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1.
Homogeneously distributed PtAu nanoalloy anchored to graphene (PtAuNA/G) was synthesized via a simple one-step electrochemical deposition process, in which Pt and Au ions and graphene oxide was simultaneously electro-reduced on the glassy carbon electrode. The morphology evolution of PtAuNA/G synthesized with different deposition times was characterized via field-emission scanning electron microscopy. X-ray diffraction and transmission electron microscopy was applied to confirm the alloy structure. The electrodeposition conditions, including the deposition time, were further optimized to explore the morphological evolution of PtAuNA/G. Based on cyclic voltammetry and chronoamperometry results, it was found that PtAuNA/G can efficiently catalyze the oxidation of methanol in alkaline media with dramatically enhanced electrocatalytic activity (7.268 mA cm?2, 3.83 times higher than that of commercial carbon-supported Pt nanoparticles, 1.894 mA cm?2), along with a considerably improved tolerance to poisoning (current decline: 69% vs 99.89%). These results indicate a great potential for PtAuNA/G in fabricating high-performance direct methanol fuel cells.  相似文献   

2.
Graphene was synthesized via electrochemical exfoliation technique of graphite rod in Poly (sodium 4-styrenesulfonate) solution. Laser Raman and X-ray Diffraction Spectroscopies were used to confirm the defects and crystal nature of graphene. The surface wettability studies based on water contact angle, further differentiates the affinity of as-prepared graphene and pristine graphite towards water. Modified Glassy carbon (GC) electrodes were prepared by electro-deposition of Platinum (Pt) on bare and graphene coated GC, denoted as GC/Pt and graphene/Pt modified GC respectively. The morphology and chemical composition of the thus synthesized graphene and graphene/Pt modified electrodes were investigated by High resolution transmission electron microscopy, Scanning electron microscopy and Energy dispersive spectroscopy. The electrochemically active surface area of the electro-deposited spherically shaped Pt particles was calculated to be 63.96 m2 g?1 and 25.10 m2 g?1 on graphene/Pt and GC/Pt, respectively. The electro-catalytic performance of modified electrodes for methanol oxidation was envisaged by cyclic voltammetry, linear sweep voltammetry and chronoamperometry. Graphene/Pt modified GC electrode showed higher oxidation peak current (42.90 mA cm?2) than GC/Pt modified electrode (16.24 mA cm?2) in forward scan of methanol oxidation because of the uniform distribution of spherically shaped Pt particles on graphene. The reaction path for methanol oxidation at different potentials was elucidated by means of Electrochemical Impedance Spectroscopy.  相似文献   

3.
Rational design and synthesis of core-shell bimetallic nanoparticles with tailored structural and functional properties is highly sought to realize clean and energy-efficient fuel cell systems. Herein, PdAu bimetallic nanoparticles (NPs) with core-shell morphology (PdCore–AuShell) were fabricated on the surface of reduced graphene oxide (RGO) support by a facile two-step protocol. In the first step, PdCore–AgShell bimetallic NPs were synthesized on RGO support by reducing Pd2+and Ag+ ions with methyl ammonia borane (MeAB). Later, PdCore–AuShell bimetallic NPs were conveniently fabricated on RGO support via a galvanic replacement strategy involving sacrificial oxidation of metallic silver and reduction of gold ions. The resulting core/shell bimetallic NPs were characterized by X-ray diffraction (XRD), High-resolution transmission electron microscopy (HR-TEM), Energy dispersive X-ray spectroscopy (EDS), Fourier-Transform Infrared Spectroscopy (FT-IR) and cyclic voltrammetry (CV). The electrocatalytic performance of core/shell nanostructures for the room temperature oxygen reduction reaction (ORR) in alkaline media were systematically performed by CV. The electrode-area-normalized ORR activity of RGO-supported PdCore–AuShell NPs was higher than the corresponding commercially available carbon-supported Pt nanoparticles (Pt/C) at ?0.8 V vs Ag/AgCl (satd. KCl) (6.24 vs 5.34 mA cm?2, respectively). Further, methanol-tolerant ORR activities of as-synthesized catalysts were also studied. The Au-on-Pd/RGO bimetallic NPs presented enhanced ORR activity both in presence and in the absence of methanol in comparison with a commercial Pt/C catalyst and as-synthesized Pd/RGO and Au/RGO catalysts. The enhanced catalytic activities of core/shell structures might be resulted owing to the optimized core/shell structure comprising of a small Pd core and a thin Au shell and synergistic effects offered by Pd and Au. The present synthesis protocol demonstrated for two-layer structure can be extended to multi-layered structures with desired functions and activities.  相似文献   

4.
As known, a good support enhances the activity and durability of any catalyst. In the current study, polypyrrole (PPY)/nanocomposite (MWCNTs and Al2O3) films were fabricated by electrochemical polymerization of pyrrole solution with a certain amount of nanoparticles on titanium substrates and were used as new support materials for Pt catalyst. The modified electrodes were characterized by Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDX) techniques. High catalytic activity and long-time stability toward methanol oxidation of Pt/PPY–MWNTs-αAl2O3 catalyst have also been verified by cyclic voltammetry results and chronoamperometric response measurements. This catalyst exhibits a vehemently high current density (345.03 mA cm?2) and low peak potential (0.74 v) for methanol oxidation. Other electrochemical measurements (electrochemical impedance spectroscopy (EIS), CO stripping voltammetry and Tafel test) clearly confirmed that Pt/PPY–MWNTs-αAl2O3/Ti electrode has a better performance toward methanol oxidation compared to the other electrodes and that can be used as a promising electrode material for application in direct methanol fuel cells (DMFCs).  相似文献   

5.
PtPd nanocubes (NCs) were uniformly deposited on the reduced graphene oxides (RGOs) via a one-pot solvothermal reduction. These PtPd NCs were enclosed with (100) facet. Their size can be tuned from 11 to 27 nm by controlling their composition. Under the optimum atomic ratio of Pt/Pd (1:5), the as-prepared RGO-supported PtPd NCs show a superior catalytic efficiency of ethanol oxidation reaction (EOR) with a specific activity of 2.3 mA cm?2 and a mass activity of 1.08 A mg?1 Pt, far above those for the RGO-supported Pt nanoparticles (0.3 mA cm?2 for specific activity and 0.018 A mg?1 Pt for mass activity). Besides, these EOR catalysts exhibit a high CO-tolerance without significant current decay during steady-state polarization at 0.6 V over 4000 s. Their durability is also remarkable with only 8.9% loss of their electrochemical surface area (ECSA) after 10 000 cycles of voltammetric test.  相似文献   

6.
Mesoporous nickel phosphate nanotube (Meso NiPO NT) and mesoporous nickel phosphate nanosheet (Meso NiPO NS) are developed as catalysts for electrochemical methanol oxidation. Conventional mesoporous nickel phosphate which is composed of stacked nanocrystals (Meso NiPO), microporous VSB-5 and commercial nickel oxide (NiO) are used as control materials. Notably, both Meso NiPO NT (40.83 mA cm?2) and Meso NiPO NS (44.97 mA cm?2) exhibit much higher oxidation current density than VSB-5 (13.41 mA cm?2), Meso NiPO (19.85 mA cm?2) and commercial NiO (0.87 mA cm?2). As for the durability test on these materials modified fluorine-doped tin dioxide transparent conductive glass (FTO) electrodes, Meso NiPO NT displays the most stable performance and still retains 91.3% electrochemical activity, which perhaps benefit from its nanotube structure and large specific surface area (99.6 m2/g). Moreover, Meso NiPO NT has higher activity and more excellent stability than many of the previously reported nickel-based materials, suggesting a potential development for direct methanol fuel cells.  相似文献   

7.
A simple method to prepare a dendritic Pt-shell coating on concave Pd nanoparticles (NPs) was successfully developed. In this study, tuning the Pt precursor concentration in the reaction mixture allowed control over the length of the outer Pt dendrites, enclosed by (211) high-index facets or (110) facets were performed. The concave Pd NPs covered by short Pt dendrites (Pd/S-Pt) and long Pt dendrites (Pd/L-Pt) were applied as catalysts for the oxygen reduction reaction (ORR) in 0.1 M HClO4 electrolyte solution. Pd/S-Pt with (211) facets had higher specific activity (0.106 mA cm?2) than that of Pd/L-Pt with (110) facets (0.066 mA cm?2) or commercial Pt/C (0.076 mA cm?2). Additionally, the accelerated durability test (ADT) results revealed that the decay for the ORR kinetic current catalysed by Pd/S-Pt was 28.21%, which was smaller than that of Pt/C (58.15%). Thus, Pd/S-Pt was effective for catalysis of the ORR.  相似文献   

8.
A novel catalyst electrode of Au nanoparticles modified Ti microrods is synthesized through a route of hydrothermal etching and electrodeposition. As substrate, the metallic Ti microrods are in-situ etched from the Ti plate using hydrochloric acid as an etching reagent. After that, Au is prepared on the metallic Ti microrods in a form of nanoparticle by electrodeposition. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) are conducted to investigate the structure and phase composition of the Au nanoparticles modified Ti microrods (Au/Ti MRs) electrode. Besides, the electrocatalytic property of the Au/Ti MRs electrode for NaBH4 oxidation is explored through chronoamperometry (CA) and cyclic voltammetry (CV). In alkaline solution, the Au/Ti MRs electrode displays excellent electrocatalytic property and good stability. At 0 V, there is a current density of 12.12 mA cm?2 on the as-prepared electrode in 2 mol L?1 NaOH and 0.1 mol L?1 NaBH4 that is twice as the current density on Au nanoparticles modified Ti plate electrode demonstrating huge potential for application in direct borohydride fuel cell.  相似文献   

9.
We have prepared a nanocomposite hybrid film to produce a collaborative network of gold (Au) nanoparticles that are highly dispersed on reduced graphene oxide (RGO) sheets, and tested it for electrocatalytic hydrogen production. The RGO/Au nanocomposite film synthesized on glassy carbon electrode (GCE) allows significant improvements to the electron-transfer process. The Au nanoparticles decorated on the surface of graphene increases the electron density, which synergistically promote the adsorption of hydrogen atoms on the graphene sheets and consequently enhance the hydrogen evolution reaction (HER) activity. The surface properties of the composite was characterized by field-emission scanning electron microscopy (FE-SEM) and the electrocatalytical performances evaluated as-prepared electrocatalyst toward (HER) by linear sweep voltammetry (LSV), Tafel polarization curves and electrochemical impedance spectroscopy (EIS) analyses. The GCE/RGO/Au nanohybrid electrode exhibited good catalytic activity for HER with an onset potential of ?0.3 V and a Tafel slope of 136 mV dec?1, achieving a current density of 10 mA cm?2 at an overpotential of ?0.43 V.  相似文献   

10.
Three-dimensional porous graphene (3D-G) is prepared by template-assembly method and employed as catalyst support for Ni nanoparticles for methanol electrooxidation. Morphology characterization confirm that Ni nanoparticles with sizes around 20 nm are uniformly scattered on the pore wall surface of the three-dimensional graphene without apparent agglomeration. Electrochemical measurements indicate that the Ni/3D-G processes higher electrocatalytic activity for methanol oxidation reaction than that of the Ni nanoparticles supported on two-dimensional graphene (Ni/2D-G) and Ni nanoparticles without graphene. The peak current density on Ni/3D-G is 64.6 mA cm?2, which is 1.5 times higher than that on Ni/2D-G. The remarkable electrocatalytic performance of the Ni/3D-G catalyst are mainly derived from the 3D graphene. As a carrier for methanol oxidation, the 3D-G with abundant pore architecture not only hinder the agglomeration of Ni particles that is beneficial to accelerating the efficient charge transport through the whole catalyst, but also offer readily accessible channels for the diffusion of CH3OH to the active sites of catalyst surface.  相似文献   

11.
Subjected to CO poisoning and weak catalytic performance, there are still large barriers to the effective use of direct methanol fuel cells. Therefore, bimetallic FeNi2P/C hybrid is synthesized by a facile hydrothermal method and low temperature phosphorization process. Subsequently, the as-synthesized FeNi2P/C is employed as catalytic support to load Pt nanoparticles. Due to the existence of phosphorus and the difunctional effects of Fe and Ni, electrochemical results demonstrate that the prepared Pt–FeNi2P/C compound exhibits an outstanding catalytic activity of 1125 mA·mg-1 Pt during methanol oxidation in acid solution, tower over that of Pt–FeP4/C (721 mA·mg-1Pt), Pt–Ni2P/C (588 mA·mg-1Pt) and Pt/C-JM (284 mA·mg-1Pt), separately. Significantly, bimetallic Pt–FeNi2P/C hybrid shows the optimal anti poisoning tolerance, which onset potential is negatively shifted 0.2 eV in comparison of Pt/C-JM. Hence, Pt-based catalyst decorated by bimetallic phosphides with excellent anti poisoning tolerance would be a superb material to flourish the catalytic field.  相似文献   

12.
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   

13.
Herein, a novel surfactant-free nanocatalyst of Pd–Fe bimetallic nanoparticles (NPs) supported on the reduced graphene oxide (Pd–Fe/RGO) were synthesized using a two-step reduction in aqueous phase. Electrochemical studies demonstrate that the nanocatalyst exhibits superior catalytic activity towards the formic acid oxidation with high stability due to the synergic effect of Pd–Fe and RGO. The optimized Pd–Fe/RGO (Pd:Fe = 1:5) nanocatalyst possess an specific activity of 2.72 mA cm?2 and an mass activity of 1.0 A mg?1(Pd), which are significantly higher than those of Pd/RGO and commercial Pd/C catalysts.  相似文献   

14.
Cobalt-titanium carbide nanoparticles (Co-TiC NPs) embedded on carbon nanofibers (composite) were prepared by electrospinning of a solution containing cobalt acetate tetrahydrate (CoAc), titanium (IV) isopropoxide (TIIP) and polyvinylpyrrolidone (PVP) in acetic acid and ethanol. It was then subjected to a carbonation process at a low temperature (850 °C) since the composite contains metal carbide. The obtained composite, as an efficient electrode, was used as an alternative to Pt-free counter electrode (CE) for fuel cells (FCs) and dye-sensitized solar cells (DSSCs). Cyclic voltammetry (CV) and chronoamperatory (CA) tests were used to measure the composite electrode's performance in methanol oxidation. The results showed that the introduced composite could enhance both methanol electro-oxidation and electrochemical stability as the low onset potential and high current density of the composite electrode were obtained at 189 mV and ~90 mA cm?2 vs. Ag/AgCl, respectively. The composite also was examined in dye-sensitized solar cells as counter electrode (CE). The results showed that the composite electrode was effective, providing stable electrocatalytic activity (ECA) and conductivity, indicating the composite can improve catalytic activity in triiodide reduction. The short-circuit current density (Jsc), open circuit voltage (VOC), fill factor (FF), and energy conversion efficiency (η) were found to be ~9.98 mA cm?2, 0.758 V, 0.507 and 3.87%, respectively. The high ECA could be attributed to the synergic effects from all the pristine components.  相似文献   

15.
Alloy structure can strongly enhance the chemical resistance of the bimetallic electrodes to be exploited as effective, low electrons transfer resistance and stable electrodes for the oxygen evolution reaction (OER) in the alkaline media. CoNi nanoparticles/carbon nanotubes (CNTs) composite was prepared by calcination of the physically well mixed nickel acetate, cobalt acetate and CNTs mixture under inert atmosphere at 850 °C. To ensure good mixing as well as strong adhesion of the metallic nanoparticles with the CNTs, the metals precursors were dissolved in ethanol first before addition of the carbonaceous partner. Due to the good absorbability of the CNTs to ethanol and the abnormal decomposition of the acetates precursors, oxides-free and well distributed CoNi nanoparticles/CNTs composite was obtained. Moreover, the XRD and TEM analyses affirmed formation of the alloy structure. The electrochemical measurements indicated that the proposed composites have very good catalytic activity toward the OER regardless the bimetallic nanoparticles composition. Numerically, the composites having bimetallic nanoparticles containing 0, 10 and 20 wt% cobalt revealed Tafel slops of 101, 159 and 111 mV dec?1, and overpotentials of 415, 461 and 485 mV at 10 mA cm?2 current density, respectively. However, the best stability in the alkaline medium was observed with the composite contains 10 wt% cobalt, while the other two formulations showed fast dissolution. Overall, the present study opens an avenue for the transition metals alloys to be invoked in the OER cells to overcome the high electron transfer resistance associated with the popularly used oxides-based electrodes.  相似文献   

16.
Au–Pt alloy particles with cauliflower-like microstructures of varying Pt/Au ratios were electrodeposited on indium tin oxide (ITO) substrates by constant potential electrolysis at E = −0.25 V. The results of X-ray diffraction and X-ray photoelectron spectroscopy confirm that the bimetallic alloys can be obtained for different Pt/Au ratios including 4/1, 1/1 and 1/4. The formation of alloyed cauliflower-like microstructures may be the result of the fast formation of gold seeds as the core and subsequent simultaneous deposition of Au and Pt from cyclic voltammetric study. The effect of surface composition of Au–Pt alloy particles on electrocatalytic methanol oxidation were investigated in H2SO4 solution. The electrocatalytic abilities including electrochemical surface area, peak current density and the turnover number of methanol oxidation follow the order of Pt4Au1 > Pt > Pt1Au1. The results can be ascribed to that electronic effect may be prominent while bifunctional effect is insignificant for Au–Pt alloy systems because the electrocatalytic activity of Au is negligible in acidic media. Additionally, the Pt4Au1 electrode has superior kinetics of methanol electro-oxidation than monometallic Pt electrode by calculating the electron transfer coefficient (α).  相似文献   

17.
A novel carbon fiber paper loaded with reduced graphene oxide (rGO) was used as the substrate, on which Pt–Ni nanoparticles were electro-deposited as to prepare an integrated electrode by two electrochemical methods (cyclic voltammetry and square wave pulse). The electrochemical tests indicated two integrated electrodes had excellent performance towards methanol oxidation. Especially, Pt-Ni-CV(A)-rGO/CFP electrode showed the highest electrocatalytic activity, and mass activity reached 5.33 A·mg?1Pt, which was about 5.6 times that of the commercial Pt/C catalyst (JM). Further, after annealing under a reducing atmosphere, two electrodes exhibited completely different changes in the aspects of morphology and electrocatalytic performance. It can be attributed to the changes of element distribution and morphology of nanoparticles after annealing. The as-prepared Pt–Ni-rGO/CFPs composite electrode is promising for integrated electrode of proton exchange membrane fuel cells. This work opens an avenue for the preparation of high-performance integrated electrode.  相似文献   

18.
Pt–Cu bimetallic nanoparticles supported on reduced graphene oxide (Pt–Cu/RGO) were synthesized through the simple one-step reduction of H2PtCl6 and CuSO4 in the presence of graphene oxide (GO) at room-temperature. The Pt–Cu/RGO was characterized with UV–vis spectrophotometer, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy and its catalytic behavior for the direct oxidation of methanol was investigated. Compared to Pt/RGO and Pt/C catalysts, Pt–Cu/RGO hybrids exhibited markedly superior catalytic activity for the electrocatalytic oxidation of methanol and ethanol. This improved catalytic activity can be attributed to the dendritic structure of the Pt–Cu bimetallic nanoparticles.  相似文献   

19.
The synthesis of carbon-supported unalloyed Au–Pt bimetallic nanoparticles using polyol method at a temperature as low as 85 °C is reported. Various compositions of Au–Pt/C bimetallic nanoparticles are characterized using transmission electron microscopy (TEM), X-ray florescence (XRF), X-ray diffraction and cyclic voltammetry. Electron microscopy shows that the particles have a near-narrow size distribution that peaks at an average size of ∼5 to 6 nm. The electrocatalytic activity of Au–Pt/C nanoparticles towards the oxygen reduction reaction (ORR) is studied by linear sweep polarization measurements obtained using a rotating disc electrode (RDE). The results reveal that a four-electron transfer pathway is mainly operative for ORR and the half-wave potential for ORR on bimetallic Au–Pt/C (20%:20%) is ∼100 mV less negative when compared with that of Pt/C (home-made and E-Tek). Studies of the methanol oxidation reaction (MOR) on these catalysts show that the MOR activity is significantly lowered with increasing content of Au in Au–Pt/C.  相似文献   

20.
Oxidative electrochemical polymerization of pyrrole at indium-doped tin oxide (ITO) is accomplished from a neat monomer solution with a supporting electrolyte (0.3 M n-tetrabutyl ammonium tetrafluoroborate) by multiple-scan cyclic voltammetry. Polypyrrole (Ppy) films containing nanometer-sized platinum and Pt/Pd bimetallic particles are electro-synthesized on ITO glass plates by voltammetric cycling between −0.1 and +1 V (versus Ag/AgCl/3 M NaCl). The electrocatalytic oxidation of methanol on the nanoparticle-modified polypyrrole films is studied by means of electrochemical techniques. The modified electrode exhibits significant eletrocatalytic activity for methanol oxidation. The enhanced electrocatalytic activities may be due to the uniform dispersion of nanoparticles in the polypyrrole film and a synergistic effect of the highly-dispersed metal particles so that the polypyrrole film reduces electrode poisoning by adsorbed CO species. The monometallic (Pt) and bimetallic (Pt/Pd) nanoparticles are uniformly dispersed in polypyrrole matrixes, as confirmed by scanning electron microscopic and atomic force microscopic analysis. Energy dispersive X-ray analysis is used to characterize the composition of metal present in the nanoparticle-modified electrodes.  相似文献   

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