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1.
A high active Pt/C(b) catalyst was prepared by chemical reduction. The experimental results showed that the Pt/C(b) catalyst formed by reduction of hexachloroplatinic acid with formic acid has excellent catalytic properties for methanol and adsorbed CO(COad) electro-oxidation. The electrocatalytic activity of the catalyst was characterized as having a specific surface activity of 33.38 mA cm−2 at 0.6 V (versus Ag-AgCl). The Pt in the catalyst was well dispersed on carbon with an electrochemically-active specific surface area (ESA) of 84.16 m2 g−1 and a BET specific surface area of 192.34 m2 g−1 and an average particle size of about 2.6 nm. The catalyst showed a very good stability for 12 h.  相似文献   

2.
The performance of high temperature polymer electrolyte fuel cell (HT-PEMFC) using platinum supported over tin oxide and Vulcan carbon (Pt/SnOx/C) as cathode catalyst was evaluated at 160-200 °C and compared with Pt/C. This paper reports first time the Pt/SnOx/C preparation, fuel cell performance, and durability test up to 200 h. Pt/SnOx/C of varying SnO compositions were characterized using XRD, SEM, TEM, EDX and EIS. The face-centered cubic structure of nanosized Pt becomes evident from XRD data. TEM and EDX measurements established that the average size of the Pt nanoparticles were ∼6 nm. Low ionic resistances were derived from EIS, which ranged from 0.5 to 5 Ω-cm2 for cathode and 0.05 to 0.1 Ω-cm2 for phosphoric acid, doped PBI membrane. The addition of the SnOx to Pt/C significantly promoted the catalytic activity for the oxygen reduction reaction (ORR). The 7 wt.% SnO in Pt/SnO2/C catalyst showed the highest electro-oxidation activity for ORR. High temperature PEMFC measurements performed at 180 °C under dry gases (H2 and O2) showed 0.58 V at a current density of 200 mA cm−2, while only 0.40 V was obtained in the case of Pt/C catalyst. When the catalyst contained higher concentrations of tin oxide, the performance decreased as a result of mass transport limitations within the electrode. Durability tests showed that Pt/SnOx/C catalysts prepared in this work were stable under fuel cell working conditions, during 200 h at 180 °C demonstrate as potential cathode catalyst for HT-PEMFCs.  相似文献   

3.
Design of novel nano-scale catalysts with high activity and low cost for methanol oxidation reaction is crucial for the development of direct methanol fuel cell. In this study, MnOx, Pt and Pb were forced to precipitate successively on the surface of carbon nanotubes for fabricating a PtPb/MnOx-CNTs catalyst. Physical characterizations indicated that there existed a mass of Mn (IV, Ⅴ), Pb (Ⅱ) and Pt (0) species, and partial alloying between Pt and Pb in this catalyst. Methanol oxidation reaction with this novel composite exhibited over 3 times higher specific activity (140.9 mA cm−2) and somewhat lower onset potential (−0.1 V vs. Hg/Hg2SO4) than the values on Pt/CNTs (44.2 mA cm−2 and 0 V, respectively). Fundamental understanding in reaction mechanisms enabled us to reveal the distinguishing functions between Pb and MnOx in methanol oxidation processes. The addition of Pb resulted in the enhanced intrinsic activity towards electro-oxidation of residual intermediate species, while dehydrogenation in methanol oxidation processes was obviously improved by using MnOx-CNTs as a support.  相似文献   

4.
A simple, rapid and energy-saving method has been used to synthesize nanostructured tungsten carbide on graphitized carbon (WC/gC) materials. The procedures include the ion exchange of the ion-exchange resin as original precursor with targeting ions and heat treatment by an intermittent microwave heating (IMH) method. The resulting product was loaded by Pt nanoparticles to form a uniformly dispersed nanocomposite (Pt-WC/gC). The samples are characterized by physical and electrochemical methods. The Pt-WC/gC as electrocatalyst for oxygen reduction reaction shows high activity proved by the Pt-mass activity of 207.4 mA mg−1Pt which is much higher than that of 107.4 mA mg−1Pt on Pt/C at 0.9 V. The onset potential for methanol oxidation is 100 mV more negative than that on Pt/C electrocatalyst. The synthesis of other types of nanomaterials based on this method is current under way to demonstrate the general suitability.  相似文献   

5.
Phase pure WC nanoparticles were synthesized on high surface area carbon black (800 m2 g−1) by a temperature programmed reaction (TPR) method. The particle size of WC can be controlled under 30 nm with a relatively high coverage on the carbon surface. The electrochemical testing results demonstrated that the corrosion resistance of carbon black was improved by 2-fold with a surface modification by phase pure WC particles. However, the WC itself showed some dissolution under potential cycling. Based on the X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis, most of the WC on the surface was lost or transformed to oxides after 5000 potential cycles in the potential range of 0.65-1.2 V. The Pt catalyst supported on WC/C showed a slightly better ORR activity than that of Pt/C, with the Pt activity loss rate for Pt/WC/C being slightly slower compared to that of Pt/C. The performance and decay rate of Pt/WC/C were also evaluated in a fuel cell.  相似文献   

6.
A direct alkaline fuel cell with a liquid potassium hydroxide solution as an electrolyte is developed for the direct use of methanol, ethanol or sodium borohydride as fuel. Three different catalysts, e.g., Pt-black or Pt/Ru (40 wt.%:20 wt.%)/C or Pt/C (40 wt.%), with varying loads at the anode against a MnO2 cathode are studied. The electrodes are prepared by spreading the catalyst slurry on a carbon paper substrate. Nickel mesh is used as a current-collector. The Pt–Ru/C produces the best cell performance for methanol, ethanol and sodium borohydride fuels. The performance improves with increase in anode catalyst loading, but beyond 1 mg cm−2 does not change appreciably except in case of ethanol for which there is a slight improvement when using Pt–Ru/C at 1.5 mA cm−2. The power density achieved with the Pt–Ru catalyst at 1 mg cm−2 is 15.8 mW cm−2 at 26.5 mA cm−2 for methanol and 16 mW cm−2 at 26 mA cm−2 for ethanol. The power density achieved for NaBH4 is 20 mW cm−2 at 30 mA cm−2 using Pt-black.  相似文献   

7.
Carbon supported Pt3Y (Pt3Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH4, the alloy catalysts exhibited 10-20% higher mass activity (mA mgPt−1) than comparably synthesized Pt/C catalyst. The specific activity (μA cmPt−2) was 23 and 65% higher for the Pt3Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 °C under a reducing atmosphere, Pt3Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 °C) catalysts exhibited specific activities of 334 and 393 μA cmPt−2, respectively, while those of the Pt3Y/C-900 and PtY/C-900 catalysts were 492 and 1050 μA cmPt−2, respectively. X-ray diffraction results revealed that both the Pt3Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt3Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation.  相似文献   

8.
Carbon supported Pt and Pt-Ni (1:1) nanoparticles were prepared by reduction of metal precursors with NaBH4. XRD analysis indicated that only a small amount of Ni alloyed with Pt (Ni atomic fraction in the alloy about 0.05). The as-prepared catalysts were submitted to chronoamperometry (CA) measurements to evaluate their activity for the oxygen reduction reaction (ORR). CA measurements showed that the ORR activity of the as-prepared Ni-containing catalyst was higher than that of pure Pt. Then, their stability was studied by submitting these catalysts to durability tests involving either 30 h of constant potential (CP, 0.8 V vs. RHE) operation or repetitive potential cycling (RPC, 1000 cycles) between 0.5 and 1.0 V vs. RHE at 20 mV s−1. After 30 h of CP operation at 0.8 V vs. RHE, loss of all non-alloyed Ni, partial dissolution of the Pt-Ni alloy and an increase of the crystallite size was observed for the Pt-Ni/C catalyst. The ORR activity of the Pt-Ni/C catalyst was almost stable, whereas the ORR activity of Pt/C slightly decreased with respect to the as-prepared catalyst. Loss of all non-alloyed and part of alloyed Ni was observed for the Pt-Ni/C catalyst following repetitive potential cycling. Conversely to the results of 30 h of CP operation at 0.8 V vs. RHE, after RPC the ORR activity of Pt-Ni/C was lower than that of both as-prepared Pt-Ni/C and cycled Pt/C. This result was explained in terms of Pt surface enrichment and crystallite size increase for the Pt-Ni/C catalyst.  相似文献   

9.
Platinum nanoparticles were electrodeposited on ordered silicon nanocones (SNCs) and used as the catalyst for methanol electro-oxidation in direct methanol fuel cells (DMFCs). Because of uniform dispersion of Pt nanoparticles and the high surface area, the Pt-SNC electrode exhibited superior electrocatalytic properties toward the methanol electro-oxidation, with the onset potential of 0.08 V (vs. SCE). According to chronoamperometric analysis and CO stripping cyclic voltammetric (CV) study, the Pt/SNC electrode had a stable electro-oxidation activity with a very good CO tolerance. The Si surface oxide surrounding the Pt nanoparticles on the SNCs was suggested to play a key role in improving the CO tolerance via the bifunctional mechanism.  相似文献   

10.
The electrochemical stability of non-precious FeCo-EDA and commercial Pt/C cathode catalysts for zinc air battery have been compared using accelerated degradation test (ADT) in alkaline condition. Outstanding oxygen reduction reaction (ORR) stability of the FeCo-EDA catalyst was observed compared with the commercial Pt/C catalyst. The FeCo-EDA catalyst retained 80% of the initial mass activity for ORR whereas the commercial Pt/C catalyst retained only 32% of the initial mass activity after ADT. Additionally, the FeCo-EDA catalyst exhibited a nearly three times higher mass activity compared to that of the commercial Pt/C catalyst after ADT. Furthermore, single cell test of the FeCo-EDA and Pt/C catalysts was performed where both catalysts exhibited pseudolinear behaviour in the 12-500 mA cm−2 range. In addition, 67% higher peak power density was observed from the FeCo-EDA catalyst compared with commercial Pt/C. Based on the half cell and single cell tests the non-precious FeCo-EDA catalyst is a very promising ORR electrocatalyst for zinc air battery.  相似文献   

11.
In this report, calcium ions in the porous hydroxyapatite (HAp) microspheres are partially exchanged with ferrous ions to form iron contained hydroxyapatite (FeHAp) on which Pt ions in H2PtCl6 solution are reduced to form Pt/FeHAp catalyst and finally mixed with carbon blacks to derive Pt/FeHAp/C catalysts. They exhibit the characteristics of Pt (1 1 0) facet with a sharp desorption peak at −0.109 V (vs. Ag/AgCl), the electrochemical surface area (ECSA) ranging from 73 to 224 m2 g−1 with little CO poisoning effect on Pt, and the mass activity ranging from 6.88 to 28.99 A gPt−1 in methanol oxidation reaction (MOR) at 0.4 V (vs. Ag/AgCl). Besides, Pt/FeHAp reveals the lower onset potential in CO-stripping than Pt/C. These better performances of Pt/FeHAp/C catalysts, compared with Pt/C, are also related to the Pt (1 1 0) facet, the content of Fe, and the coexistence of Pt0 and Pt2+ in Pt/FeHAp.  相似文献   

12.
The effect of an anodic treatment on the methanol oxidation activity of PtRu/C (50:50 at.%) and PtNiCr/C (Pt:Ni:Cr = 28:36:36 at.%) catalysts was investigated for various potential limits of 0.9, 1.1, 1.3 and 1.4 V (vs. reference hydrogen electrode, RHE). NaBH4 reduced catalysts were further reduced at 900 °C for 5 min in an argon balanced hydrogen flow stream. Improved alloying was obtained by the hydrogen reduction procedure as confirmed by X-ray diffraction results. In the PtRu/C catalyst, a decrease of irreversible Ru (hydrous) oxide formation was observed when the anodic treatment was performed at 1.1 V (vs. RHE) or higher potentials. In chronoamperometry testing performed for 60 min at 0.6 V (vs. RHE), the highest activity of the PtRu/C catalyst was observed when anodic treatment was performed at 1.3 V (vs. RHE). The current density increased from 1.71 to 4.06 A gcat.−1 after the anodic treatment. In the PtNiCr/C catalyst, dissolution of Ni and Cr was observed when potentials ≥1.3 V (vs. RHE) were applied during the anodic treatment. In MOR activity tests, the current density of the PtNiCr/C catalyst dramatically increased by more than 13.5 times (from 0.182 to 2.47 A gcat.−1) when an anodic treatment was performed at 1.4 V. On an A gnoble metal−1 basis, the current density of PtNiCr-1.4V is slightly higher than the best anodically treated PtRu-1.3V catalyst, suggesting the PtNiCr catalyst is a promising candidate to replace the PtRu catalysts.  相似文献   

13.
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   

14.
The structure of Pt nanoparticles and the composition of the catalyst-Nafion films strongly determine the performance of proton exchange membrane fuel cells. The effect of Nafion content in the catalyst ink, prepared with a commercially available carbon-supported Pt, in the kinetics of the hydrogen oxidation reaction (HOR), has been studied by the thin layer rotating disk electrode technique. The kinetic parameters have been related to the catalyst nanoparticles structure, characterized by X-ray diffraction and high-resolution transmission electron microscopy. The size-shape analysis is consistent with the presence of 3D cubo-octahedral Pt nanoparticles with average size of 2.5 nm. The electrochemically active surface area, determined by CO stripping, appears to depend on the composition of the deposited Pt/C-Nafion film, with a maximum value of 73 m2 gPt−1 for 30 wt.% Nafion. The results of CO stripping indicate that the external Pt faces are mainly (1 0 0) and (1 1 1) terraces, thus confirming the cubo-octahedral structure of nanoparticles. Cyclic voltammetry combined with the RDE technique has been applied to study the kinetic parameters of HOR besides the ionomer resistance effect on the anode kinetic current at different ionomer contents. The kinetic parameters show that H2 oxidation behaves reversibly with an estimated exchange current density of 0.27 mA cm−2.  相似文献   

15.
A series of Pt-Ir thin films envisaged for application as fuel cell cathodic catalysts are deposited by dc co-sputtering from pure metal targets. To achieve different metal ratios, the sputtering power applied on the iridium target (PIr) is varied in the range 0-100 W at constant power of the Pt target (PPt). The influence of the sputtering power on the film composition, morphology, and surface structure is analysed by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The catalytic activity towards oxygen reduction reaction (ORR) is evaluated in sulphuric acid solutions applying the methods of cyclic voltammetry and potentiodynamic polarization curves. The performed morphological and electrochemical investigations reveal that catalytic efficiency of the co-sputtered Pt-Ir films is superior compared to pure Pt. The ORR is most intensive on the sample deposited at power ratio PPt:PIr = 100:30 W containing 11 at.% Ir that has also the most developed active surface. The ORR current density for this film achieved at 0.825 V in acid solution (4.1 mA cm−2) is about 6 times higher than for pure Pt (0.67 mA cm−2). The improved activity of the thin co-sputtered Pt-Ir over Pt allows for essential reduction of the catalyst loading at preserved performance.  相似文献   

16.
The Pt nanoparticles have been well dispersed on electrospinning-derived carbon fibrous mats (CFMs) by using formaldehyde vapor as reducer to react with H2PtCl6·6H2O adsorbed on the CFMs at 160 °C. The prepared electrodes of Pt-CFMs have been characterized by using scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectroscopy, and the performance of the electrodes for methanol oxidation has been investigated by using cyclic voltammetry, chronoamperometry, quasi-steady state polarization and electrochemical impedance spectroscopy techniques. The results demonstrate that Pt-CFMs electrodes exhibit peak current density of 445 mA mg−1 Pt, exchange current of 235.7 μA cm−2, charge transfer resistance of 16.1 Ω cm2 and better stability during the process of methanol oxidation, which are superior to the peak current density of 194 mA mg−1 Pt, exchange current of 174.7 μA cm−2 and charge transfer resistance of 39.4 Ω cm2 obtained for commercial Pt/C supported on CFMs. It indicates that the novel process in which formaldehyde vapor is used as reducer to prepare Pt catalyst with high performance can be developed.  相似文献   

17.
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   

18.
Preparation and characterization of a platinum (Pt)-based catalyst using a redox polymer, poly(vinylferrocenium) (PVF+), as the support material was described. Pt was obtained from aqueous solution of K2PtCl4 in the complex form. Pt particles were reduced by chemical and electrochemical means. Chemical reduction was performed using aqueous hydrazine solution and electrochemical reduction was carried out in H2SO4 solution. The Pt/PVF+ catalyst system showed catalytic activity towards methanol oxidation. Cyclic voltammetry was used for the electrochemical characterization of the catalyst system. Scanning electron microscopy (SEM) images and energy dispersive X-ray spectrum (EDS) of the catalyst system were also recorded. The system was tested in a single fuel cell configuration at ambient temperature and atmospheric pressure. The open circuit voltage (OCV) was 680 mV for the system and the maximum power density was 0.31 mW cm−2 at a current density of 0.63 mA cm−2. Catalytic activity of Pt/PVF+ system towards methanol oxidation was comparable with the related catalysts in the literature.  相似文献   

19.
This work reports the electrochemical measurements of 20 wt.% RuxSey/C for oxygen reduction reaction (ORR) in presence of different concentration of HCOOH and its use as cathode catalyst in a microfluidic formic acid fuel cell (μFAFC). The results were compared to those obtained with commercial Pt/C. Half-cell electrochemical measurements showed that the chalcogenide catalyst has a high tolerance and selectivity towards ORR in electrolytes containing up to 0.1 M HCOOH. The depolarization effect was higher on Pt/C than on RuxSey/C by a factor of ca. 23. Both catalysts were evaluated as cathode of a μFAFC operating with different concentrations of HCOOH. When 0.5 M HCOOH was used, maximum current densities of 11.44 mA cm−2 and 4.44 mA cm−2 were obtained when the cathode was RuxSey/C and Pt/C, respectively. At 0.5 M HCOOH, the peak power density of the μFAFC was similar for both catalysts, ca. 1.9 mW cm−2. At 5 M HCOOH the power density of the μFAFC using RuxSey, was 9.3 times higher than the obtained with Pt/C.  相似文献   

20.
Carbon supported binary Pt-Ti alloys were investigated for application in methanol electro-oxidation (MOR) and oxygen electro-reduction reactions (ORR). Various compositions of Pt100−xTix/C (x = 0, 25, 50, and 75) catalysts were synthesized by sequential impregnation of Pt and Ti followed by annealing at 900 °C for 30 min under H2/Ar flow. X-ray diffraction results showed formation of the Pt3Ti intermetallic phase in Pt50Ti50 and Pt25Ti75 catalysts after annealing at 900 °C. The Pt50Ti50/C-900 and Pt25Ti75/C-900 catalysts (the ‘-900’ designation indicates the catalyst was annealed at 900 °C) exhibited 103% () and 198% () higher MOR activity, respectively, than in the Pt/C-900 catalyst () at 0.7 V (vs. reversible hydrogen electrode (RHE)). These two catalysts also showed high ORR activity. From a specific activity basis, the Pt50Ti50/C-900 and Pt25Ti75/C-900 catalysts exhibited , respectively, which were 171 and 154% higher than the value of the Pt/C catalyst at 0.8 V (vs. RHE). Methanol-tolerant ORR activity was also investigated, but in the presence of methanol, the Pt50Ti50/C-900 and Pt25Ti75/C-900 catalysts both exhibited poor ORR activity.  相似文献   

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