, which is 216 mV lower than for pure water splitting. Furthermore, after 16 h of urea electrolysis in 1.0 M KOH with 0.5 M urea, the current density remains at 98% of the original value. Thus, the catalyst is not only favorable for H2 production, but also has great significance for the problem of urea-rich wastewater treatment.  相似文献   

19.
In this study, nickel cobalt oxide (NiCo2O4) microspheres were prepared by using facile hydrothermal route. The structural confirmation of bimetal oxide formation was acquired by X-ray powder diffraction and Raman studies. The formation of microspheres combined via irregular nanosheets was confirmed by scanning electron microscopy. Highly oriented NiCo2O4 microspheres yielded a high current density (258 mA/g) at 10 mV/s and low overpotential (224 V). The highly active electrode showed efficient electron transportation towards oxygen evolution reaction. Long-term stability over 16 h was achieved by the fabricated high-performance NiCo2O4 electrode. It is recommended that NiCo2O4 microspheres obtained from 3:1 stoichiometry ratio of Ni and Co would lead to new electrocatalysts that give best performance than expensive catalysts used currently in the water oxidation process.  相似文献   

20.
The development of high-performance, low-cost, and non-noble metal catalysts for the urea oxidation reaction (UOR) as an alternative to oxygen evolution reaction (OER) has received much attention but remains a huge challenge. In this work, NiSe2/TiN@Ni12P5/NF catalysts with a stalactite structure were prepared by chemical vapor deposition to obtain the integrated electrode Ni12P5/NF on the nickel foam (NF), and subsequently NiSe2/TiN was formed on the Ni12P5/NF surface by the hydrothermal method. The designed catalyst delivers an ultra-low potential of 1.270 V at 10 mA cm?2, and a Tafel slope of 33.3 mV dec?1 for UOR. Furthermore, the catalyst only shows a 1.7% decrease in potential after an 80-h stability test, which demonstrates its excellent stability. The prepared NiSe2/TiN@Ni12P5/NF shows a high specific surface area, and the strengthening effect between TiN and NiSe2, endowing the catalyst a high activity and durability.  相似文献   

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