首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
One promising preparative method that offers the potential for improved platinum (Pt) dispersion of electrocatalysts is electroless deposition (ED). In this study, the effects of multiwalled carbon nanotubes (MWCNTs) pretreatment and synthesis procedure on properties of the four catalysts, synthesized by ED method, have been considered. The results of energy-dispersive X-ray spectroscopy (EDS), X-ray dot-mapping, X-ray fluorescence (XRF) and cyclic voltammetry (CV) analyses showed that using palladium (Pd) precursor during two-step sensitization-activation coating procedure gives uniform Pt particles distribution on MWCNTs with low aggregation and high specific surface area (∼80 m2 g−1). In addition, to investigate the performance of the synthesized catalysts in experimental fuel cell system, thin-film method was used to fabricate the membrane electrode assemblies (MEAs). Obtaining the polarization curves for the fabricated MEAs (Pt loading ∼0.4 mg cm−2) and a commercial MEA (ElectroChem, Pt loading ∼1 mg cm−2) demonstrated that the catalyst prepared by two-step sensitization-activation coating procedure possesses a good performance despite of its lower Pt content.  相似文献   

2.
The performance of proton exchange membrane fuel cells (PEMFC) fed with CO-contaminated hydrogen was investigated for anodes with PtWOx/C and phosphotungstic acid (PTA) impregnated Pt/C electrocatalysts. A quite high performance was achieved for the PEMFC fed with H2 + 100 ppm CO with anodes containing 0.4 mg PtWOx cm−2 and also for those with 0.4 mg Pt cm−2 impregnated with ca. 1 mg PTA cm−2. A decay of the single cell performance with time is observed, and this was attributed to an increase of the membrane resistance due to the polymer degradation promoted by the crossover of the tungsten species throughout the membrane.  相似文献   

3.
The performance of a proton exchange membrane fuel cell (PEMFC) with gas diffusion cathodes having the catalyst layer applied directly onto Nafion membranes is investigated with the aim at characterizing the effects of the Nafion content, the catalyst loading in the electrode and also of the membrane thickness and gases pressures. At high current densities the best fuel cell performance was found for the electrode with 0.35 mg Nafion cm−2 (15 wt.%), while at low current densities the cell performance is better for higher Nafion contents. It is also observed that a decrease of the usual Pt loading in the catalyst layer from 0.4 to ca. 0.1 mg Pt cm−2 is possible, without introducing serious problems to the fuel cell performance. A decrease of the membrane thickness favors the fuel cell performance at all ranges of current densities. When pure oxygen is supplied to the cathode and for the thinner membranes there is a positive effect of the increase of the O2 pressure, which raises the fuel cell current densities to very high values (>4.0A cm−2, for Nafion 112—50 μm). This trend is not apparent for thicker membranes, for which there is a negligible effect of pressure at high current densities. For H2/air PEMFCs, the positive effect of pressure is seen even for thick membranes.  相似文献   

4.
The article reports on the results of a 780 h life test of high temperature MEA with PBI-H3PO4 membrane. The MEA was loaded by current density 0.2 A cm−2 for 763 h at 160 °C in hydrogen-air feed. The load was discontinued 14 times during the life test including three complete shut downs. In the course of the life test MEA characteristics were studied by electrochemical methods. Pt particle size growth was evaluated by ex situ measurements of electrochemical hydrogen adsorption/desorption with the cathode catalyst sampled after the life test and with pristine catalyst. Possible changes of electrochemically active surface area (ESA) of carbon support were monitored by electrochemical impedance studies (EIS) performed in the course of the MEA life test. Average Pt particle diameter was found 3.8 and 7.8 nm for pristine catalyst and for catalyst sampled after the life test, respectively. ESA of carbon support remained unchanged, membrane resistance decreased by ∼20%, hydrogen crossover increased by a factor of 14, although remained insignificant. Voltage loss rate in the life test was ∼25 μV h−1. The major cause of the MEA degradation was identified as a loss of Pt ESA by particle size growth.  相似文献   

5.
ATR-FTIRAS measurements were conducted to investigate nature of water molecules co-adsorbed with CO on highly dispersed PtRu alloy and Pt catalysts supported on carbon black in the temperature range between 23 °C and 60 °C. Each catalyst was uniformly dispersed and fixed by Nafion® film of 0.0125 μm thickness on a chemically deposited gold film. Adsorption of CO was conducted and monitored by ATR-FTIRAS for 30 min in 1% CO saturated 0.1 M HClO4 after stepping the potential from 1.2 V and 1.0 V to 0.05 V on Pt/C and PtRu/C, respectively. Similar atop and bridge bonded CO bands were observed on both PtRu/C and Pt/C, but a smaller relative band intensity, bridge bonded vs. atop CO, was observed on PtRu/C compared to Pt/C. A distinct O-H stretching band was found around 3643 cm−1 and 3630 cm−1 on PtRu/C and Pt/C, respectively, upon CO adsorption. They are assigned to non-hydrogen bonded water molecules co-adsorbed with CO on these catalysts. We found that the number of non-hydrogen bonded water molecules co-adsorbed with a given number of CO molecules decreases with increasing temperature and is higher on PtRu/C than Pt/C at each temperature. We interpret the higher ability of water co-adsorption at PtRu/C over Pt/C is due to stronger H2O-metal interactions on the alloy surface. We present a model of the CO-H2O co-adsorbed layer based on the bilayer model of water on metal surfaces.  相似文献   

6.
CO tolerance of H2-air single cell with phosphoric acid doped polybenzidazole (PA-PBI) membrane was studied in the temperature range 140-180 °C using either dry or humidified fuel. Fuel composition was varied from neat hydrogen to 67% (vol.) H2-33% CO mixtures. It was found that poisoning by CO of Pt/C and Pt-Ru/C hydrogen oxidation catalysts is mitigated by fuel humidification. Electrochemical hydrogen oxidation at Pt/C and Pt-Ru/C catalysts in the presence of up to 50% CO in dry or humidified H2-CO mixtures was studied in a cell driven mode at 180 °C. High CO tolerance of Pt/C and Pt-Ru/C catalysts in FC with PA-PBI membrane at 180 °C can be ascribed to combined action of two factors—reduced energy of CO adsorption at high temperature and removal of adsorbed CO from the catalyst surface by oxidation. Rate of electrochemical CO oxidation at Pt/C and Pt-Ru/C catalysts was measured in a cell driven mode in the temperature range 120-180 °C. Electrochemical CO oxidation might proceed via one of the reaction paths—direct electrochemical CO oxidation and water-gas shift reaction at the catalyst surface followed by electrochemical hydrogen oxidation stage. Steady state CO oxidation at Pt-Ru/C catalyst was demonstrated using CO-air single cell with Pt-Ru/C anode. At 180 °C maximum CO-air single cell power density was 17 mW cm−2 at cell voltage U = 0.18 V.  相似文献   

7.
Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H3PW12O40 (PW12). Comparison was made to bare (PW12-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm−3 H2SO4 electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm−2) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW12 proceeded at ca. 30-60 mV more positive potential (depending on the PW12 content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW12-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm−2) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW12 relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.  相似文献   

8.
The rotating disk electrode (RDE) is a useful technique for precise determination of exchange current density (j0) in electrochemistry. For the study of powder catalysts, a common practice is to apply the powder onto an inert disk substrate (such as glassy carbon). However, this approach in its usual version will lead to wrong results for the exchange current density of hydrogen electrode reactions at carbon-supported Pt nanoparticles (Pt/C) because of the poor utilization of the loaded Pt nanoparticles. Our new approach is to dilute the Pt/C powder with a large amount of pristine carbon support to make the catalyst layer. In this way, all the catalyst particles in the catalyst layer have nearly the same and much enhanced mass transport so that rational exchange current density can be obtained. Using the new approach, the current density for hydrogen electrode reactions at Pt/C in 0.1 M perchloric acid at 25 °C is found to be 27.2 ± 3.5 mA/cm2 with an apparent activation energy 43 kJ/mol. These results are in agreement with the j0 estimation based on real fuel cell experiments.  相似文献   

9.
A new procedure has been introduced to enhance catalytic activity of ruthenium-selenium electro-catalysts for oxygen reduction, in which materials are treated under hydrogen atmosphere at elevated temperatures. The characterisation using scanning electron microscopy, energy dispersive spectroscopy or energy dispersive X-ray spectroscopy exhibited that the treatment at 400 °C made catalysts denser while their porous nature remained, led to a good degree of crystallinity and an optimum Se:Ru ratio. The half cell test confirms feasibility of the new procedure; the catalyst treated at 400 °C gave the highest reduction current (55.9 mA cm−2 at −0.4 V) and a low methanol oxidation effect coefficient (3.8%). The direct methanol fuel cell with the RuSe 400 °C cathode catalyst (2 mg RuSe cm−2) generated a power density of 33.8 mW cm−2 using 2 M methanol and 2 bar oxygen at 90 °C. The new procedure produced the catalysts with low decay rates. The best sample was compared to the Pt and to the reported ruthenium-selenium catalyst. Possible reasons for the observations are discussed.  相似文献   

10.
Micro- and mesoporous carbide-derived carbon (CDC) was synthesised from molybdenum carbide (Mo2C) powder by gas phase chlorination in the temperature range from 400 to 1200 °C. Analysis of XRD results show that C(Mo2C), chlorinated at 1200 °C, consist mainly on graphitic crystallites of mean size, La = 9 nm and Lc = 7.5 nm. The first-order Raman spectra showed the graphite-like absorption peak at ∼1587 cm−1 and the disorder-induced (D) peak at ∼1348 cm−1. The low-temperature N2 adsorption experiments were performed and a specific surface area up to 1855 m2 g−1 and total pore volume up to 1.399 cm3 g−1 were obtained. Sorption measurements showed the presence of both micro- and mesopores after chlorination at 400-900 °C and only mesopores after chlorination at 1000°-1200 °C. Stepwise formation of micro- and mesopores was achieved and the peak pore size can be shifted from 0.8 nm up to 4 nm by increasing the chlorination temperature.  相似文献   

11.
Alar Jänes  Heisi Kurig  Enn Lust 《Carbon》2007,45(6):1226-1233
Commercial nanoporous carbon RP-20 was activated with water vapor in the temperature range from 950 °C to 1150 °C. The XRD analysis was carried out on nanoporous carbon powder samples to investigate the structural changes (graphitisation) in modified carbon that occurred at activation temperatures T ? 1150 °C. The first-order Raman spectra showed the absorption peak at 1582 cm−1 and the disorder (D) peak at 1350 cm−1. The low-temperature N2 adsorption experiments were performed at −196 °C and a specific surface area up to 2240 m2g−1 for carbon activated at T = 1050 °C was measured. The cell capacitance for two electrode activated nanoporous carbon system advanced up to 60 F g−1 giving the specific capacitance ∼240 F g−1 to one electrode nanoporous carbon ∣1.2 M (C2H5)3CH3NBF4 + acetonitrile solution interface. A very wide region of ideal polarisability for two electrode system (∼3.2 V) was achieved. The low frequency limiting specific capacitance very weakly increases with the rise of specific area explained by the mass transfer limitations in the nanoporous carbon electrodes. The electrochemical characteristics obtained show that some of these materials under discussion can be used for compilation of high energy density and power density non-aqueous electrolyte supercapacitors with higher power densities than aqueous supercapacitors.  相似文献   

12.
This study bridges the structure/composition of Pt-Co/C nanoparticles with their surface reactivity and their electrocatalytic activity. We show that Pt3Co/C nanoparticles are not stable during PEMFC operation (H2/air; j = 0.6 A cm−2, T = 70 °C) but suffer compositional changes at the nanoscale. In the first hours of operation, the dissolution of Co atoms at their surface yields to the formation of a Pt-enriched shell covering a Pt-Co alloy core (“Pt-skeleton”) and increases the affinity of the surface to oxygenated and hydrogenated species. This structure does not ensure stability in PEMFC conditions but is rather a first step towards the formation of “Pt-shell/Pt-Co alloy core” structures with depleted Co content. In these operating conditions, the Pt-Co/C specific activity for the ORR varies linearly with the fraction of Co alloyed to Pt present in the core and is severely depreciated (ca. −50%) after 1124 h of operation. This is attributed to: (i) the decrease of both the strain and the ligand effect of Co atoms contained in the core (ii) the changes in the surface structure of the electrocatalyst (formation of a multilayer-thick Pt shell) and (iii) the relaxation of the Pt surface atoms.  相似文献   

13.
A new approach based on stepwise oxidation of o-anisidine is explored for generating nanoporous films of poly(o-anisidine), POA and loading of Pt nanoparticles that are subsequently used for electrocatalysis of methanol oxidation are presented and compared with bulk Pt. POA film can easily be prepared by stepwise electro-oxidation procedure with very high porosity consisting of nanofibrillar structure using without templates. Controlled sizes of Pt nanoparticles were entrapped into POA matrix by a two-step process in which first PtCl62− ions are sorbed into the pores of polymer matrix followed by electroreduction at −0.55 V in a 0.5 M H2SO4 solution. Loading of Pt nanoparticles (10-200 μg/cm2) onto POA matrix were accomplished by varying the concentration (2-10 mM) of the sorbate, i.e., H2PtCl6. The sizes of the Pt nanoparticles were determined from TEM analysis and Pt particles were found to be in the range of 10-20 nm. The crystallite phase of Pt particles in POA was examined from XRD pattern. AFM image further supports Pt particles embedded in POA matrix.  相似文献   

14.
Membrane electrode assemblies (MEA) were prepared using PtRu black and 60 wt.% carbon-supported platinum (Pt/C) as their anode and cathode catalysts, respectively. The cathode catalyst layers were fabricated using various amounts of Pt (0.5 mg cm−2, 1.0 mg cm−2, 2.0 mg cm−2, and 3.0 mg cm−2). To study the effect of carbon support on performance, a MEA in which Pt black was used as the cathode catalyst was fabricated. In addition, the effect of methanol crossover on the Pt/C on the cathode side of a direct methanol fuel cell (DMFC) was investigated. The performance of the single cell that used Pt/C as the cathode catalyst was higher than single cell that used Pt black and this result was pronounced when highly concentrated methanol (above 2.0 M) was used as the fuel.  相似文献   

15.
Nanotubes were coated on the surface of active LiCoO2 particles using electrostatic heterocoagulation to enhance the electrochemical properties of a Li-ion battery. Only 0.5 wt% of multiwalled carbon nanotubes (MWCNTs) was added as a conducting agent into the LiCoO2 cathode, which had a density of 4.0 g cm−3. We found that our electrode that was prepared using heterocoagulation with 0.5 wt% of thin MWCNTs maintained a volumetric capacitance of 403 mAh cm−1 after 40 cycles from the initial 624 mAh cm−1, compared with previous result of 310 mAh cm−1 obtained from simple mixing with 3 wt% MWCNTs. The high volumetric capacity with smaller swelling using less amount of MWCNTs was attributed to the self-assembled nanotube network formed between active particles during coagulation, which was maintained with volume expansion during cycle testing.  相似文献   

16.
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   

17.
Some ternary ferrites with molecular formula, CoFe2−xCrxO4 (0≤x≤1.0) have been synthesized at 70 °C by a precipitation method and were transformed into the film form at the pretreated Ni support (1.5×1.0 cm2) using an oxide-slurry painting technique. The study showed that Cr-substitution from 0.2 to 1.0 mol increased the electrocatalytic activity of the oxide towards the oxygen evolution reaction (OER), the optimum improvement in apparent electrocatalytic activity being with 0.8 mol Cr. At E=600 mV versus Hg/HgO in 1 M KOH (25 °C), the apparent oxygen evolution current density (ja) with the catalyst, CoFe1.2Cr0.8O4, was ∼80 times greater than that observed with the base oxide (i.e. CoFe2O4). The OER on Cr-substituted oxides showed two Tafel slopes, one (b=42±1 mV per decade) at low overpotential and the other (b=66±6 mV per decade) at higher potential. The reaction order with respect to OH concentration was ∼1.3±0.1 for each electrocatalyst. The thermodynamic parameters for the OER, namely, standard apparent electrochemical enthalpy of activation (ΔH°el#), standard enthalpy of activation (ΔH°#) and standard entropy of activation (ΔS°#) have also been determined. It was observed that values of the ΔH°el# and ΔH°# decreased with Cr-substitution in the CoFe2O4 lattice; the decrement, however, being the greatest with 0.8 mol Cr. The ΔS°# values were largely negative varying between ∼−61 and −126 J deg−1 mol−1.  相似文献   

18.
An anhydrous proton conductor, Sn0.95Al0.05P2O7 (SAPO), composed of polystyrene-b-poly(ethylene/propylene)-b-polystyrene (SEPS), was developed and characterized using morphological, structural, and electrochemical analyses. In the composite membrane with 20 wt% SEPS, a homogeneous distribution of SAPO particles in the matrix was obtained in the thickness range of 65-90 μm, yielding a proton conductivity of 3.4 × 10−3 S cm−1 at 200 °C, tensile strength of 4.6 MPa and an elongation at break of 711.0% at room temperature. Fuel cell tests verified that the open-circuit voltage was maintained at a constant value of approximately 1 V between 100 and 250 °C. The peak power densities achieved with unhumidified H2 and air were 77.0 mW cm−2 at 100 °C, 121.0 mW cm−2 at 150 °C, and 163.1 mW cm−2 at 225 °C.  相似文献   

19.
Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO2 nanowires (SnO2NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO2NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO2NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of COads. For a carbon paper electrode loaded with 0.1 mg cm−2 Pt and 0.4 mg cm−2 SnO2NW, a conversion of 54% SnO2NW into Sn metal (0.17 mg cm−2) initiates the COads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO2NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.  相似文献   

20.
2,4,6-Tris(2-pyridyl)-1,3,5-triazine (TPTZ) was used as a ligand to prepare iron-TPTZ (Fe-TPTZ) complexes for the development of a new oxygen reduction reaction (ORR) catalyst. The prepared Fe-TPTZ complexes were then heat-treated at temperatures ranging from 400 °C to 1100 °C to obtain carbon-supported Fe-N catalysts (Fe-N/C). These catalysts were characterized in terms of catalyst composition, structure, and morphology by several instrumental methods such as energy dispersive X-ray, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. With respect to the ORR activity, the Fe-N/C catalysts were also evaluated by cyclic voltammetry, as well as rotating disk and ring-disk electrodes. The results showed that among the heat-treated catalysts, that obtained at a heat-treatment temperature of 800 °C is the most active ORR catalyst. The overall electron transfer number for the catalyzed ORR was determined to be between 3.5 and 3.8, with 10-30% H2O2 production. The ORR catalytic activity of this catalyst was also tested in a hydrogen-air proton exchange membrane (PEM) fuel cell. At a cell voltage of 0.30 V, this fuel cell can give a current density of 0.23 A cm−2 with a maximum MEA power density of 0.070 W cm−2 indicating that this catalyst has potential to be used as a non-noble catalyst in PEM fuel cells.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号