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1.
In this work, a melt-spun amorphous Fe73.5Si13.5B9Cu1Nb3 alloy is subjected to high-pressure torsion (HPT) treatment under 6 GPa in order to enhance the alkaline hydrogen evolution reaction (HER) performance. Different HPT turns, including 1, 2, 5 and 10, are selected and the samples are marked as HPT-1N, HPT-2N, HPT-5N and HPT-10 N, respectively. The HPT treatment can lead to a significant structural change such as partial crystallization and defect generation on the Fe-based amorphous alloy with a considerable increase in the HER electrocatalytic activity. The HPT-5N sample shows the best catalytic performance, with an overpotential of only 174 mV at 10 mA cm?2 current density in 1 M KOH, which is 244 mV lower than that of the melt-spun alloy at the same condition. Moreover, it was established that the HPT-treated amorphous alloy shows good stability during the HER cycling process.  相似文献   

2.
Using cost-effective materials to replace precious Pt-based hydrogen evolution reaction (HER) catalysts holds great foreground for energy saving and environmental protection. In this work, we successfully prepared an urchin-like Co0.8-Mn0.2-P nanowires array supported on carbon cloth (CC) through a hydrothermal-phosphatization strategy and we also systematically studied its electrocatalytic HER performance. Electrochemical tests demonstrate that our urchin-like Co0.8-Mn0.2-P/CC possesses outstanding HER activity in acidic and alkaline media. In 0.5 M H2SO4, this urchin-like Co0.8-Mn0.2-P/CC only requires an overpotential of 55 mV to drive a current density of 10 mA cm−2, with the Tafel slope of 55.9 mV dec−1. Similarly, when reaching the same current density, just a particularly low overpotential of 61 mV is required with a corresponding Tafel slope of 41.7 mV dec−1 in 1 M KOH. Furthermore, this electrocatalyst exhibits superior stability with 1000 cycles of cyclic voltammetry and 24 h in the I-T test. Such excellent HER catalytic performance can be attributed to the synergistic effect between Co and Mn atoms and high electrochemical active surface area (ECSA). Our work provides a valuable synthesis strategy of non-precious and high HER performance catalytic material.  相似文献   

3.
Using low-cost nonprecious metals to replace Pt as hydrogen evolution reaction (HER) electrocatalyst is promising, but still limited by their efficiency and stability. Herein, with low-cost dicyandiamide and metal salts as precursor, FeCo alloy nanoparticles encapsulated in nitrogenated carbon nanotubes (FeCo-NCNTs) were facially synthesized as efficient HER electrocatalyst. Addition of iron as second element, though not facilitating the formation of carbon nanotube, was utilized to improve the physicochemical properties of metals. Via optimizing the atomic molar ratios of Fe/Co nanoparticles, the optimal Fe0.4Co0.6-NCNTs with thin carbon shell (c.a. 5–10 layer) and equally distribution of embedded alloy nanoparticles was found with outstanding HER activity. To achieve a current density of 10 mA cm−2, only overpotential of 50 mV, 157 mV and 202 mV were needed in acidic (0.5 M H2SO4), alkaline (1 M KOH), and neutral solutions. Its higher electrochemically active surface areas and lower electron transfer resistance may contribute to the excellent electrocatalytic HER. Furthermore, the illustrated current density slightly changed over 20 h, suggesting excellent stability. Hence, the present method provides cost-effective, high efficiency, and stable materials in developing the sustainable energy conversion systems.  相似文献   

4.
Developing an effective and low-cost bifunctional electrocatalyst for both OER and HER to achieve overall water splitting is remaining a challenge to meet the needs of sustainable development. Herein, an electroless plating method was employed to autogenous growth of ultrathin Ni–Fe2B nanosheet arrays on nickel foam (NF), in which the whole liquid phase reduction reaction took no more than 20 min and did not require any other treatments such as calcination. In 1.0 M KOH electrolyte, the resulted Ni–Fe2B ultrathin nanosheet displayed a low overpotential of 250 mV for OER and 115 mV for HER to deliver a current density of 10 mA cm?2, and both OER and HER activities remained stable after 26 h stability testing. Further, the couple electrodes composed of Ni–Fe2B could afford a current density of 10 mA cm?2 towards overall water splitting at a cell voltage of 1.64 V in 1.0 M KOH and along with excellent stability for 26 h. The outstanding electrocatalytic activities can be attributed to the synergistic effect of electron-coupling across Ni and Fe atoms and active sites exposed by large surface area. The effective combination of low cost and high electrocatalytic activity brings about a promising prospect for Ni–Fe2B nanosheet arrays in the field of overall water splitting.  相似文献   

5.
Recent development on two-dimensional (2D) heterostructured graphene and MXene materials were explored for electrochemical water splitting hydrogen evolution reaction (HER) activity. The hybrid MXene/reduced graphene oxides as two-dimensional (2D) hybrid structures were prepared by facile hydrothermal techniques at 150 °C with MXene and RG hybrid layered composites. As-prepared electrocatalytic active materials have been confirmed through structural and surface morphological studies such as XRD, RAMAN, FT-IR and SEM analysis. The prepared 2D materials were carried out for HER activities due to attractive conductivity and mass transfer process. HER performance were tested from linear sweep voltammetry (LSV) cures. The prepared MX, RG and MX@RG hybrid electrocatalyst exhibited overpotential values as observed as 220 mV, 193 mV, 121 mV respectively at 10 mAcm?2 cathodic on set. MX@RG hybrid heterostructure exhibited enhanced HER action with lowest overpotential (η = 121 mV) and good H2 productions as an active future electrocatalyst for energy storage and conversion applications.  相似文献   

6.
Ternary Fe-Mo-R (R = Rare Earth metal) crystalline alloys, Fe75Mo20Gd5, Fe75Mo20Dy5, Fe75Mo20Er5 and Fe75Mo20MM5 (MM = mischmetal: 50.2% Ce, 26.3% La, 17.5% Nd, 6.0% Pr, atomic %) have been characterized by means of microstructural and electrochemical techniques in view of their possible applications as electrocatalytic materials for hydrogen evolution reaction (HER). The microstructure of the alloys was examined by scanning electron microscopy coupled with electron probe microanalysis; XRD measurements were also performed. The electrochemical efficiency of the electrodes has been studied on the basis of electrochemical data obtained from steady-state polarization and electrochemical impedance spectroscopy (EIS) techniques in 1 M NaOH solution at 298 K. The results were compared with those obtained on a binary Fe-Mo commercial alloy (Fe80Mo20, atomic %). Moreover, literature data concerning the electrocatalytic activity of the Ni75Mo25 and Co75Mo25 crystalline alloys, which are considered good electrocatalyst materials for the HER, were also reported for comparison. The microstructural features play a fundamental role in determining the electrocatalytic activity of the investigated alloys. The overall experimental data indicate that interesting electrocatalytic performances are displayed by the Fe75Mo20MM5 electrode, which exhibits the highest activity towards the HER.  相似文献   

7.
The development of highly active and low-cost catalysts for hydrogen evolution reaction (HER) is significant for the development of clean and renewable energy research. Owing to the low H adsorption free energy, molybdenum disulfide (MoS2) is regarded as a promising candidate for HER, but it shows low activity for oxygen evolution reaction (OER). Herein, graphene-supported cobalt-doped ultrathin molybdenum disulfide (Co–MoS2/rGO) was synthesized via a one-pot hydrothermal method. The obtained hybrids modified electrode exhibits a high HER catalytic activity with a low overpotential of 147 mV at the current density of 10 mA cm−2, a small Tafel slope of 49.5 mV dec−1, as well as good electrochemical stability in acidic electrolyte. Meanwhile, the catalyst shows remarkable OER activity with a low overpotential of 347 mV at 10 mA cm−2. The superior activity is ascribed not only to the high conductivity originated from the reduced graphene, but also to the synergistic effect between MoS2 and cobalt.  相似文献   

8.
The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N2 adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm−2 and a low Tafel slope of 45 mV dec−1. In OER, the optimized sample performs better than a state-of-the-art RuO2 catalyst and produces an overpotential of 337 mV at 10 mA cm−2, lower than that of RuO2. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in overall water splitting.  相似文献   

9.
Binary Co–W crystalline alloys, Co95W5, Co90W10, Co85W15, Co80W20 and Co70W30 (atomic %) were investigated in view of their possible applications as electrocatalytic materials for hydrogen evolution reaction (HER). The electrocatalytic efficiency of the electrodes was studied on the basis of electrochemical data obtained from steady-state polarization and electrochemical impedance spectroscopy (EIS) techniques in oxygen-free 1 M NaOH solution at 298 K. The results were compared with those obtained on polycrystalline Co. Moreover, literature data concerning the electrocatalytic activity of polycrystalline Ni and Ni–Mo alloys, which are considered good electrocatalyst materials for the hydrogen evolution reaction in alkaline solutions, were also reported for comparison. The values of Tafel slope, b, exchange current density, j0, and overpotential at the current density of 250 mA cm−2, η250, indicated outstandingly high electrocatalytic activity of Co–W electrodes. The best performance towards the HER demonstrates the Co90W10 alloy in accordance with the prediction based on the electronic structure calculations and the enhanced density of states at the Fermi level of the 3d Co band.  相似文献   

10.
In realm of renewable energy, development of an efficient and durable electrocatalyst for H2 production through electrochemical hydrogen evolution reaction (HER) is indispensable. Herein, we demonstrate a simple preparation of carbon-supported nanoporous Pd with surface coated Pt (CS–PdPt) by a simple galvanic replacement reaction (GRR). The phase purity and porosity have been confirmed by XRD, HRTEM, and N2 sorption techniques. As HER electrocatalyst, CS-PdPt showed a low overpotential of 26 mV in 0.5 M H2SO4 at current density of 10 mA cm−2, which is lower than the commercial Pt/C electrode. The CS-PdPt catalyst exhibits an overpotential of 46 mV in 1 M KOH, and 50 mV in neutral buffer (1 M PBS) at 10 mA cm−2. The CS-PdPt furnished with small Tafel values of 33, 88, and 107 mV dec−1 in acidic, alkaline, and neutral medium, respectively. Accelerated durability test at 100 mV s−1 for 1000 cycles demonstrated a negligible change in HER activity.  相似文献   

11.
Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (FexNi1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe0.2Ni0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe0.2Ni0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm−2 at a voltage of only 1.62 V. Further, the Fe0.2Ni0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.  相似文献   

12.
Hydrogen is considered as a viable alternative to traditional fossil fuels. Hydrogen evolution reaction (HER) by electrochemical water splitting is the most reliable and effective way for the sustainable production of pure hydrogen. The design and synthesis of highly active and stable non-noble-metal-based electrocatalysts is the core of the large-scale application of this technology. Herein, peony petal-like CoMnP/NF nanomaterials growing on nickel foam (NF) are prepared via facile hydrothermal and phosphorization methods. The results showed that CoMnP/NF had excellent HER activity in acidic and alkaline media. In 0.5 M H2SO4, CoMnP/NF only needed 66.6 mV overpotential to drive the current density of 10 mA cm?2, with a Tafel slope of 38.8 mV dec?1. In addition, a particularly low overpotential of 53.9 mV and Tafel slope of 63 mV dec?1 are required to achieve the same current density in the 1 M KOH electrolyte. Meanwhile, the electrocatalyst showed good stability after 1000 cyclic voltammetry tests and 12 h I-T tests. In the 1 M KOH electrolyte, the current density of 10 mA cm?2 achieved with only 1.70 V battery voltage, and the electrocatalyst showed excellent stability. The performance of CoMnP/NF can be attributed to the synergistic effect between Co and Mn atoms and the high electrochemical surface area (ECSA). This study provides a valuable strategy for the synthesis of non-precious metals and high-performance catalytic materials.  相似文献   

13.
High-efficiency and economical electrocatalysts for electrochemical water splitting are the core component of the renewable energy conversion. Herein, a simple and economical strategy is described to synthesize a series of metal oxide decorated nitrogen-doped carbon nanotubes materials (N-CNT@Cu–Fe Oxide Alloy NPs) by utilizing carbon nanotubes as the substrate carrier material. Additionally, the polypyrrole (PPy) was served as both the nitrogen resource and the localizing agent to load the Cu–Fe oxide alloy. Moreover, the theoretical and test results indicated that the superior HER and ORR performance is mainly related to the synergistic effect between the nitrogen-doped CNT and metallic oxide alloy. In the series of catalysts we prepared, N-CNT@Cu1–Fe1 Oxide Alloy NPs exhibits more significant catalytic activity and better durability than other catalysts that we synthesized. Meanwhile, the catalyst shows the low Tafel slope of 68.28 mV dec?1 for HER and reaches 10 mA cm?2 at the overpotential of 375 mV. The K–L plot shows that the electron transfer number of N–CNF@Cu1–Fe1 Alloy NPs is 3.43.  相似文献   

14.
Transition metal selenides are regarded as promising materials for the production of clean energy through electrocatalytic water splitting. Creation of defects in these metal selenides is one of the prudent strategies to enrich the active sites which in turn enhances the electrocatalytic activity of these materials and makes them viable for broader applications. Herein, defect-induced, iron-doped nickel selenide nanoparticles were prepared for the first time and their electrocatalytic efficacy towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been demonstrated. FexNi1-xSe2 nanoparticles (x = 0.25, 0.50, 0.75) were prepared using a facile hydrothermal method, in which defects were induced by annealing at 300 °C to obtain DI-FexNi1-xSe2. The structural and morphological investigations confirmed the size reduction and creation of defects after annealing, without any significant change in the crystal structure, which in turn is expected to promote the electrocatalytic activity. Accordingly, among all the materials investigated, DI-Fe0.25Ni0.75Se2 has shown the highest HER activity in 0.5 M H2SO4 at a lesser overpotential of 128 mV at 10 mA cm?2 and the Tafel slope was calculated to be 37.9 mV dec?1. Interestingly, the same material has displayed high performance towards OER in 1 M KOH with a lesser overpotential at 205 mV and a Tafel slope of 55.5 mV dec?1. Thus obtained electrocatalytic activity was much better than the reported nickel selenide based electrocatalysts. Further, the DI-Fe0.25Ni0.75Se2 electrocatalyst has demonstrated impressive stability in the acidic and alkaline medium during continuous electrolysis even up to 12 h.  相似文献   

15.
Carbon nanomaterials that are electrochemically bifunctional and active in supercapacitor and hydrogen-evolution-reaction (HER) applications have attracted recent research attention. We have prepared porous carbon spheres - doped Ni, Co - alloys by using a hydrothermal method with melamine and pectin as precursors and with the addition of nickel nitrate and cobalt nitrate. The corresponding materials exhibit good electrochemical performance and excellent electrocatalytic activity for HER. The overpotential (OP) of the as-prepared materials can achieve 240 mV keeping a Tafel slope (TS) of 55 mV dec−1 at 10 mA cm−2 in an acid (0.5 M H2SO4) solution. The corresponding samples maintain stability after 24 h and 5000 cycles in the chronovoltage and cyclic voltammetry methods, respectively. When the as-prepared materials are oxidized by 30% H2O2 for 12 h, the corresponding as-prepared oxidation samples exhibit excellent electrochemical performance in a supercapacitor application. The specific capacitance (SC) of the as-obtained materials reaches 312 F g−1 at 1 A g−1 with decent rate capability and cyclic stability. This work provides new applications for bifunctional electrochemically active materials.  相似文献   

16.
It is extremely necessary to develop highly efficient and low-cost non-noble metal electrocatalysts for hydrogen evolution reaction (HER) under a pH-universal condition in the realm of sustainable energy. Herein, we have successfully prepared phosphorus doped Fe3O4 nanoflowers on three-dimensional porous graphene (denoted as P–Fe3O4@3DG) via a simple hydrothermal and low-temperature phosphating reaction. The P–Fe3O4@3DG hybrid composite not only demonstrates superior performance for HER in 1.0 M KOH with low overpotential (123 mV at 10 mA/cm2), small Tafel slope (65 mV/dec), and outstanding durability exceeding 50 h, but also exhibits satisfying performances under neutral and acidic medium as well. The 3D graphene foam with large porosity, high conductivity, and robust skeleton conduces to more active sites, and faster electron and ion transportation. The phosphorus dopant provides low Gibbs free energy and ability of binging H+. The synergistic effect of 3DG substrate and P–Fe3O4 active material both accelerates the catalytic activity of Fe-based hybrid composite for HER.  相似文献   

17.
Binder-free NiFe-based electrocatalyst with aligned pore channels has been prepared by freeze casting and served as a bifunctional catalytic electrode for oxygen and hydrogen evolution reaction (OER and HER). The synergistic effects between Ni and Fe result in the high electrocatalytic performance of porous NiFe electrodes. In 1.0 M KOH, porous Ni7Fe3 attains 100 mA cm−2 at an overpotential of 388 mV with a Tafel slope of 35.8 mV dec−1 for OER, and porous Ni9Fe1 exhibits a low overpotential of 347 mV at 100 mA cm−2 with a Tafel slope of 121.0 mV dec−1 for HER. The Ni9Fe1//Ni9Fe1 requires a low cell voltage of 1.69 V to deliver 10 mA cm−2 current density for overall water splitting. The excellent durability at a high current density of porous NiFe electrodes has been confirmed during OER, HER and overall water splitting. The fine electrocatalytic performances of the porous NiFe-based electrodes owing to the three-dimensionally well-connected scaffolds, aligned pore channels, and bimetallic synergy, offering excellent charge/ion transfer efficiency and sizeable active surface area. Freeze casting can be applied to design and synthesize various three-dimensionally porous non-precious metal-based electrocatalysts with controllable multiphase for energy conversion and storage.  相似文献   

18.
Electrocatalytic hydrogen evolution reaction (HER) is one of the green and effective method to produce clean hydrogen energy. However, the development of non-Pt HER catalysts with excellent catalytic activity and long-term stability still remains a great challenge. Herein, a vertically aligned core-shell structure material with hollow polypyrrole (PPy) nanowire as a core and Ru-doped MoS2 (Ru–MoS2) nanosheets as a shell is firstly reported as a highly efficient and ultra-stable catalyst for HER in alkaline solutions. Results indicate that Ru–MoS2@PPy catalyst demands a low overpotential of 37 mV at 10 mA cm?2. In addition, the overpotential at 100 mA cm?2 is 157 mV and it is almost unchanged after 40,000 cyclic voltammetry cycles. The existence of PPy core not only ensures the vertical growth of MoS2 nanosheets to expose more edge sites, but also promotes the rapid transfer of electrons, contributing to the improvement of catalytic activity. More importantly, the strong interface interaction between MoS2 and PPy prevents the collapse of the vertical structure of MoS2 sheets in the electrocatalytic process and greatly enhances the stability of catalysts, which offers an effective strategy to design and synthesize the HER catalysts with superior catalytic stability.  相似文献   

19.
The new La8Fe28B24-, La15Fe77B8- and La17Fe76B7-type alloys have multiphase structures including LaNi5, La3Ni13B2 and (Fe, Ni) phases. The amount of La3Ni13B2 phase increased and that of (Fe, Ni) phase decreased with an increasing La/(Fe + B) atomic ratio. The measurement of P–C–I curves revealed that the maximum hydrogen capacity exceeded 1.12 wt% at 313 K in the pressure range of 10−3 MPa–2.0 MPa. The alloys exhibited good absorption/desorption kinetics at room temperature, and electrochemical experiments showed that all of the alloy electrodes exhibited good activation characteristics, high-rate dischargeability (HRD) and low-temperature (233 K) dischargeability (LTD).  相似文献   

20.
In this work, nitrogen doped carbon dots (NDCDs) and nitrogen doped carbon dots supported palladium nanoparticles composite (n-Pd@NDCDs) were synthesized through hydrothermal carbonization and thermolytic reduction using Morinda citrifolia (M. citrifolia) fruit and palladium chloride as carbon and Pd precursors, respectively. The synthesized materials viz., n-Pd@NDCDs and NDCDs were duly characterized by high resolution transmission electron microscopy (HR-TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). The optical properties of NDCDs were studied by ultraviolet visible (UV–Vis), and fluorescence spectroscopy techniques. Further, the electrocatalytic hydrogen evolution reaction (HER) performance of n-Pd@NDCDs was evaluated by linear sweep voltammetry (LSV), Tafel, and electrochemical impedance spectroscopy (EIS) measurements in 0.5 M aqueous H2SO4. The onset potential of n-Pd@NDCDs was about −0.195 VRHE, which was lower than NDCDS (−0.392 VRHE) and bare glassy carbon (−0.603 VRHE). The calculated Tafel slope values of n-Pd@NDCDs were 135 and 141.8 mV/dec, from the voltammetric and EIS methods, respectively. Moreover, the n-Pd@NDCDs exhibited small overpotential of 0.291 V to attain a current density of 10 mA/cm2. The EIS studies revealed that the HER charge transfer resistance was dropped from 84.3 to 18.3 Ω/cm2 while increasing of potential, which revealed good conductivity and electrocatalytic activity of n-Pd@NDCDs. Thus the present work vouched for the candidature of n-Pd@NDCDs as an effective electrocatalyst for the HER in acidic medium.  相似文献   

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