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1.
Precious-metal catalysts (predominantly Pt or Pt-based alloys supported on carbon) have traditionally been used to catalyze the electrode reactions in polymer electrolyte membrane (PEM) fuel cells. However as PEM fuel systems begin to approach commercial reality, there is an impending need to replace Pt with a lower cost alternative. The present study investigates the performance of a carbon-supported tantalum oxide material as a potential oxygen reduction reaction (ORR) catalyst for use on the cathode side of the PEM fuel cell membrane electrode assembly. Although bulk tantalum oxide tends to exhibit poor electrochemical performance due to limited electrical conductivity, it displays a high oxygen reduction potential; one that is comparable to Pt. Analysis of the Pourbaix electrochemical equilibrium database also indicates that tantalum oxide (Ta2O5) is chemically stable under the pH and applied potential conditions to which the cathode catalyst is typically exposed during stack operation. Nanoscale tantalum oxide catalysts were fabricated using two approaches, by reactive oxidation sputtering and by direct chemical synthesis, each carried out on a carbon support material. Nanoscale tantalum oxide particles measuring approximately 6 nm in size that were sputtered onto carbon paper exhibited a mass-specific current density as high as one-third that of Pt when measured at 0.6 V vs. NHE. However, because of the two-dimensional nature of this particle-on-paper structure, which limits the overall length of the triple-phase boundary junctions where the oxide, carbon paper, and aqueous electrolyte meet, the corresponding area-specific current density was quite low. The second synthesis approach yielded a more extended, three-dimensional structure via chemical deposition of nanoscale tantalum oxide particles on carbon powder. These catalysts exhibited a high ORR onset potential, comparable to that of Pt, and displayed a significant improvement in the area-specific current density. Overall, the highest mass-specific current density of the carbon-powder supported catalyst was ˜9% of that of Pt.  相似文献   

2.
The electrochemical stability of tungsten carbide (WC), Pt-modified WC, molybdenum carbide (Mo2C), and Pt-modified Mo2C has been examined using an in situ electrochemical half-cell in combination with X-ray photoelectron spectroscopy (XPS). The WC surface, created via the carburization of a tungsten foil, was electrochemically stable to ∼0.8 V with respect to the normal hydrogen electrode (NHE) when exposed to dilute sulfuric acid. At higher potentials, XPS confirmed the surface oxidation of WC to form WxOy species. The deposition of submonolayer coverage of Pt on the WC surface increased the region of stability of WC, extending the onset of catalyst oxidation to ∼1.0 V (NHE). These results suggest that both WC and Pt/WC have the potential to be used as anode electrocatalysts. In contrast, both Mo2C and Pt-modified Mo2C underwent oxidation at ∼0.4 V (NHE), indicating that molybdenum carbides are not stable enough for applications as anode electrocatalysts.  相似文献   

3.
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   

4.
Tellurium (Te)-modified carbon catalyst for oxygen reduction reaction was prepared through chemical reduction of telluric acid followed by the pyrolysis process at elevated temperatures. The catalyst was found to be active for oxygen reduction reaction. High-temperature pyrolysis plays a crucial role in the formation of the active sites of the catalysts. When the pyrolysis was conducted at 1000 °C, the catalyst exhibited the onset potential for oxygen reduction as high as 0.78 V vs. NHE and generated less than 1% H2O2 during oxygen reduction. The performance of the membrane–electrode assembly prepared with the Te-modified carbon catalyst was also evaluated.  相似文献   

5.
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   

6.
Nitrogen-modified carbon-based catalysts for oxygen reduction were synthesized by modifying carbon black with nitrogen-containing organic precursors. The electrocatalytic properties of catalysts were studied as a function of surface pre-treatments, nitrogen and oxygen concentrations, and heat-treatment temperatures. On the optimum catalyst, the onset potential for oxygen reduction is approximately 0.76 V (NHE) and the amount of hydrogen peroxide produced at 0.5 V (NHE) is approximately 3% under our experimental conditions. The characterization studies indicated that pyridinic and graphitic (quaternary) nitrogens may act as active sites of catalysts for oxygen reduction reaction. In particular, pyridinic nitrogen, which possesses one lone pair of electrons in addition to the one electron donated to the conjugated π bond, facilitates the reductive oxygen adsorption.  相似文献   

7.
The electrochemical performance of an unsupported PtIr electrocatalyst was evaluated as a bifunctional oxygen electrode in a unitized regenerative fuel cell (URFC). The catalyst was a mixture of unsupported Pt black and Ir black catalysts in varying proportions. The performance of the unsupported PtIr catalyst was studied by using a rotating ring disc electrode (RRDE) and linear sweep voltammetry (LSV). In addition, a unit cell test was performed simultaneously in the electrolyzer and in the fuel cell mode to evaluate the performance and durability of PtIr catalysts. The catalyst composition consisting of 85 wt.% Pt and 15 wt.% Ir showed high oxygen evolution reactivity and comparable electrochemical activity compared to the unsupported Pt black catalyst. The URFC using Pt85Ir15 catalyst showed the highest round-trip efficiency when estimated at different current densities. The cycle performance of URFC with Pt85Ir15 catalyst was stable for 120 h at an applied current density of 0.5 A cm−2.  相似文献   

8.
Shape controlled Pt particles were synthesized onto tungsten monocarbide (WC) substrates using a pulse electrodeposition method. The particle shape was strongly influenced by the deposition potential, with cubic particles formed using 0.14 V vs. NHE (normal hydrogen electrode) and dendritic particles formed at 0.04 V vs. NHE. The crystalline orientation and active surface area of the Pt particles were estimated using Cu stripping voltammetry. Finally, cyclic voltammetry and chronoamperometry were used to determine the methanol electrooxidation activity, which revealed that the dendritic Pt showed much higher electrochemical activity than the cubic particles. These results demonstrated the possibility of more effectively utilizing Pt electrocatalysts by controlling the shape of Pt particles.  相似文献   

9.
The role of Ru on the oxygen reduction reaction in the presence of methanol has been investigated. To this end a series of carbon supported Pt based electrocatalysts containing Ru and Co have been prepared and thoroughly characterized. The catalytic performance on the oxygen reduction reaction (ORR) both in the presence and in the absence of methanol by linear sweep voltammetry on rotating disk electrode has been studied. In spite of its documented ability towards methanol and CO oxidation, when Ru-containing catalysts are subjected to excursions to potentials more positive than 0.8 V vs. NHE they develop a certain tolerance to the presence of methanol. This feature is attributed to the formation of upper oxide Ru species that impede the methanol oxidation reaction to occur under the typical reaction conditions of the oxygen reduction process, i.e. potentials more positive than 0.7 V vs. NHE and oxygen saturated atmospheres. The evolution of Ru species with the applied potential has been investigated by XPS, identifying the presence of upper oxidized Ru phases.  相似文献   

10.
Non-precious metal catalysts (NPMCs) synthesized from the precursors of carbon, nitrogen, and transition metals were investigated as an alternate cathode catalyst for alkaline fuel cells (AFCs). The procedures to synthesize the catalyst and the post-treatment were tailored to refine its electrocatalytic properties for oxygen reduction reaction (ORR) in alkaline electrolyte. The results indicated that the performance of NPMCs prepared with carbon-supported ethylenediamine-transition metal composite precursor and subjected to heat-treatment shows comparable activity for oxygen reduction with Pt/C catalyst. The NPMC exhibits an open circuit potential of 0.97 V and a maximum power density of 177 mW cm−2 at 50 °C when tested in anion exchange membrane (AEM) fuel cells.  相似文献   

11.
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   

12.
Highly active and stable carbon composite catalysts for oxygen reduction in PEM fuel cells were developed through the high-temperature pyrolysis of Co–Fe–N chelate complex, followed by the chemical post-treatment. A metal-free carbon catalyst was used as the support. The carbon composite catalyst showed an onset potential for oxygen reduction as high as 0.87 V (NHE) in H2SO4 solution, and generated less than 1% H2O2. The PEM fuel cell exhibited a current density as high as 0.27 A cm−2 at 0.6 V and 2.3 A cm−2 at 0.2 V for a catalyst loading of 6.0 mg cm−2. No significant performance degradation was observed over 480 h of continuous fuel cell operation with 2 mg cm−2 catalyst under a load of 200 mA cm−2 as evidenced by a resulting cell voltage of 0.32 V with a voltage decay rate of 80 μV h−1. Materials characterization studies indicated that the metal–nitrogen chelate complexes decompose at high pyrolysis temperatures above 800 °C, resulting in the formation of the metallic species. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface doped with nitrogen groups is catalytically active for oxygen reduction.  相似文献   

13.
Carbon xerogels prepared by the resorcinol-formaldehyde (RF) sol-gel method with ambient-pressure drying were explored as Pt catalyst supports for polymer electrolyte membrane (PEM) fuel cells. Carbon xerogel samples without Pt catalyst (CX) were characterized by the N2 sorption method (BET, BJH, others), and carbon xerogel samples with supported Pt catalyst (Pt/CX) were characterized by thermogravimetry (TGA), powder X-ray diffraction (XRD), electron microscopy (SEM, TEM) and ex situ cyclic voltammetry for thin-film electrode samples supported on glassy carbon and studied in a sulfuric acid electrolyte. Experiments on Pt/CX were made in comparison with commercially obtained samples of Pt catalyst supported on a Vulcan XC-72R carbon black support (Pt/XC-72R). CX samples had high BET surface area with a relatively narrow pore size distribution with a peak pore size near 14 nm. Pt contents for both Pt/CX and Pt/XC-72R were near 20 wt % as determined by TGA. Pt catalyst particles on Pt/CX had a mean diameter near 3.3 nm, slightly larger than for Pt/XC-72R which was near 2.8 nm. Electrochemically active surface areas (ESA) for Pt as determined by ex situ CV measurements of H adsorption/desorption were similar for Pt/XC-72R and Pt/CX but those from CO stripping were slightly higher for Pt/XC-72R than for Pt/CX. Membrane-electrode assemblies (MEAs) were fabricated from both Pt/CX and Pt/XC-72R on Nafion 117 membranes using the decal transfer method, and MEA characteristics and single-cell performance were evaluated via in situ cyclic voltammetry, polarization curve, and current-interrupt and high-frequency impedance methods. In situ CV yielded ESA values for Pt/XC-72R MEAs that were similar to those obtained by ex situ CV in sulfuric acid, but those for Pt/CX MEAs were smaller (by 13-17%), suggesting that access of Nafion electrolyte to Pt particles in Pt/CX electrodes is diminished relative to that for Pt/XC-72R electrodes. Polarization curve analysis at low current density (0.9 V cell voltage) reveals slightly higher intrinsic catalyst activity for the Pt/CX catalyst which may reflect the fact that Pt particle size in these catalysts is slightly higher. Cell performance at higher current densities is slightly lower for Pt/CX than the Pt/XC-72R sample, however after normalization for Pt loading, performance is slightly higher for Pt/CX, particularly in H2/O2 and at lower cell temperatures (50 °C). This latter finding may reflect a possible lower mass-transfer resistance in the Pt/CX sample.  相似文献   

14.
The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H2SO4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.  相似文献   

15.
Transition metal and heteroatom codoped carbon materials have become the most promising materials to replace commercial platinum carbon (Pt / C) catalysts due to their low cost, high stability, and methanol resistance. In this work, iron-nitrogen and phosphorus codoped carbon nanorod-layer composites (N, P-CNL) derived from phosphorus-doped polyaniline (P-PANI) by phytic acid (PA) and iron salt were successfully obtained after high-temperature pyrolysis. As a result, the N, P-CNL materials exhibited good electrocatalytic performance due to abundant active sites. The N, P-CNL with 50% mass filling ratio of iron salt (named as N, P-CNL-1:1) displayed an enhanced limiting current density of −5.97 mA cm−2 at 1600 rpm and outstanding onset potential (−0.004 V) and oxygen reduction peak potential (−0.144 V). In general, this work can give insights into understanding the mechanism of codoped catalysts and synthesis the catalyst with excellent long-term stability and resistance to methanol crossover and poisoning better than commercial Pt/C.  相似文献   

16.
Porous silver membranes were investigated as potential substrates for alkaline fuel cell cathodes by the means of polarization curves and electrochemical impedance spectroscopy measurements. The silver membranes provide electrocatalytic function, mechanical support and a means of current collection. Improved performance, compared to a previous design, was obtained by increasing gas accessibility (using Teflon AF instead of PTFE suspension) and by adding a catalyst (MnO2 or Pt) in the membrane structure to increase the cathode activity. This new cathode design performed significantly better (∼55 mA cm−2 at 0.8 V, ∼295 mA cm−2 at 0.6 V and ∼630 mA cm−2 at 0.4 V versus RHE) than the previous design (∼30 mA cm−2 at 0.8 V, ∼250 mA cm−2 at 0.6 V and ∼500 mA cm−2 at 0.4 V) in the presence of 6.9 M KOH and oxygen (1 atm(abs)) at room temperature. The hydrophobisation technique of the porous structure and the addition of an extra catalyst appeared to be critical and necessary to obtain high performance. A passive air-breathing hydrogen-air fuel cell constructed from the membranes achieves a peak power density of 65 mW cm−2 at 0.40 V cell potential when operating at 25 °C showing a 15 mW cm−2 improvement compared to the previous design.  相似文献   

17.
In the present paper, a proton exchange membrane fuel cell (PEMFC) using 20 wt.% Pt/C as anode and cathode catalysts, and ambient air at cathode was operated at a current density of 160 mA cm−2 for 2250 h. The measurement results showed that electrochemically active specific areas (SEAS) of both electrode catalysts calculated from CV curves after test evidently decreased. The decay rate of SEAS of anode catalyst was much lower than that of cathode one. X-ray diffraction (XRD), energy dispersive analysis of X-ray (EDAX), and X-ray photoelectron spectrometry (XPS) were employed to characterize the anode and cathode catalysts before and after the life test. The XRD results showed that their crystal structures were perfect, the particle size of new Pt/C catalyst was about 2.5 nm, however, the particle sizes of anode and cathode ones markedly increased, and were about 4.9 nm and 6.8 nm, respectively, after the life test. Furthermore, the size of cathode catalyst was much bigger than that of anode one after test. The Pt element was also found in Nafion® film as shown in EDAX result. The XPS results presented that the content of Pt oxidation states in cathode was much more than that in anode, and the corrosion of carbon support in cathode was also more severe than that in anode after the life test. The experimental results indicated that the increase of particle size of Pt/C catalyst was illustrated with the dissolution/redeposition mechanism. The degradation of cathode catalyst for oxygen electroreduction was one of the main factors affecting on the performance decay of PEMFC.  相似文献   

18.
The degradation in performance of proton-exchange membrane fuel cells (PEMFCs) under open circuit conditions was investigated. The oxygen reduction reaction (ORR) kinetic current density at 0.9 V was found to decrease from 36 to 4 mA cm−2 (geometric) without significant crossover increase or loss in the electrochemically active surface area. Cyclic voltammograms for the electrodes show characteristic changes, e.g. appearance of peaks at ∼0.2 V and shift of the onset of platinum oxide formation to higher potentials. It was identified that the large ORR kinetic decay has its origins in the reduction of available Pt sites due to adsorption of anions, which are postulated to be membrane decomposition products such as sulfate ions. Procedures carried out to condense water in the fuel cell led to the expulsion of anions out of the membrane electrode assembly (MEA) resulting in the partial recovery of ORR kinetic current density to 15 mA cm−2. In order to attain complete performance recovery of the catalyst, a more effective and practical method to flush out the anions is desirable.  相似文献   

19.
Life test of the proton exchange membrane fuel cell (PEMFC) was carried out at a current density of 160 mA cm−2. After an operation up to 2250 h, the performance of the single PEMFC shown by a current-time curve did not decay significantly. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to characterize both anodic and cathodic catalysts before and after the life test. Cyclic voltammetric (CV), polarization, and power density curves were plotted with the cell at different periods during long-term operation. The results showed that the electrochemically active surface areas (SEAS) of anodic and cathodic catalysts firstly increased, and then decreased with the operation time. The SEAS loss of anodic catalyst was evidently smaller than that of cathodic one. The thickness of Nafion® film decreased with working time as shown by SEM. The particle size of cathodic Pt/C catalyst was evidently bigger than that of anodic one. The degradation of cathodic catalyst for oxygen electroreduction was one of the main factors affecting the performance decay of PEMFC.  相似文献   

20.
A Pt/WC/C catalyst is developed to increase the methanol electro-oxidation (MOR) and oxygen electro-reduction (ORR) activities of the Pt/C catalyst. Cyclic voltammetry and CO stripping results show that spill-over of H+ occurs in Pt/WC/C, and this is confirmed by comparing the desorption area values for H+ and CO. A significant reduction in the potential of the CO electro-oxidation peak from 0.81 V for Pt/C to 0.68 V for Pt/WC/C is observed in CO stripping test results. This indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support with WC. Preferential deposition of Pt on WC rather than on the carbon support is investigated by complementary analysis of CO stripping, transmission electron microscopy and concentration mapping by energy dispersive spectroscopy. The Pt/WC/C catalyst exhibits a specific activity of 170 mA m−2 for MOR. This is 42% higher than that for the Pt/C catalyst, viz., 120 mA m−2. The Pt/WC/C catalyst also exhibits a much higher current density for ORR, i.e., 0.87 mA cm−2 compared with 0.36 mA cm−2 for Pt/C at 0.7 V. In the presence of methanol, the Pt/WC/C catalyst still maintains a higher current density than the Pt/C catalyst.  相似文献   

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