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1.
One-dimensional platinum (Pt) nanostructures with different shape, size, and morphology were synthesized by galvanic displacement of sacrificial Cu nanowires in chloroplatinic acid baths. By increasing the concentration of H2PtCl6, the morphology of Pt nanostructures greatly altered from Pt nanoparticles decorated Cu nanowires, Pt coated Cu core-shell nanowires, dense Pt nanotubes to porous Pt nanotubes. At low concentration of H2PtCl6 (<1 mM), the Pt content monotonically increased with an increase in [H2PtCl6] (upto approx. 80 at.%). The Pt content became independent of [H2PtCl6] at higher concentration. The average external diameter and wall thickness of Pt nanotubes decreased with increasing [H2PtCl6] suggesting that the dissolution of copper is strongly dependent on [Cl], which led to changes in the morphology of Pt nanostructures.  相似文献   

2.
The synthesis of polyaniline/platinum composites (PANI/Pt) has been achieved using both chemical and electrochemical methods. The direct chemical synthesis of PANI/Pt proceeds through the oxidation of aniline by PtCl62− in the absence of a secondary oxidant. SEM images of these samples indicate that the Pt particles are on the order of ∼1 μm for the chemically prepared composite. Electrochemical PANI/Pt synthesis is initiated by the uptake and reduction of PtCl62− into an a priori electrochemically deposited PANI film. This method produces a uniform dispersion of Pt particles with smaller particles with diameters ranging between 200 nm and 1 μm. The results indicate that electrochemical methods may be more suitable for controlling particle dimension. Both materials show reduced proton doping relative to PANI without Pt, indicating the metal particles directly influence proton doping and the oxidation state of the polymer. The electrochemical data indicate that the conductivity in solution is sufficient such that the normal acid doping is attainable for PANI/Pt produced using either synthetic method.  相似文献   

3.
We have developed a novel preparation method for Pt-based nanoparticles by means of double potential step electrolysis (DPSE), in which Pt-Ni alloy deposited at the first step and Ni dissolved at the following step. A cycle of the DPSE in a nickel plating bath containing PtCl62− led to the formation of the Pt-Ni nanoparticles with size of about 5.4 ± 1.5 nm, which gradually grew up with repeating the DPSE process, and surface Ni content of the particles by XPS was controllable by changing some parameters of the DPSE. The Pt-Ni nanoparticles deposited by the DPSE were covered with a Pt skin layer, which influence the improvement of both catalytic activity for oxygen reduction reaction (ORR) and corrosion resistance. The Pt-Ni nanoparticles by the DPSE exhibit ca. two times higher electrocatalytic activity for ORR than Pt nanoparticles, and further, of which catalytic activity was maintained high even with more than 1000 cycles of potential cycling test in H2SO4 solution, showing good corrosion resistance.  相似文献   

4.
For the first time, poly (o-anisidine-co-metanilic acid) (PASM) was deposited on mild steel substrate by electrochemical polymerization of o-anisidine and metanilic acid monomers in aqueous solution of 0.1 M H2SO4. The electrochemical polymerization of o-anisidine takes place in the presence of metanilic acid monomer and uniform, strongly adherent coating was obtained on the substrate. The electroactivity of copolymer was studied by cyclic voltammetry and AC impedance techniques. There is an increasing anodic current due to oxidation of metanilic acid monomer at the surface of the electrode when the applied potential is cycled from −0.2 V to 0.8 V. These deposits were characterized by Fourier transform infrared (FTIR) spectroscopy, UV-vis and TG/DTA techniques. The effect of various concentrations of PASM copolymer solution in acid rain corrosive media has been studied through potentiodynamic polarization, AC impedance and I-E curve methods. The soluble form of polymeric solution provided better anti-corrosive behavior in artificial acid rain solution.  相似文献   

5.
A simple surfactant-stabilized method was investigated for the preparation of well-dispersed platinum nanoparticles supported on carbon black (Pt/C), using 3-(N, N-dimethyldodecylammonio) propanesulfonate (SB12) as the stabilizer. First, TEM analysis demonstrated that Pt dispersion can be improved by the increase of molar ratio of SB12 to Pt precursor. Moreover, pH environment plays a crucial role in Pt dispersion, and the optimal dispersion with an average Pt particle size of 2.2 nm was obtained under neutral or slightly alkaline environment. Pt dispersion mechanism was shown to involve the electrosteric stabilization of Pt nanoparticles by the zwitterionic surfactant SB12, which is highly pH-dependent. At pH ≥ 7, a stable electrosteric repulsion exists between the Pt particles covered by SB12, where the positively charged part is adsorbed on the particle surface and the negatively charged part (SO3) and the bulky alkyl chain (C12H25) are pointed away from particles. At pH < 7, protons H+ directly interact with Pt particles or SO3 groups of SB12, resulting in the destruction of the electrosteric stabilization and the following agglomeration of Pt nanoparticles. Furthermore, XPS and cyclic voltammetry showed that the surfactant on Pt particles can be efficiently removed by ethanol wash without any destruction on the dispersion and particle size of Pt, when compared to heat treatment and centrifugation. Electrochemical measurements showed that the ethanol-washed pH-controlled Pt/C catalyst has higher electrochemical surface area and catalytic performance than the commercial one.  相似文献   

6.
A novel layered manganese oxide/poly(aniline-co-o-anisidine) nanocomposite [MnO2/P(An-co-oAs)] was successfully synthesized by a delamination/reassembling process using P(An-co-oAs) ionomer and layered manganese oxide in aqueous solution. This nanocomposite obtained was then characterized by Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD), electron microscopy (SEM), and thermogravimetric (TG) analysis. X-ray diffraction and electron microscope analysis showed that the MnO2/P(An-co-oAs) nanocomposite had a lamellar structure with increasing interlayer spacing. The MnO2/P(An-co-oAs) nanocomposite exhibited substantially improved conductivity, which was near 100 times greater than that of its pristine MnO2 (3.5 × 10−7 S cm−1). The specific capacitance of the MnO2/P(An-co-oAs) nanocomposite reached 262 F g−1 in 1 M Na2SO4 at a current density of 1 A g−1, which was significantly higher than that of either of its two pristine materials [MnO2 (182 F g−1) or P(An-co-oAs) (127 F g−1)] owing to the synergic effect between the two pristine components. The fabrication mechanism of the nanocomposite was also proposed and discussed in this paper.  相似文献   

7.
Zhan Lin 《Electrochimica acta》2009,54(27):7042-9377
Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles directly onto electrospun carbon nanofibers. The morphology and size of Pt nanoparticles were controlled by the electrodeposition time. The resulting Pt/carbon composite nanofibers were characterized by running cyclic voltammograms in 0.20 M H2SO4 and 5.0 mM K4[Fe(CN)6] + 0.10 M KCl solutions. The electrocatalytic activities of Pt/carbon composite nanofibers were measured by the oxidation of methanol. Results show that Pt/carbon composite nanofibers possess the properties of high active surface area and fast electron transfer rate, which lead to a good performance towards the electrocatalytic oxidation of methanol. It is also found that the Pt/carbon nanofiber electrode with a Pt loading of 0.170 mg cm−2 has the highest activity.  相似文献   

8.
Guojin Lu 《Electrochimica acta》2006,51(12):2531-2538
Platinum nanoparticles were electrochemically deposited onto highly oriented pyrolitic graphite (HOPG) from H2PtCl6 solutions and observed by tapping mode atomic force microscopy. Spontaneous Pt deposition, which resulted in a wide particle size distribution, would occur on HOPG at open-circuit potential but could be suppressed by using anodic bias of the substrate before and after deposition. Nanoparticles with a narrow size distribution could be obtained when spontaneous reduction was avoided. Pt nucleated both at step edges and on terraces, with a preference for the former. The density of Pt nanoparticles on HOPG was 109-1010 cm−2. Increasing the deposition overpotential or adding HCl as supporting electrolyte resulted in more uniform particles and less aggregation. These findings confirm previous results obtained by our group using only electrochemical methods [G. Lu, G. Zangari, J. Phys. Chem. B 109 (2005) 7998].  相似文献   

9.
This study uses rotating ring-disk electrode (RRDE) and linear sweep voltammetry (LSV) to characterize oxygen reduction kinetics in alkaline solution on platinum electrodes with various thickness of hydrous oxide (oxyhydroxy) film. Oxyhydroxy films are created on Pt electrodes by pretreatment in 1.0 mol dm−3 KOH at a constant voltage. The pretreatment voltage ranges from −1.2 to 1.0 V and is increased stepwise before each new experimental run to produce seven discreet films. LSV plots show oxyhydroxy film thickness strongly inhibits oxygen reduction and is inversely proportional to RRDE oxygen reduction current ID for LSV voltages ED from −0.1 to −0.46 V, but this trend reverses at ED more negative than −0.46 V so that the worst-performing electrode becomes the best. However, this improvement disappears at around −0.8 V, suggesting this change involves a negatively charged ion, possibly embedded into the metal in the top few atomic layers either interstitially or substitutionally. The 1.0 V-pretreated electrode in the ED range from −0.46 to −0.9 V of highest oxygen reduction current also exhibits the lowest hydrogen peroxide production, with zero H2O2 produced at −0.6 V, indicating the brief presence of the oxyhydroxy film on the Pt surface has strong lingering effects. The post-oxyhydroxy Pt surface is very different than the native Pt for oxygen reduction pathway and efficiency. Reaction order with respect to oxygen is close to 1. The rate constants of the direct O2 to H2O electroreduction reaction are increased with decreasing the potential from −0.2 to −0.6 V, but the O2 to H2O2 electroreduction is contrary to this expectation. The rate constants of H2O2 decomposition on the oxyhydroxy film-covered Pt electrode are near constant around 1 × 10−4 cm s−1 at ED > −0.5 V.  相似文献   

10.
A cuprous oxide (Cu2O) nanoparticles modified Pt rotating ring-disk electrode (RRDE) was successfully fabricated, and the electrocatalytic determination of p-nitrophenol (PNP) using this electrode was developed. Cu2O nanoparticles were obtained by reducing the copper-citrate complex with hydrazine hydrate (N2H4·H2O) in a template-free process. The hydrodynamic differential pulse voltammetry (HDPV) technique was applied for in situ monitor the photoelectrochemical behavior of PNP under visible light using nano-Cu2O modified Pt RRDE as working electrode. PNP undergoes photoelectrocatalytic degradation on nano-Cu2O modified disk to give electroactive p-hydroxylamino phenol species which is compulsive transported and can only be detected at ring electrode at around 0.05 V with oxidation signal. The effects of illumination time, applied bias potential, rotation rates and pH of the reaction medium have been discussed. Under optimized conditions for electrocatalytic determination, the anodic current is linear with PNP concentration in the range of 1.0 × 10−5 to 1.0 × 10−3 M, with a detection limit of 1.0 × 10−7 M and good precision (RSD = 2.8%, n = 10). The detection limit could be improved to 1.0 × 10−8 M by given illumination time. The proposed nano-Cu2O modified RRDE can be potentially applied for electrochemical detection of p-nitrophenol. And it also indicated that modified RRDE technique is a promising way for photoelecrocatalytic degradation and mechanism analysis of organic pollutants.  相似文献   

11.
Fang Ye  Lishi Wang 《Electrochimica acta》2008,53(12):4156-4160
5-[o-(4-Bromine amyloxy)phenyl]-10,15,20-triphenylporphrin (o-BrPETPP) was electropolymerized on a glassy carbon electrode (GCE), and the electrocatalytic properties of the prepared film electrode response to dopamine (DA) oxidation were investigated. A stable o-BrPETPP film was formed on the GCE under ultrasonic irradiation through a potentiodynamic process in 0.1 M H2SO4 between −1.1 V and 2.2 V versus a saturated calomel electrode (SCE) at a scan rate of 0.1 V s−1. The film electrode showed high selectivity for DA in the presence of ascorbic acid (AA) and uric acid (UA), and a 6-fold greater sensitivity to DA than that of the bare GCE. In the 0.05 mol L−1 phosphate buffer (pH 6.0), there was a linear relationship between the oxidation current and the concentration of DA solution in the range of 5 × 10−7 mol L−1 to 3 × 10−5 mol L−1. The electrode had a detection limit of 6.0 × 10−8 mol L−1(S/N = 3) when the differential pulse voltammetric (DPV) method was used. In addition, the charge transfer rate constant k = 0.0703 cm s−1, the transfer coefficient α = 0.709, the electron number involved in the rate determining step nα = 0.952, and the diffusion coefficient Do = 3.54  10−5 cm2 s−1 were determined. The o-BrPETPP film electrode provides high stability, sensitivity, and selectivity for DA oxidation.  相似文献   

12.
Two electrochemically assisted variants of the Bönneman organosol method were developed for Pt-Sn nanoparticle synthesis and in situ deposition on graphite felt electrodes (e.g. thickness up to 2 mm). Tetraoctylammonium triethylhydroborate N(C8H17)4BH(C2H5)3 was employed as colloid stabilizer and reductant dissolved in tetrahydrofuran (THF). The role of the electric field at a low deposition current density of 1.25 mA cm−2 was mainly electrophoretic causing the migration and adsorption of N(C8H17)4BH(C2H5)3 on the graphite felt surface where it reduced the PtCl2-SnCl2 mixture. Faradaic electrodeposition was detected mostly for Sn. Typical Pt-Sn loadings were between 0.4 and 0.9 mg cm−2 depending on the type of pre-deposition exposure of the graphite felt: surfactant-adsorption and metal-adsorption variant, respectively. The catalyst surface area and Pt:Sn surface area ratio was determined by anodic striping of an underpotential deposited Cu monolayer. The two deposition variants gave different catalyst surfaces: total area 233 and 76 cm2 mg−1, with Pt:Sn surface area ratio of 3.5:1 and 7.7:1 for surfactant and metal adsorption, respectively. Regarding electrocatalysis of ethanol oxidation, voltammetry and chronopotentiometry studies corroborated by direct ethanol fuel cell experiments using 0.5 M H2SO4 as electrolyte, showed that due to a combination of higher catalyst load and Pt:Sn surface ratio, the graphite felt anodes prepared by the metal-adsorption variant gave better performance. The catalyzed graphite felt provided an extended reaction zone for ethanol electrooxidation and it gave higher catalyst mass specific peak power outputs compared to literature data obtained using gas diffusion anodes with carbon black supported Pt-Sn nanoparticles.  相似文献   

13.
This work reports on the kinetics of the hydrogen oxidation reaction (HOR) on model Pd nanoparticles supported on a low surface area carbon substrate. Two Pd/C samples, with the average particle size 2.6 and 4.0 nm were used. The structure of the catalysts was characterized with the ex situ (electron microscopy) and in situ (electrochemical) methods. We utilized the electrochemical impedance spectroscopy (EIS) and the rotating disk electrode (RDE) voltammetry to study the kinetics of the HOR on Pd/C. The relevance of these techniques for elucidating the kinetics and the mechanism of the HOR on Pd/C was explored. The experimental results suggest that the catalytic activity of Pd in the HOR is more than 2 orders of magnitude lower than that of Pt, and does not depend on the particle size in the range from 2.6 to 4.0 nm. Computational modeling of the experimental steady-state (RDE) and non-steady-state (EIS) data shows that the reaction kinetics can be adequately described within Heyrovsky-Volmer mechanism, with the rate constants υ0H = (8.8 ± 1.5) × 10−10 mol cm−2 s−1 and υ0V = (1.0 ± 0.3) × 10−8 mol cm−2 s−1. The model suggests that underpotentially deposited hydrogen HUPD is unlikely to be the active intermediate Had of the HOR. It is concluded that the surface coverage of Had deviates from that of HUPD with increasing overpotential, and the lateral interactions within Had adlayer are weak.  相似文献   

14.
Pt nanoparticles are synthesized by the alcoholic reduction of H2PtCl6 in the presence of a polycation, poly(diallyldimethylammonium chloride) (PDDA). The size of the PDDA-Pt nanoparticle colloids is in the range of 2-4 nm, depending on the PDDA to Pt ratio in the solution. The PDDA-Pt nonoparticles can be self-assembled to the sulfonic acid group, SO3, at the Nafion membrane surface by the electrostatic interaction, forming a self-assembled monolayer (SAM). The study shows that such SAM reduced the methanol crossover and enhanced the power output of direct methanol fuel cells (DMFC) by as much as 34% as compared to the cell based on an un-modified Nafion membrane. In addition, PDDA-Pt nanoparticles synthesized with low PDDA/Pt ratios show considerable catalytic activity for the methanol oxidation reaction (MOR) in comparison to a commercial Pt/C catalyst. However, the electrocatalytic activity of PDDA-Pt nanoparticles decreased significantly with the increase in the PDDA/Pt molar ratio, indicating that the excess PDDA inhibits the MOR.  相似文献   

15.
Qingfeng Yi  Fengjuan Niu 《Fuel》2011,90(8):2617-2623
Novel porous Pd particles (nanoPd-PEG, nanoPd-PEG-EDTA, nanoPd-HCHO-EDTA, nanoPd-EG, nanoPd-HCHO and nanoPd-EG-EDTA) were synthesized by a hydrothermal method using different reduction agents in the absence and presence of EDTA and investigated as electrocatalysts for ethanol oxidation in alkaline solutions. Results showed that PdCl2 was hydrothermally reduced to nano-scale palladium particles and a three-dimensional texture was formed for Pd particles. Presence of EDTA was favorable for the formation of Pd nanoparticles with small sizes of ca. 70 nm. Ethanol oxidation on the present Pd catalysts took place at a more negative anodic potential in 1 M NaOH solution. Among the electrocatalysts investigated, the electrocatalytic activity of the nanoPd-HCHO-EDTA was the greatest, which was characterized by the largest anodic peak current density of 151 mA cm−2 and lowest onset oxidation potential of −0.788 V (vs. SCE) for the positive scan. Very low charge transfer resistances on the nanoPd-HCHO-EDTA in 1 M NaOH containing various concentrations of ethanol were obtained according to the analysis for electrochemical impedance spectra (EIS). The prepared porous Pd catalysts were promising alternatives to Pt electrodes applied in alkaline direct alcohol fuel cells.  相似文献   

16.
The electrosynthesis of polyaniline on the bare aluminum and pre-treated aluminum surface achieved in aqueous H2PtCl6 solution saturated with NaF for few seconds is described. The effect of some factors such as pre-treatment time, aniline and sulfuric acid concentrations on the electropolymerization process was investigated and optimum conditions were obtained. The stability of polyaniline film on the pre-treated aluminum electrode (Al-Pt) was studied as function of the potential imposed on the electrode. For applied electrode potentials of 0.1-0.7 V, the first-order degradation rate constant, k, of polyaniline film varies between 1 × 10−6 and 2 × 10−5 s−1, and a relatively low slope (i.e. 2.1) was obtained for the plot of log k versus E. The coatings were characterized by scanning electron microscopy (SEM), and cyclic voltammetric behavior of the polyaniline-deposited Al electrode (Al/PANI) and polyaniline-deposited Al-Pt electrode (Al-Pt/PANI) in 0.1 H2SO4 solutions is described. The electrocatalytic activity of the Al-Pt/PANI electrode against para-benzoquinone/hydroquinone (Q/H2Q) and Fe(CN)63−/Fe(CN)64− redox systems was investigated and the obtained results are compared with those obtained on Al/PANI and bulk Pt electrodes.  相似文献   

17.
Micelle-encapsulated multi-walled carbon nanotubes (MWCNTs) with sodium dodecyl sulfate (SDS) were used as catalyst support to deposit platinum nanoparticles. High resolution transmission electron microscopy (HRTEM) images reveal the crystalline nature of Pt nanoparticles with a diameter of ∼4 nm on the surface of MWCNTs. A single proton exchange membrane fuel cell (PEMFC) with total catalyst loading of 0.2 mg Pt cm−2 (anode 0.1 and cathode 0.1 mg Pt cm−2, respectively) has been evaluated at 80 °C with H2 and O2 gases using Nafion-212 electrolyte. Pt/MWCNTs synthesized by using modified SDS-MWCNTs with high temperature treatment (250 °C) showed a peak power density of 950 mW cm−2. Accelerated durability evaluation was carried out by conducting 1500 potential cycles between 0.1 and 1.2 V with 50 mV s−1 scan rate, H2/N2 at 80 °C. The membrane electrode assembly (MEA) with Pt/MWCNTs showed superior performance stability with a power density degradation of only ∼30% compared to commercial Pt/C (70%) after potential cycles.  相似文献   

18.
Cubic Pt nanoparticles were prepared from a solution of K2PtCl4 containing sodium polyacrylate as a capping reagent. The effects of the Pt/polymer molar ratio, the average molecular weight (Mw) of the polymer, and reaction temperature on the shape and size were investigated. When the polymer of Mw = 5100 was added at a molar ratio of Pt/polymer = 1/12, cubic platinum nanoparticles of an average size of 10.3 nm were predominantly formed (ca. 50% in number) at 25 °C. The electron diffraction pattern of the cubic nanoparticles revealed that they are single crystals with Pt {1 0 0} faces on the surface.The cubic nanoparticles were electrochemically active, and showed strong features of Pt {1 0 0} faces on cyclic voltammogram under argon atmosphere. After repeated potential cycling in the range 0.05-1.4 V, the features of Pt {1 0 0} were gradually lost, and changed to those of polycrystalline Pt. Rotating ring disk electrode measurements in O2-saturated H2SO4 solution revealed that the cubic nanoparticles had a high catalytic activity for oxygen reduction reaction (ORR). After polycrystallization by repeated potential cycling, the activity for ORR and hydrogen peroxide formation decreased slightly, which were attributed to the surface structural change from Pt {1 0 0} to polycrystalline.  相似文献   

19.
The ruthenium oxide nanoparticles dispersed on multi-wall carbon nanotubes (CNTs) were successfully synthesized via microwave-polyol process combined with forced hydrolysis without additional thermal oxidation or electrochemical oxidation treatment. The HRTEM, Raman spectra and TGA curve indicate that CNTs were uniformly coated with crystalline and partially hydrous RuO2·0.64H2O nanoparticles of 2 nm diameter and the loading amount of ruthenium oxide in the composite could be controlled up to 70 wt.%. The specific capacitance was 450 Fg−1 of ruthenium oxide/CNT composite electrode with 70 wt.% ruthenium oxide at the potential scan rate of 10 mV s−1 and it decreased to 362 Fg−1 by 18% at 500 mV s−1. The specific capacitance of ruthenium oxide in the composite was 620 Fg−1 of ruthenium oxide at 10 mV s−1. The ruthenium oxide nanoparticles in ruthenium oxide/CNT nanocomposite electrode had a high ratio of outer charge to total charge of 0.81, which confirmed its high-rate capability of the composite through the preparation of the nano-sized ruthenium oxide particles on the external surface of CNTs.  相似文献   

20.
Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La0.8Sr0.2)(Co0.8Fe0.2)O3 cathode using H2 fuel containing 3 vol% H2O. A maximum power density, 436 mW/cm2, was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N2 atmosphere of 10−15-100 Pa oxygen partial pressures (Po2) at 773-1073 K was independent of Po2, which indicated the diffusion of oxide ions. The conductivity of GDC in H2O/H2 atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H2 → 2H+ + 2e). The hole conductivity was observed at 873 K in Po2 = 100-104 Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H2 fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.  相似文献   

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