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1.
Low cost non-noble metal electrocatalysts are highly desirable for the sustainable production of hydrogen as a renewable energy source. Molybdenum carbide (Mo2C) has been considered as the promising non-noble metal electrocatalyst for the hydrogen production via hydrogen evolution reaction (HER) through water splitting. The nanostructured nitrogen (N) incorporated carbon (C) coupled with Mo2C is the potential candidate to boost the HER activity and electrode material for the energy conversion applications. In this work, nitrogen incorporated carbon coated Mo2C (Mo2C@C/N) has been synthesized in an eco-friendly way using waste plastic as the carbon source. The pure phase Mo2C@C/N has been synthesized at 700 and 800 °C for 10 h. The relatively higher temperature synthesized phase shows enhanced HER activity with lower Tafel slope (72.9 mVdec−1) and overpotential of 186.6 mV to drive current density of 10 mAcm−2. It also exhibits stability up to 2000 cyclic voltammetry (CV) cycles and retains the current density with negligible loss for 10 h. The higher temperature synthesized phase exhibits higher electrochemical active surface area (ECSA) and enhanced HER kinetics.  相似文献   

2.
Developing cost-effective and remarkable electrocatalysts toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performs excelling role in boosting the hydrogen energy application. Herein, a novel in-situ one-pot strategy is developed for the first time to synthesize molybdenum carbide nanoparticles (Mo2C NPs) incorporated on nitrogen (N) and phosphorous (P) co-doped stereotaxically carbon (SC). The optimized Mo2C NPs/N, P–SC–800 electrocatalyst exhibits lower overpotentials of 131 and 287 mV for HER and OER to deliver a current density of 10 mA cm?2 in 1.0 M KOH medium with smaller Tafel slopes of 58.9 and 74.4 mV/dec, respectively. In addition, an electrolyzer using Mo2C NPs/N, P–SC–800 electrode as cathode and anode delivers a current density of 10 mA cm?2 at a small voltage of 1.64 V for overall water splitting. The excellent water splitting performance could be ascribed to optimum Mo2C NPs for more accessible active sites, highly active N, P-SC networks for accelerated electron transfers, and synergetic effect between Mo2C NPs and N, P-SC networks. The N, P-SC network not only enhances the overall dispersion of Mo2C NPs but also contributes numerous electroactive edges to enhance the performance of HER, OER, and overall water splitting activity. This research work explores the in-situ one-step strategies of advanced, cost-effective, and non-precious metal electrocatalysts for efficient water splitting and motivates the consideration of a novel class of heteroatom doped stereotaxically carbon nanocomposites for sustainable energy production.  相似文献   

3.
Developing high performance, good stability and noble-metal-free electrocatalysts for renewable hydrogen evolution reaction (HER) remain a substantial challenge. Herein, we introduce a novel facile one-step in-situ strategy through pyrolysis for the synthesis of Co2P nanoparticles encapsulated Boron, Nitrogen, and Phosphorous tri-doped carbon nanotubes (Co2P/BNP-CNTs). The synergetic effect between Co2P nanoparticles and heteroatom doped CNTs contributes to the remarkable HER performance. The Co2P/BNP-CNT-900 electrocatalyst shows a low overpotential of 133 mV at a current density of 10 mA cm−2 and a small Tafel slope of 90 mV dec−1 in 0.1 M KOH media. More importantly, the Co2P/BNP-CNT-900 electrocatalyst exhibits superior long-term stability in alkaline solution at −0.25 V versus Reversible Hydrogen Electrode (RHE) for 15 h and up to 1000 cycles with negligible performance loss. Overall, our works suggest a one-pot facile synthesis strategy for rational designing high-performance electrocatalysts with enhanced HER performance.  相似文献   

4.
Designing porous active materials and enhancing their contact with conductive substrates is an effective strategy to improve electrolytic water splitting performance of noble metal-free catalysts. Herein, a facile nanostructured electrode, composed of porous Co2P films coated on carbon fiber (CF@P–Co2P), is designed and prepared. The unique three-dimensional interconnected pore structure of Co2P and the close contact between porous Co2P and CF not only increase specific surface areas to expose abundant catalytic sites but also stimulate the transport of electron, mass and gaseous products in catalytic process. Benefit from the reasonable electrode structure, the self-supported CF@P–Co2P electrodes present perfect performance with only needing overpotentials of 107.7/175.5/141.8 mV for hydrogen evolution reaction (HER) in acidic/neutral/alkaline solution and 269.4 mV for oxygen evolution reaction (OER) in alkaline solution to get current density of 20 mA cm?2. In addition, alkaline electrolyzer equipped with CF@P–Co2P bifunctional electrodes only needs a cell voltage of 1.657 V to get water-splitting current density of 20 mA cm?2. Even better, the electrolyzer can continuously electrolyze over 50 h with negligibly decreasing current density and the Faraday efficiency is close to 100% toward both HER and OER.  相似文献   

5.
Herein, we report the development of a simple, scalable, and cost-effective strategy for the synthesis of 2D sheets of molybdenum carbide and carbon (Mo2C–C) nanocomposite, by spray drying, as an efficient electrocatalyst. The synthetic methodology contains spray drying of clear aqueous precursor solution mixture of ammonium carbonate, ammonium heptamolybdate, and glucose followed by calcination under N2 atmosphere. The desired Mo2C nanoparticle and carbon were synthesized through carbothermal reduction of spray-dried carbonaceous mass, where partially decomposed glucose serves as carbon source. The synthesized Mo2C–C sheets calcined at an optimized temperature of 800 °C (Mo2C–C 800) are thin, porous and contain homogeneously dispersed Mo2C nanoparticles (8–15 nm) in carbon. The Mo2C–C 800 modified glassy carbon electrode exhibited excellent electrocatalytic activity for hydrogen evolution reaction (HER) with reduced over-potential of 110 mV at 10 mA/cm210) having reduced Tafel slope 69 mV dec−1 in 0.5 M aqueous H2SO4 solution. The catalyst also showed long term stability in an acidic as well as in the red-ox environment.  相似文献   

6.
Development of an inexpensive electrocatalyst for hydrogen evolution (HER) and oxygen evolution reactions (OER) receives much traction recently. Herein, we report a facile one-pot ethyleneglycol (EG) mediated solvothermal synthesis of orthorhombic Co2P with particle size ~20–30 nm as an efficient HER and OER catalysts. Synthesis parameters like various solvents, temperatures, precursors ratios, and reaction time influences the formation of phase pure Co2P. Investigation of Co2P as an electrocatalyst for HER in acidic (0.5 M H2SO4) and alkaline medium (1.0 M KOH), furnishes low overpotential of 178 mV and 190 mV, respectively to achieve a 10 mA cm?2 current density with a long term stability and durability. As an OER catalyst in 1.0 M KOH, Co2P shows an overpotential of 364 mV at 10 mA cm?2 current density. Investigation of Co2P NP by XPS analysis after OER stability test under alkaline medium confirms the formation of amorphous cobalt oxyhydroxide (CoOOH) as an intermediate during OER process.  相似文献   

7.
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   

8.
In this study, we demonstrated the active electrocatalysts of CoS2 coated by N-doped carbon microspheres, CoS2@NHCs-x (x = 600, 700, 800, and 900; x is pyrolysis temperature). Results show that the obtained electrocatalyst has good catalytic activity and cyclic stability for the reaction of hydrogen evolution (HER) when the pyrolysis temperature is 800 °C. At a current density of 10 mA cm−2, the overpotential of CoS2@NHCs-800 was only 98 mV in 0.5 M H2SO4, and 118 mV in 1 M KOH, respectively. In addition, CoS2@NHCs-800 also revealed excellent electrochemical stability, with only 32.7% performance degradation after continuous reaction in 0.5 M H2SO4 for 20 h, and the later current density almost no longer deceased with time as the reaction process stabilized. The excellent HER catalytic performance of CoS2@NHCs-800 is mainly attributed to the rich active sites of CoS2, the unique porous core-shell structure, and the enhanced conductivity of the carbon carrier caused by N and S co-doping. This work opens up an opportunity for advanced CoS2-based electrocatalysts for HER.  相似文献   

9.
Reversible oxygen electrodes with high efficiencies for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are of great significance for a variety of energy conversion devices, such as fuel cells and metal-air batteries. Herein, Co2P nanoparticles supported on cobalt-embedded N-doped carbon materials (Co2P/Co–N–C) have been prepared by pyrolysis of cobalt zeolitic imidazolate framework and phosphating post treatment. The optimal Co2P/Co–N–C composite shows excellent bifunctional electrocatalytic activities for both OER (the potential of 1.65 V at 10 mA cm?2) and ORR (half-wave potential of 0.82 V). As a practical demonstration, Co2P/Co–N–C catalyst is used as an air electrode in liquid Zn-air battery, which displays a large open-circuit voltage of 1.50 V, a high peak-power density of 158 mW cm?2 and excellent reversibility of over 205 h at 5 mA cm?2. Moreover, the flexible Zn-air battery with Co2P/Co–N–C exhibits a high open-circuit voltage of 1.46 V and the good flexibility with different angles. This work provides inspiration to explore new strategies for electrochemical energy conversion and storage.  相似文献   

10.
Design of cost-effective and high-efficient electrocatalysts for hydrogen evolution reaction (HER) is of vital significance for the current renewable energy devices — fuel cells. Herein, we report a facile strategy to prepare partial phosphorization of Co–Ni–B material with porous structure via a water-bath boronizing and subsequent phosphorization process at moderate temperature. The optimal atomic proportion of Co to Ni is investigated via physical and electrochemical characterization. As a result, Co9–Ni1–B–P exhibits the best HER activity, which require an lower overpotential of ~192 mV to deliver a current density value of 10 mA cm−2 and a smaller Tafel slope of 94 mV dec−1 in alkaline media, relative to P-free Co–Ni–B catalysts, Co9–Ni1–B–P with other Co: Ni proportion and mono metallic borides The excellent electrocatalytic performance of Co9–Ni1–B–P is mainly ascribed to the three-dimensional (3D) porous structure and the coordinate functionalization between the borides and phosphides. This work provides a promising strategy for the exploration of quaternary composites as efficient and cost-effective electrocatalysts for HER.  相似文献   

11.
The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co2P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and P-containing polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co2P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm−2 and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm−2, which endows Co2P/NPSC-800 with good catalytic activity in overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co2P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties.  相似文献   

12.
The design and fabrication of highly active, robust and cost-efficient electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great significance towards overall water splitting, but remains challenging as well. Herein, we report, for the first time, heterostructural Co/CeO2/Co2P/CoP@NC dodecahedrons as bifunctional electrocatalyst, in which abundant interfaces are formed between different components. Typical ZIF-67 (ZIF = zeolitic imidazolate framework) dodecahedrons with pre-inserted CeO2 nanowires were selected as precursors to synthesize Co/CeO2/Co2P/CoP@NC via a direct carbonization process followed by phosphidation, simultaneously generating the strong coupled heterojunction interfaces through interactions between CeO2 and CoxP species. Abundant porous structure leads to the exposure of more active sites and the carbon encapsulation of nanodomains sustains the high robustness and conductivity and the synergistic effect between the multi-components heterostructure. Benefiting from the above collective advantages, the Co/CeO2/Co2P/CoP@NC electrocatalysts exhibit small overpotentials of 307 and 195 mV to derive 10 mA cm−2 for OER and HER, respectively. Furthermore, an alkaline electrolyzer assembled by using Co/CeO2/Co2P/CoP@NC as both cathode and anode can achieve a current density of 10 mA cm−2 at a low voltage of 1.76 V and work continuously for over 15 h. This work would provide a rational protocol for fabrication multi-phase interface enriched electrocatalysts toward highly efficient energy conversion.  相似文献   

13.
Developing highly efficient, low-cost, and robust water splitting hydrogen production catalysts is critical for hydrogen energy applications. This study presents the synthesis of Co3O4/VO2 heterogeneous nanosheet structures on carbon cloth (Co3O4/VO2/CC). The obtained Co3O4/VO2/CC hybrid catalyst has a low overpotential of 108 mV at a current density of 10 mA cm?2, a Tafel slope of 98 mV dec?1, and high stability in 1.0 M KOH for 10 h. The experimental results and density functional theory (DFT) calculations results also show that Co3O4 coupled with VO2 in Co3O4/VO2/CC can optimize hydrogen adsorption energy and facilitate electron transport, thereby accelerating the catalytic kinetics for hydrogen evolution reaction (HER). This work also provided an alternative method to design and construct non-noble metal oxide-based catalysts for alkaline hydrogen production.  相似文献   

14.
For electrochemical splitting of water, highly active and non-precious metal electrocatalysts towards the oxygen evolution reaction (OER) are direly needed to address the cost and stability issues. Herein, polypyrrole (PPy) with 3D flower-like structure has been prepared to obtain N-doped porous carbon sheets (N–C) and to implant with cobalt oxides (Co3O4) via simple and cost-effective hydrothermal reaction. Benefitting from the 3D flower-like porous carbon structure, Co3O4/N–C demonstrates enlarged surface area replenished with more electrocatalytic active sites. What's more, Co3O4 nanoparticles are evenly dispersed onto the N-doped carbon surface which effectively prevents their aggregation and detachment. These exclusive structural features render amazing catalytic activity for Co3O4/N–C towards OER with an onset potential of ~1.31 V (vs RHE), low overpotential of 120 mV at 10 mA cm−2 and a Tafel slope of only 33 mV dec−1 in basic media. This work presents a simple approach to meet an ideal catalytic material with better morphology and advantageous properties for the possible energy and environmental applications.  相似文献   

15.
Electrocatalytic hydrogen evolution under alkaline media holds great promising in hydrogen energy production. Transition-metal sulfides (TMSs) are attractive for electrocatalytic alkaline hydrogen evolution, yet their catalytic performance is unsatisfactory owing to the sluggish water dissociation kinetics. Herein, a Mn/N co-doping strategy is proposed to regulate the water dissociation kinetics of Co9S8 nanowires array grown on nickel foam thus improve the activity of hydrogen evolution reaction (HER). The optimal Mn/N co-doping Co9S8 (Mn–N–Co9S8) catalyst achieves low overpotentials of 102 and 238 mV at 10 and 100 mA cm?2 in the 1 M KOH solution, respectively, remarkably higher than the single-doping Mn–Co9S8 and N–Co9S8 as well as superior to many reported Co9S8-based HER electrocatalysts. Density functional theory (DFT) calculation results confirm that the water dissociation barrier of the Mn–N–Co9S8 is reduced significantly owing to the synergistic co-doping of Mn and N, which accounts for the enhanced alkaline HER performance. This study offers an effective strategy to enhance the alkaline HER activity of TMSs by accelerating water dissociation kinetic via the cation and anion co-doping strategy.  相似文献   

16.
Ultrafine Ni2P/Co2P nanoparticles encapsulated in hollow porous N-doped carbon nanospheres are synthesized through a facile two-step access. Firstly, metallic Ni and Co coated by hollow N-doped spheres as precursors are obtained through a high temperature calcination route of organic polymer and inorganic Ni and Co salts. Then bimetal Ni2P/Co2P supported on N-doped carbon nanospheres are acquired by a facile phosphorization process. It is worth to note that aniline-pyrrole polymer can prevent fast growth and severe aggregation of Ni2P/Co2P, which implies more exposed active sites. Moreover, the calcination of hollow polymer spheres lead to the formation of ultrathin NC shell on the surface of Ni2P/Co2P hybrids, which can tune electronic structures, improve the conductivity and protect active sites from corrosion in harsh conditions. When used as HER catalyst, it displays remarkable catalytic activity in both acidic and alkaline solutions, which needs an onset potential of only 164 mV and 168 mV, respectively. Therefore, this work may propose a new strategy to design unique inorganic-organic heterostructures to combine ultrafine metal phosphides with porous carbon for efficient HER.  相似文献   

17.
As a new generation of non-precious metal catalysts, nickel phosphide is regarded as an ideal substitute for precious metal platinum in electrochemical hydrogen evolution. Here, a hydrogen evolution reaction (HER) electrocatalyst is developed by in situ growth of Ni2P/Ni5P4 heterostructures on porous N decorated rGO foam (named Ni2P/Ni5P4/N-rGO). The porous rGO foam structure provides a larger surface area and abundant active sites. The Ni2P/Ni5P4 nanoparticles with heterostructures are uniformly distributed on the rGO sheet, which enhance the charge transfer ability. The decorating of N element also correspondingly improves the HER performance. The as-prepared Ni2P/Ni5P4/N-rGO exhibits excellent HER performance in alkaline medium. When the current density is 10 mA cm?2, the overpotential is only 22 mV. No obvious loss of HER activity after 2000 cyclic voltammetry indicates that the composite has excellent stability. This work presents a valuable route for fabricating inexpensive and high-performance catalysts for electrocatalysis.  相似文献   

18.
Phosphonium-based ionic liquid, containing cobalt ion, was applied as novel phosphorus and metal dual-source for fabrication of cobalt phosphide. Trihexyl(tetradecyl)phosphonium tetrachlorocobaltate(II) ([P6,6,6,14]2[CoCl4]) with carbon nanotubes (CNTs) was utilized to obtain the Co2P/CNTs via one step phosphidation. This material exhibits a good catalytic activity toward hydrogen evolution reaction (HER) including an onset overpotential of 85 mV, a Tafel slope of 47 mV dec−1, current densities of 10 and 20 mA cm−2 at overpotentials of 150 and 178 mV, and it has a good stability to keep the HER activity. All experimental results confirmed that [P6,6,6,14]2[CoCl4] can form Co2P without adding other reagent and CNTs can improve the electrical conductivity and contribute to the formation of cobalt phosphide.  相似文献   

19.
Exploring noble-free electrocatalyst for hydrogen evolution by electrolysis of water is significant. Herein, porous Ni(OH)2@Ni spherical particles are electrodeposited on carbon papers as efficient electrocatalysts for hydrogen evolution reaction (HER) from water. Due to the porous and composite structure, the HER activity of Ni(OH)2@Ni/CP is better than the single phase Ni or Ni(OH)2 particles on the carbon paper. The overpotential of Ni(OH)2@Ni/CP is 106 mV at the current density of 10 mA cm?2 and the Tafel slope is 88 mV dec?1. Moreover, the stability of the catalysts tested for 12 h is also good for HER. Furthermore, the small Rct (1.65 Ω) of Ni(OH)2@Ni/CP provides the evident for its excellent catalytic performance. The method of electrodeposition provides the controllable uniform size for porous spherical Ni(OH)2@Ni particles. Moreover, the Faradaic efficiency for hydrogen evolution is 100%.  相似文献   

20.
Increasing world energy demands and crises led to alternative energy production methods, such as fuel cells using hydrogen gas which is the half electrochemical reaction of water splitting process. Herein, we synthesize polyvinylpyrrolidone coated Pd, Co and PdxCo1-x (x: 0.5, 0.12, 0.23, 0.49, 0.55, 0.62) metallic and bimetallic nanoparticles (NPs) via polyol process alternative to Pt-based catalysts for hydrogen evolution reaction (HER). Detailed structural analyses of Pd, Co and PdxCo1-x NPs revealed that fcc-Pd, fcc/hcp-Co and fcc-PdCo NPs crystal structures, and the lattice parameters were calculated as 3.5358 Å for Co NPs and 3.9777 Å for Pd NPs. The average size confirmed below 9 nm via TEM imaging and XPS data confirmed the formation of a bimetallic PdCo structure. Although Pd catalyst is mostly responsible for HER process, Pd62Co38 catalysts reduced the onset potential to about 197 mV and provided greater current density. Although Ea values were slightly higher against the Pt/C (20 wt %) benchmark which is reported as 16 kJ mol−1, PdCo NPs provided considerably reduced activation energy (Ea) values compared to Pd/C catalyst of 31 kJ mol−1. The best onset potential was recorded for Pd62Co38 catalysts for HER activity which is 16 mV higher compared to commercially available Pt/C catalyst.  相似文献   

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