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1.
The high activity electrocatalysts with low cost are crucial for large-scale direct alcohol fuel cells (DAFCs) applications. In this study, the “self-doping-defects” mesoporous carbon (SDMC) as support of uniformly-dispersed Pd nanoparticles (Pd/SDMC) was prepared for high active electrooxidation by a simple route without additional surfactant and acid treatment. According to the mutually corroborated experimental and theoretical calculation results, our route can significantly increase the carbon defect, which is conducive to the anchoring and uniform distribution of Pd nanoparticles. Meanwhile, the uniquely and hierarchically mesoporous nanostructure of SDMC provides abundant pathways for mass transport in the electrooxidation reaction. Benefitting from the above advantages, Pd/SDMC exhibits superior activity than commercial Pd/C and previously reported carbon-based electrocatalysts. The mass activities and specific activities of Pd/SDMC toward ethanol oxidation reaction (EOR) are 3404.3 mA mg−1, 4.48 mA cm−2, respectively. The mass activities and specific activities of Pd/SDMC for ethylene glycol oxidation reaction (EGOR) are 4002 mA mg−1, 5.26 mA cm−2, respectively. We believe that the facile strategy to synthesis mesoporous carbon with “self-doping” defects would promote large-scale DAFCs applications in the future.  相似文献   

2.
Electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and methanol oxidation reaction (MOR) are essential for energy conversion applications such as water electrolysis and fuel cells. Furthermore, Pt or Ir-related materials have been extensively utilized as electrocatalysts for the OER, ORR, and MOR. To reduce the utilization of precious metals, innovative catalyst structures should be proposed. Herein, we report a bi-metallic phosphide (Ni2P and PdP2) structure surrounded by graphitic carbon (Ni–Pd–P/C) with an enhanced electrochemical activity as compared to conventional electrocatalysts. Despite the low Pd content of 3 at%, Ni–Pd–P/C exhibits a low overpotential of 330 mV at 10 mA cm?2 in the OER, high specific activity (2.82 mA cm?2 at 0.8 V) for the ORR, and a high current density of 1.101 A mg?1 for the MOR. The superior electrochemical performance of Ni–Pd–P/C may be attributed to the synergistic effect of the bi-metallic phosphide structure and core-shell structure formed by graphitic carbon.  相似文献   

3.
A novel and high-efficiency Pd/TMxOy-rGO/CFP (TMxOy = Co3O4, Mn3O4, Ni(OH)2) electrocatalyst for directly integrated membrane electrode was synthesized by controllable cyclic voltammetry electrodeposition combined with hydrothermal process. The results showed excellent performance towards methanol oxidation reduction. The Pd/Co3O4-rGO/CFP as-prepared catalyst has the best electrocatalytic activity, and mass activity is 5181 mA·mg−1Pd, which is about 40 times and 4.3 times that of the commercial Pd/C and Pt/C catalyst (JM). It can be attributed that the small size of Pd nanoparticle, uniformity of distribution, and the synergistic interaction between transition metal oxide on the support surface and Pd nanoparticles. The prepared Pd/TMxOy-rGO/CFP composite electrode is a promising catalyst for integrated membrane electrode assembly of proton exchange membrane fuel cells in the future.  相似文献   

4.
In this work, a facile Fe- and N-containing porous carbon derived from sewage sludge was prepared and served as the support of Pt nanoparticles for the electrooxidation of methanol. Both the sludge-derived carbon (denoted as SC) and the resultant Pt/SC catalyst was physically characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrocatalytic performance for methanol oxidation reaction (MOR) of the Pt/SC was examined by cyclic voltammetry (CV) and chronoamperometric method. The results showed that the Pt/SC possessed slightly larger Pt particle size (5.5 nm) and lower electrochemical active surface area (ECA) compared to common Pt/C catalyst. However, the mass activity of Pt/SC for MOR was up to 201 mA mg−1, which was much higher than that of Pt/C (93 mA mg−1), indicating the synergistic effect of the sewage sludge-derived carbon with Fe and N species on methanol electrooxidation. Furthermore, Pt/SC showed enhanced durability towards MOR compared to common Pt/C, implying its potential for using in direct methanol fuel cell (DMFC) for energy conversion, which also demonstrated a promising solution for the utilization of sewage sludge resources.  相似文献   

5.
Designing rational nanostructures of metal-organic frameworks to speed up the methanol oxidation reaction and promote their application in methanol oxidation is highly desired but still remains a great challenge. In this study, we report a novel N-doped carbon coated CoP nanoparticles/carbon nanotube Pt-based catalyst (Pt–CoP-NCZ/CNT). This composite is produced through in situ growth of CoZn-ZIF on carbon nanotubes, subsequent carbonization and phosphorization treatment and microwave-assisted Pt supporting synthesis. The high specific surface area and N-doped structure endow the prepared catalysts with ideal conditions for supporting of Pt as well as good electrical conductivity. In addition, the evaporation of Zn2+ in CoZn-ZIF not only makes a contribution to a higher specific surface area of the material but also is favorable for uniform distribution of CoP nanoparticles, which gives CoP nanoparticles an excellent co-catalysis effect. Thus, the composite exhibits wonderful mass activity in both acid (930 mA mg−1) and alkaline (3622.5 mA mg−1) environments. Furthermore, the Pt–CoP-NCZ/CNT catalyst also shows better CO tolerance and long-time stability compared with other catalysts in this study. Thereby, the fabrication of the composite catalyst makes wider application of metal-organic frameworks in methanol oxidation possible and provides inspiration for designing efficient catalysts for methanol oxidation.  相似文献   

6.
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   

7.
The development of highly active and efficient heterogeneous catalytic oxidation system has become an attractive research field. In this paper, a catalyst (RuCo/N-CNT@PEDOT-OH/Pt) from platinum nanoparticles (Pt NPs) supported on hydroxyl-grafted poly(3,4-ethylenedioxythiophene) (PEDOT–OH)-modified RuCo, N-tridoped bamboo-like carbon nanotubes (RuCo/N-CNT) are used for direct methanol fuel cell (DMFC). The electrocatalytic activity of RuCo/N-CNT@PEDOT-OH/Pt is systematically compared with RuCo/N-CNT/Pt (Pt NPs supported on RuCo/N-CNT without PEDOT-OH) in the methanol oxidation reaction (MOR). The growth mechanism of carbon nanotubes and the role of heteroatom doping in the electrocatalytic process is explored. The catalysts show excellent electrocatalytic performance with high stability for MOR. It is found that the mass activity (MA) of the RuCo/N-CNT@PEDOT-OH/Pt (1961.3 mA mg?1Pt) for MOR was higher than that of RuCo/N-CNT/Pt (1470.1 mA mg?1Pt) and the commercial Pt/C catalysts (281.0 mA mg?1Pt), indicating the positive effect of the PEDOT-OH in the electrocatalytic MOR. In addition, density functional theory (DFT) calculations verify the possible mechanism pathways of the obtained RuCo/N-CNT@PEDOT-OH/Pt catalyst. This presented catalyst offers new inspiration for designing efficient electrocatalysts for methanol oxidation.  相似文献   

8.
Despite amounts of researches in recent years, it is still desirable but challenging to fabricate well-defined bifunctional catalysts with high performance towards alcohol oxidation and hydrogen evolution reaction (HER). Herein, a unique trimetallic PdCuIr catalyst with a nanocage (NC) structure is synthesized to be an excellent bifunctional catalyst by a seed-mediated growth strategy. The as-prepared PdCuIr NC catalyst exhibits remarkably enhanced mass activity and durability towards glycerol oxidation reaction (GOR) and ethylene glycol oxidation reaction (EGOR) as compared with commercial Pd/C catalyst. The optimal Pd58Cu32Ir10 NCs show electrocatalytic activities of 2565.79 mA mgPd−1 and 4498.30 mA mgPd−1 for GOR and EGOR, respectively. Meanwhile, the well-defined PdCuIr NC catalyst also displays outstanding electrocatalytic performance for HER, and the overpotential of Pd58Cu32Ir10 NCs only requires 54 mV to arrive at a current density of 10 mA cm−2, along with excellent electrochemical durability. The enhancement of electrocatalytic properties is attributed to the introduction of Cu and Ir atoms, which could modify the electronic structure of Pd to optimize the adsorption of reactants and intermediates. Moreover, the unique NC structure also significantly increases the number of reaction active sites as well as accelerates mass transport. Following this method, the trimetallic PdCuRu NCs and PdCuRh NCs are also synthesized. This work not only offers a general strategy for the fabrication of well-defined ternary alloy nanocatalysts, but also presents an advanced class of bifunctional catalysts for polyalcohol electrooxidation and HER.  相似文献   

9.
In the present work, a porous carbonaceous platform containing zirconium oxide was used for spreading Ni nanoparticles, and applied to methanol oxidation. The platform was obtained by calcination of a metal-organic framework (MOF) attached to graphene oxide. Nickel nanoparticles were then deposited on the nanocomposite by chemical reduction from a Ni2+ solution. The obtained electrocatalyst was characterized by different methods. An excellent electrocatalytic behavior was observed towards methanol oxidation in alkaline medium (j ~ 240 mA cm?2 or ~ 626 mA mg?1 in 1.0 M methanol). The results of methanol oxidation by various electrochemical studies (cyclic voltammetry, electrochemical impedance spectroscopy, chronoamperometry and chronopotentiometry) revealed the effective synergy between reduced graphene oxide, porous carbon material, ZrO2 metal oxide and Ni nanoparticles. Good durability and stability of the proposed electrocatalyst and significantly increased current density of methanol oxidation suggest it as a potential alternative for Pt-based electrocatalysts in direct methanol fuel cells.  相似文献   

10.
Platinum (Pt) is often used as anodic catalyst for direct methanol fuel cell (DMFC). However, platinum is difficult to achieve large-scale application because of its low stability and high cost. In this work, the electrocatalytic activity and stability of the Pt-based catalyst for methanol oxidation (MOR) are significantly improved by adding Ce and Ni to the catalyst. Additionally, the rare earth element-Pr (Dy) is also chosen to be added into the catalysts for comparison. A series of PtMNi (M = Ce, Pr, Dy) catalysts are prepared by impregnation and galvanic replacement reaction methods using carbon black as support. The electrocatalytic mass activity of PtCeNi/C, PtDyNi/C, PtPrNi/C and Pt/C is 3.92, 1.86, 1.69 and 0.8 A mgPt−1, respectively. The mass activity of these the above four catalysts after stability measurement is 3.14, 1.49, 1.27 and 0.72 A mgPt−1. Among them, PtCeNi/C has the highest catalytic activity. These as-prepared catalysts are also characterized by various analyzing techniques, such as TEM, HRTEM, XRD, XPS, ICP-OES, STEM, STEM-EDS elemental mapping and line-scanning etc. It shows that PtCeNi/C exhibits best catalytic activity (3.92 A mgPt−1) among the as-obtained catalysts, 4.9 times higher than that of commercial Pt/C (0.8 A mgPt−1). PtCeNi/C is also with excellent anti-CO poisoning ability. The outstanding catalytic performance of PtCeNi/C for the MOR is mainly attributable to uniform-sized PtCeNi nanoparticles, uniform Ni, Ce and Pt element distribution, and electron interaction among Pt-, Ni- and Ce-related species (electron transferring from Pt to CeO2).  相似文献   

11.
Developing efficient, durable, and economical electro-catalysts for large-scale commercialization of hydrogen evolution (HER) is still challenging. Herein, we report for the first time, to the best of our knowledge, a Pd-based ternary metal phosphide as an active and stable HER catalyst. The face-centered-cubic Pd–Ni–P nanoparticles (NPs) annealed at 400 °C show the best HER activity with a low overpotential of 32 mV to realize a current density of 10 mA cm−2 and a high mass activity of 1.23 mA μg−1Pd, superior to Pd NPs, Pd–P NPs, Pd–Ni NPs, and Pd–Ni–P NPs annealed under different temperatures. Moreover, this catalyst is also highly stable during 20 h of continuous electrolysis. Notably, the easily fabricated Pd–Ni–P NPs are among the most active Pd-based HER catalysts. This work indicates that Pd-based metal phosphides could be potentially applied as a type of practical HER catalyst and might inform the fabrication of analogous materials for hydrogen-related applications.  相似文献   

12.
Development of highly effective and stable electrocatalysts is urgent for various energy conversion applications. Herein, a facile co-reduction approach was developed to fabricate three-dimensional (3D) hyperbranched PtRh nanoassemblies (NAs) under solvothermal conditions, where creatinine and cetyltrimethylammonium chloride (CTAC) were employed as the structure-directing agents. The as-synthesized nanocatalyst exhibited intriguing catalytic characters for hydrogen evolution reduction (HER) with a low overpotential (20 mV) at 10 mA cm−2 and a small Tafel slope (49.01 mV dec−1). Meanwhile, the catalyst showed remarkably enlarged mass activity (MA: 2.16/2.02 A mg−1) and specific activity (SA: 4.16/3.88 mA cm−2) towards ethylene glycol and glycerol oxidation reactions (EGOR and GOR) alternative to commercial Pt black and homemade Pt3Rh nanodendrites (NDs), PtRh3 NDs and Pt nanoparticles (NPs). This method offers a feasible platform to fabricate bifunctional, efficient, durable and cost-effective nanocatalysts with finely engineered structures and morphologies for renewable energy devices.  相似文献   

13.
In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres(DLHCs)with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m2 g−1 and 807 mA mg−1 in 0.5 M H2SO4 containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.  相似文献   

14.
Tri-metallic MnNiFe alloy nanoparticles with four different Mn:Ni:Fe weight ratios (0.5:2.0:0.5, 0.5:1.0:0.5, 1.0:1.0:1.0, and 2.0:0.5:2.0) on reduced graphene oxide (rGO) supports were synthesized using a one-pot hydrothermal method. The as-prepared catalysts were characterized by X-ray diffraction, inductively coupled plasma-mass spectroscopy, Brunauer-Emmett-Teller analysis, scanning electron microscopy, and transmission electron microscopy, and their catalytic activities were measured by cyclic voltammetry and chronoamperometry. In urea electro-oxidation, the Mn0.5Ni2.0Fe0.5/rGO catalyst exhibited superior electrocatalytic activity compared to Ni/rGO and commercial Ni/C. The Mn0.5Ni2.0Fe0.5/rGO catalyst exhibited a mass activity of 1753.97 mA mg−1Ni, along with an onset potential of 0.34 V (vs. Ag/AgCl) in 1.0 M KOH and 0.33 M urea solution, which is ~4.2 times and 9.8 times higher than those of Ni/rGO and commercial Ni/C, respectively. Furthermore, a single cell comprising of Mn0.5Ni2.0Fe0.5/rGO catalyst exhibited a peak power density of 30.08 mW cm−2 in 0.33 M urea and 1.0 M KOH at 50 °C.  相似文献   

15.
Cost-effective hierarchical electrocatalysts with excellent performance and high stability for water splitting play an important role in promoting social sustainable development. Herein, we report a three-dimensional (3D) trimetallic nickel-iron-cobalt phosphide with a hierarchical nanoarray structure grown in situ on carbon cloth via a combined method of two-step hydrothermal reaction and following low-temperature phosphating using a carbon cloth as a conductive substrate. The synthesized NiFeP/CoP/CC exhibits excellent oxygen evolution reaction (OER) catalytic performance, giving small overpotentials of 250 mV, 270 mV and 320 mV at current densities of 20 mA cm−2, 50 mA cm−2 and 200 mA cm−2 in alkaline electrolyte, respectively, with a small Tafel slope of 51 mV dec−1. In addition, the catalytic activity of the material remains stable for at least 50 h, and the turnover frequency (TOF) is 0.466 mol O2 s−1 at an over potential of 300 mV. These properties of the material are comparable to those of the noble metal catalyst RuO2/CC, which may be ascribed to the hierarchical microstructure, good conductivity and desirable synergistic effect among metal ions.  相似文献   

16.
Pd-based catalysts have received wide attention due to their outstanding anti-CO poisoning property, whereas the structural instability limits their application. The hierarchical porous PdRuCu nanosheets (HP PdRuCu NSs) with large electrochemically active surface area, abundant active sites, and stable structures are synthesized through continuous access to CO bubbles. HP PdRuCu NSs exhibit excellent hydrogen evolution reaction (HER) catalytic activity with an ultralow overpotential of 25 mV at 10 mA cm?2 and a Tafel slope of 87.5 mV dec?1 in alkaline·media. Meanwhile, the peak mass activity and specific activity of HP PdRuCu NSs for glycerol oxidation reaction (GOR) are 1083 mA mg?1Pd and 38.8 A m?2, respectively, superior to that of PdRu nanosheets (PdRu NSs), Pd nanosheets (Pd NSs), and commercial Pd black. The introduction of Ru and Cu atoms facilitates the C–C bond cleavage and the complete oxidation of glycerol to CO2, as well as the accelerated oxidation/removal of the poisonous COads in between.  相似文献   

17.
The effect of carbon monoxide (CO) on the reduction of Pt ion to metallic Pt is studied. The modified GC electrode with platinum metal synthesized in the presence of CO shows excellent activity for hydrogen evolution reaction (HER). Despite the decrease in the loading of platinum (4.5 × 10−4 mg cm−2) a substantial increase in its electrocatalytic activity towards HER is observed in a sulfuric acid environment. The observed electrocatalytic activity is comparable to available commercial catalysts like Pt/C. Tafel slope was obtained to be 34 mV.dec−1, and the overpotential was acquired to be 31 mV at the mass activity of 10 mA mg−1 were observed which was very close to kinetic parameters of Pt/C catalyst.  相似文献   

18.
Carbon particles modified macroporous Si/Ni composite (MP-Si/Ni/C) is easily obtained via a facile fabrication of porous Si/Ni precursor by dealloying SiNiAl alloy followed by a surface growth of carbon nanoparticles. MP-Si/Ni/C composite possesses the multiply conductivity modification that are built through mixing Ni dispersoid and growing one layer of carbon particles. Coupled with the structural advantages of interconnected network backbone, rich voids, and the coated carbon particles, MP-Si/Ni/C exhibits dramatically enhanced lithium storage performances with excellent reversible capacity, enhanced rate performance, as well as outstanding cycling stability compared with pure MP-Si and MP-Si/Ni. Especially, the reversible capacity remains up to 1113.1 and 708.8 mA h g−1 at the current densities of 200 and 1000 mA g−1 after 120 cycles, respectively. Besides, it shows excellent rate capability even when continuously cycled at high current density of 3000 mA g−1. With the advantages of unique structure, excellent performances, and facile preparation, the as-made MP-Si/Ni/C composite shows promising application potential as an alternative anode for lithium ion batteries.  相似文献   

19.
High cost and poor durability of Pt-based cathode catalysts for oxygen reduction reaction (ORR) severely hamper the popularization of proton exchange membrane fuel cells (PEMFCs). Tailoring carbon support is one of effective strategies for improving the performance of Pt-based catalysts. Herein, petroleum vacuum residue was used as carbon source, and nitrogen-doped porous carbon (N-PPC) was synthesized using a simple template-assisted and secondary calcination method. Small Pt nanoparticles (Pt NPs) with an average particles size of 1.8 nm were in-situ prepared and spread evenly on the N-PPC. Interestingly, the lattice compression (1.08%) of Pt NPs on the N-PPC (Pt/N-PPC) was clearly observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), which was also verified by the shift of (111) crystal plane of Pt on N-PPC to higher angles. The X-ray photoelectron spectroscopy (XPS) results suggest that the N-PPC support had a strong effect on anchoring Pt NPs and endowing surface Pt NPs with lowered d band center. Thus, the Pt/N-PPC as a catalyst simultaneously boosted the ORR activity and durability. The specific activity (SA) and mass activity (MA) of the Pt/N-PPC at 0.9 V reached 0.83 mA cm−2 and 0.37 A mgPt−1, respectively, much higher than those of the commercial Pt/C (0.21 mA cm−2 and 0.11 A mgPt−1) in 0.1 M HClO4. The half-wave potential (E1/2) of Pt/N-PPC exhibited only a minimal negative shift of 7 mV after 30,000 accelerated durability tests (ADT) cycles. More importantly, an H2–O2 fuel cell with a Pt/N-PPC cathode achieved a power density of 866 mW cm−2, demonstrating that the prepared catalyst has a promising application potential in working environment of PEMFCs.  相似文献   

20.
Pt-based catalysts are still most attractive and could be the major driving force for facile electrochemical reactions in direct methanol fuel cells (DMFCs). In this work, a Pt3Mn nanowire network structures (NWNs) catalyst was successfully synthesized by a soft template (CTAB) method. The morphology and elemental composition of the Pt3Mn NWNs were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The electrocatalytic behavior of the synthesized Pt3Mn NWNs catalyst towards methanol oxidation reaction (MOR) was studied by cyclic voltammetry (CV) and chronoamperometry (CA). The results reveal that the Pt3Mn NWNs has superior MOR activity and durability compared to Pt NWNs and commercial Pt/C. The mass and specific activities of Pt3Mn NWNs are 0.843 A mg−1 and 1.8 mA cm−2 respectively, which are twice that of commercial Pt/C. Additionally, the results of CA test indicate that the Pt3Mn NWNs possesses better durability than Pt NWNs and commercial Pt/C catalysts in acidic media, which is expected to be a new alternative anode material in DMFCs.  相似文献   

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