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1.
The direct ethanol fuel cell has been attracting increased attention due to its safety and the wider availability of ethanol as compared with methanol. The present work investigates the anodic oxidation of ethanol on a core-shell structured Ru@PtPd/C catalyst in alkaline media. The catalyst shows high activity toward the anodic oxidation of ethanol; with 18 wt.% ruthenium as the core and 12 wt.% PtPd (Pt:Pd = 1:0.2) as the active shell, its activity in terms of PtPd loading is 1.3, 3, 1.4, and 2.0 times as high as that of PtPd/C, PtRu/C, Pd/C, and Pt/C, respectively, indicating high utilization of Pt and Pd. The ratio of forward peak current density to backward peak current density (If/Ib) reaches 1.5, which is 1.9 times that of PtPd/C catalyst, revealing high poisoning tolerance to the intermediates in ethanol electrooxidation. In addition, the stability of Ru@PtPd/C is higher than that of Pt/C and PtPd/C, as evidenced by chronoamperometric evaluations. The catalyst is extensively characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy. The core-shell structure of the catalyst is revealed by XRD and TEM.  相似文献   

2.
The present work addresses the potentialities of Pt–Ru nanoparticles deposited on a graphene oxide (RGO) and TiO2 composite support towards electrochemical oxidation of ethanol in acidic media relevant for fuel cell applications. To immobilize platinum–ruthenium bimetallic nanoparticles on to an RGO-TiO2 nanohybrid support a simple solution-phase chemical reduction method is utilized. An examination using electron microscopy and energy dispersive X-ray spectroscopy (EDS) indicated that Pt–Ru particles of 4–8 nm in diameter are dispersed on RGO-TiO2 composite support. The corresponding Pt–Ru/RGO-TiO2 nanocomposite electrocatalyst was studied for the electrochemical oxidation of ethanol in acidic media. Compared to the commercial Pt–Ru/C and Pt/C catalysts, Pt–Ru/RGO-TiO2 nanocomposite yields higher mass-specific activity of about 1.4 and 3.2 times, respectively towards ethanol oxidation reaction (EOR). The synergistic boosting provided by RGO-TiO2 composite support and Pt–Ru ensemble together contributed to the observed higher EOR activity and stability to Pt–Ru/RGO-TiO2 nanocomposite compared with other in-house synthesized Pt–Ru/RGO, Pt/RGO and commercial Pt–Ru/C and Pt/C electrocatalysts. Further optimization of RGO-TiO2 composite support provides opportunity to deposit many other types of metallic nanoparticles onto it for fuel cell electrocatalysis applications.  相似文献   

3.
Direct glucose fuel cells (DGFCs) received great interest due to non-toxicity, low cost, and renewability. Herein, we demonstrated the synthesis of novel porous AuPtPd nanocrystals (NCs) via plausible one-pot synthesis route. This was implemented by reduction of the metal precursors with l-ascorbic acid in the presence of polyvinylpyrrolidone (PVP) as a structure-directing agent. TEM (transmission electron microscopy) images of the as-synthesized nanocrystals depicted porous nanodendritic morphology with particle size ranging from 20 to 30 nm. The catalytic performance of AuPtPd NCs was investigated towards glucose oxidation reaction (GOR) in alkaline medium compared to AuPt, PtPd, and Pt/C. The delivered maximum oxidation current density over AuPtPd was 10.1 mA cm−2, which is nearly 1.4, 1.8, and 3.5 times greater than AuPt, PtPd, and Pt/C, respectively. Additionally, the ternary electrocatalyst exhibited higher electrochemical stability compared to binary alloys and Pt/C counterparts. Furthermore, AuPtPd revealed lower Tafel slope for GOR compared to binary alloys and Pt/C which affirm enhanced GOR kinetics. The outstanding catalytic performance of AuPtPd NCs was attributed to the synergistic effect of the alloying elements and the high anti-poisoning effect of Au and Pd metals which facilitates the adsorption of surface hydroxyls (OH)ads on the catalyst active sites and enhances the oxidation kinetics.  相似文献   

4.
Bimetallic PtPd nanospheres strongly fabricated on reduced graphene oxide (rGO) sheets (rGO-PtPd) by simple one pot wet reflux method for superior methanol electro-oxidation. There is no any other polymer or seed involved for preparation of nanocomposite. The as-synthesized materials structure and morphology was calibrated by Powdered X-ray diffraction (P-XRD), Raman, X-ray photo electron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The PtPd nanoparticles supported rGO sheets displays superior electro-catalytic activity and stability towards methanol electro-oxidation (MOR) because of their large electrochemical surface area (ECSA, which is 1.68 times greater than that of commercial Pt/C black) and synergistic effect of the bimetallic alloy. The rGO-PtPd showed enhanced electro-catalytic performances towards MOR in acidic media due to particle size and uniform distribution of particles, which rGO-Pt1Pd1 (Pt/Pd molar ratio 1/1) showed the more specific activity, mass activity and stability for MOR. Thus, as-synthesized rGO-PtPd catalyst could apply potential applications in direct methanol fuel cells (DMFCs) to lower their cost and advance their cycle ability, which make it promising for practical catalysis in energy conversion and storage.  相似文献   

5.
This research aims to investigate Pd-based catalysts as a replacement for Pt-based catalysts for ethanol electrooxidation in alkaline media. The results show that Pd/C has a higher catalytic activity and better steady-state behaviour for ethanol oxidation than that of Pt/C. The effect of the addition of CeO2 and NiO to the Pt/C and Pd/C electrocatalysts on ethanol oxidation is also studied in alkaline media. The electrocatalysts with a weight ratio of noble metal (Pt, Pd) to CeO2 of 2:1 and a noble metal to NiO ration 6:1 show the highest catalytic activity for ethanol oxidation. The oxide promoted Pt/C and Pd/C electrocatalysts show a higher activity than the commercial E-TEK PtRu/C electrocatalyst for ethanol oxidation in alkaline media.  相似文献   

6.
In direct alcohol fuel cells, ethanol crossover causes a less serious effect compared to that of methanol because of both its smaller permeability through the Nafion® membrane and its slower electrochemical oxidation kinetics on a Pt/C cathode. The main interest in direct ethanol fuel cells (DEFCs) is to find an anode catalyst with high activity for the oxidation of ethanol. However, due to the low activity of pure platinum for the oxygen reduction reaction (ORR), research on cathode electrocatalysts with improved ORR and the same or improved ethanol tolerance than that of Pt are also in progress. In this work, a commercial carbon supported Pt–Co (3:1) electrocatalyst (E-TEK) was investigated as cathode material in DEFCs and the activity compared to that of Pt. In the cathodic potential region (0.7–0.9 V versus RHE) Pt/C and Pt–Co/C showed the same activity for the oxidation of crossover ethanol. But the performance of Pt–Co/C as cathode material in DEFCs in the temperature range 60–100 °C is better than that of Pt/C both in terms of mass activity and specific activity, due to an improved activity of the alloy for oxygen reduction.  相似文献   

7.
Palladium (Pd) as an efficient anodic catalyst has been extensively investigated in direct formic acid fuel cells (DFAFCs); while, Pd catalyst is electrochemically unstable in acidic electrolyte resulting in low stability retarding the widespread application of DFAFCs. In this study, a new method is invented to prevent the Pd nanoparticles from rapid dissolution by carbon layer originated from the carbonization of glucose. Ascribing to the presence of carbon layer, Pd electrocatalyst demonstrates much higher stability in comparison with Pd electrocatalyst without carbon layer in the course of stability tests. Robust electrocatalytic activities toward formic acid and methanol/ethanol oxidation are observed for carbon-stabilized Pd electrocatalyst resulted from the higher content of metallic Pd atoms coming from the carbonization process, in which Pd (II) species are further reduced. Moreover, the fuel cell performance of carbon-stabilized Pd electrocatalyst reaches 90 mW cmPd−2 measured with 1 M formic acid; while, power density of bare Pd electrocatalyst is only 74 mW cmPd−2. This work highlights that carbon layer carbonized from glucose improves not only the stability of Pd electrocatalyst, but also the electrocatalytic activity.  相似文献   

8.
Electrocatalytic preparation of Pt-based nanocomposites has been investigated for improvement of direct ethanol fuel cells (DEFCs). In this study, new alternative catalysts of Pt-decorated cerium zirconium oxide-modified multiwalled carbon nanotubes (Pt/CeZrO4/MCNT) were successively prepared to improve the activity of the ethanol oxidation reaction (EOR). The prepared CeZrO4 with a face-centered cubic (fcc) structure compatibly dispersed onto MCNT provides abundant active Pt sites for highly active catalysts. The fcc-structured Pt was also satisfactorily decorated onto CeZrO4/MCNT, resulting in highly active Pt. The Ce4+/Ce3+ redox property can promote oxygen vacancies to improve the electrochemical activity for oxidation of carbonaceous species. An increase in roughness and a stabilized catalyst structure can also be produced by inserting Zr4+ into the ceria metal oxide. The prepared Pt/20%CeZrO4/MCNT catalysts present excellent electrochemical active surface area, mass activity, CO tolerance and high electron kinetic transfer with low resistance and high stability over commercial PtRu/C toward EOR. This promising catalyst material could be introduced to enhance the anodic oxidation reaction in DEFCs.  相似文献   

9.
Palladium nanoparticles (Pd NPs) were successfully electrodeposited on a reduced graphene oxide/poly(melem-formaldehyde) nanocomposite (rGO/PMF) NC as a catalyst for ethanol electrooxidation in alkaline media; melem was used as a nitrogen-rich source in the substrate structure for the first time. The specific surface area and average pore diameter of (rGO/PMF) NC were 481.61 m2 gr?1 and 10.23 nm, respectively. High nitrogen doping and structural defects improved the dispersion and anchoring of Pd NPs on (rGO/PMF) NC. The onset potential (Eonset) of Pd/(rGO/PMF) NC was shifted negatively to 110 mV, in comparison to Pd/rGO. Also, the current density and electrochemical active surface area (EASA) of Pd/(rGO/PMF) NC were enhanced to 44 mA cm?2 and 67.58 m2 gr?1, respectively, as compared to Pd/rGO. Furthermore, the stability of Pd/(rGO/PMF)NC was indicated against ethanol oxidation intermediates during 7000 s. This work also produced a superior graphene-based material for direct ethanol fuel cell anode catalysts applications.  相似文献   

10.
Direct ethanol fuel cells (DEFCs) technology as a promising clean-energy, is obstructed by unsatisfactory activity of ethanol oxidation reaction (EOR) nanocatalysts. Traditional shape-controllers usually lead to regular nanoparticles. Three-dimensional dendrimers, like hyperbranched polyamide (HBPA), however, have superiorities to form irregular morphologies, due to their multitudinous terminal functional groups and irregular interior cavities. Considering the lack of researches, herein, a novel HBPA was utilized to facilely and controllably synthesize irregular gravel-like PtPd nanoparticles (g-PtPd-NPs) with rich active sites. The synthetic mechanism was studied by both experiments and density functional theory calculations. N atoms of HBPA were proven essential. In EOR tests, the activity of g-PtPd-NPs was 2.05-fold of commercial Pt/C, and higher than PtPd catalysts of control sets and reports. The durability was excellent, too. This study is promotive for DEFCs into practice, and may enlighten more nanomaterials' synthesis.  相似文献   

11.
Herein, we report the synthesis of Sm2O3 incorporated palladium based electrocatalyst, supported over reduced graphene oxide (rGO). PdxSmy nanoparticles (20 wt %) are distributed over rGO surface by using sodium borohydride reduction technique. Different physicochemical analyses are used to characterize the PdxSmy/rGO electro-catalysts (x = 2,4,6 and y = 8,6,4). The synthesized materials (PdxSmy/rGOs) are investigated for their catalytic capabilities toward electro-oxidation of formic acid. The results show that adding Sm2O3 to the Pd/rGO electrocatalyst boosts electrochemical activities of the materials toward formic acid oxidation. The optimized catalyst (Pd6Sm4/rGO) shows excellent activity towards formic acid oxidation with current density of 46.70 mA/cm2 compared to reference catalysts i.e., Pd/rGO (28.78 mA/cm2) and Pd/C (22.22 mA/cm2). The optimized catalyst also demonstrates high CO tolerance and great stability during formic acid oxidation reaction. The enhanced activity and stability are attributed to the synergistic interaction between Sm2O3, and palladium nanoparticles supported over reduced graphene oxide.  相似文献   

12.
PtRu, PtPd and PtSn with weight ratios of (2:1) on carbon black (Vulcan XC-72) supported bimetallic catalysts were prepared by using microwave method via chemically reduction of H2PtCl6·6H2O, RuCl3, PdCl2 and SnCl2·2H2O precursors with ethylene glycol (EG). These prepared catalysts were systematically investigated and obtained results were compared with commercial Pt black, PtRu black catalysts and with each other. The catalysts were characterized with XRD, ICP-MS, EDS and TEM. The electrocatalytic activities, stability and impedance of the catalysts were investigated in sulfuric acid/methanol and sulfuric acid/formic acid mixtures using electrochemical measurements. The results showed that PtSn/C catalyst showed comparable activity and durability with commercial Pt/C catalyst toward methanol oxidation. The synthesized PtRu/C catalyst was found to completely oxidize methanol and it showed more catalytic activity than commercial PtRu catalyst. Bimetallic PtPd/C catalyst gave better activity than both commercial Pt black and synthesized Pt/C catalyst for oxidation of formic acid. Higher electrochemical active surface areas were obtained with supported bimetallic catalysts.  相似文献   

13.
Pd–Ni–Fe nanoparticles supported on MnO2/Vulcan XC-72 R (carbon black powder) as the electrocatalyst for the anodic oxidation of ethanol in a direct ethanol alkaline fuel cell (DEAFC) has been conducted. Electrocatalyst structures and morphologies are investigated by XRD, FE-SEM, EDX and elemental mapping techniques and subsequently electrochemical performance of electrocatalysts for ethanol oxidation reaction (EOR) are studied by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). Pd/MnO2/Vulcan, Pd–Ni/MnO2/Vulcan and Pd–Ni–Fe/MnO2/Vulcan efficiently advanced ethanol electro-oxidation reaction under alkaline conditions. Pd/MnO2/Vulcan revealed best potential window and low charge transfer resistance (Rct) for EOR. Pd–Ni/MnO2/Vulcan and Pd–Ni–Fe/MnO2/Vulcan electrocatalysts have a good anti CO-poisoning capability. Pd–Ni–Fe/MnO2/Vulcan has significantly high current density, excellent catalyst durability and cyclic stability for ethanol oxidation which encourage researchers for application of such exceptional materials as anode electrocatalysts in DEFC.  相似文献   

14.
Developing highly active and stable ethanol oxidation electrocatalysts is crucial for direct ethanol fuel cells. Herein, platinum/molybdenum disulfide nanoflower (Pt/MoS2) nanocomposite is synthesized through a facile method and is first applied as catalyst for ethanol oxidation reaction. In situ electrochemical nuclear magnetic resonance is carried out to investigate the electrocatalytic activity of Pt/MoS2 and the detailed mechanism of ethanol oxidation reaction. Experimental results indicate that in situ electrochemical nuclear magnetic resonance possesses great advantages for real-time investigation of ethanol oxidation reaction, and Pt/MoS2 is found to exhibit better electrocatalytic performances in terms of higher current density, better stability, and stronger anti-poisoning activity compared to commercial Pt/C and pure Pt catalysts in acid electrolyte, suggesting its potential for application in direct ethanol fuel cells. Density functional theory calculations indicate that MoS2-supported Pt atom has a smaller energy barrier for the dissociation of ethanol compared to those of Pt and C-supported Pt atom, leading to the enhancement of catalytic activity. This work reveals the importance of the supporting materials for high performance direct ethanol fuel cells catalysts.  相似文献   

15.
Direct Ethanol Fuel Cells (DEFCs) have fascinated remarkable attention on account of their high current density and being environmentally friendly. Developing efficient and durable catalysts with a simple and fast method is a great challenge in the practical applications of DEFCs. To this end, the bimetallic Pd–Ag with adjustable Pd:Ag ratios were synthesized via a simple and one-pot strategy on activated carbon as a support in this study. The Pd–Ag/C catalysts with different molar ratios were synthesized by simultaneous reduction of Pd and Ag ions in the presence of the ethanolic sodium hydroxide as a green reducing agent for the first time. Several different methods, including FE-SEM, HR-TEM, XRD, XPS EDX, ICP-OES, and BET were used to confirm the structure and morphology of the catalysts. The performance of catalysts was also examined in ethanol oxidation. Obtained results of electrochemical experiments revealed that the Pd3–Ag1/C catalyst had superior catalytic activity (2911.98 mAmg?1Pd), durability, and long-stability compared to the other catalysts. The excellent catalytic characteristic can be attributed to the synergistic effect between Pd and Ag. We presume that our simple method have the chance to be utilized as a proper method for the synthesis of fuel cell catalysts.  相似文献   

16.
The influence of Pt: Pd atomic ratios (1:2–1:8) on a carbon support upon its suitability as a cathode for a proton exchange membrane (PEM) fuel cell was evaluated at a constant membrane electrocatalyst loading of 0.15 mg/cm2. The results clearly demonstrated that the different Pt: Pd atomic ratios had a significant effect on both the electrocatalyst activity and also on the performance in a H2/O2 fuel cell. Decreasing the Pt: Pd atomic ratio led to an increase in the particle size of the electrocatalyst but a decrease in the particle dispersion and electrochemical surface area (ESA). With respect to the performance in a PEM fuel cell, decreasing the Pt: Pd atomic ratio led to a decreased exchange current density (j0), electrocatalytic activity and also mass activity (MA), but to an increased total resistance (R) of the cell. The maximum activity of the oxygen reduction reaction (ORR) and the peak power (492 mW/cm2) were obtained with an electrocatalyst with a Pt: Pd atomic ratio of 1:2. Finally, the rotating disk electrode (RDE) analysis showed that the mechanism of oxygen reduction on the prepared Pt–Pd/C electrocatalyst involved a four-electron pathway with high oxygen permeability in the Nafion film.  相似文献   

17.
Considering the disadvantages of conventional compressors, which are widely used in the world, it is thought that the electrochemical hydrogen purifier and compressor system (EHPC) to be developed will provide great advantages in hydrogen technologies. The electrocatalyst, which is one of the main components of the EHPC system, is critical for both the performance and applicability of the system. In this study, commercial carbon black supported Pt and Pd containing catalysts were prepared for the EHPC system by using microwave heating method. The synthesized catalysts were mono and bimetallic and were named as Pt/C, Pd/C and PtPd/C, respectively. By characterizing the prepared catalysts with ICP-MS, SEM-EDS, TEM, XRD and XPS, information about the distribution, amount, morphology and composition of metal nanoparticles on the support material was obtained. In addition, electrochemical properties of the catalysts were determined by CV analysis. The physical characterization results revealed that the catalysts were successfully synthesized by microwave method and that different ratios of metals and bimetallic could be loaded on the support material. It was also seen that the electrochemical activity of the PtPd/C bimetallic catalyst was better than the others.  相似文献   

18.
Ammonia has attracted attention as a possible fuel for direct fuel cells since it is easy to handle and to transport as liquid or as concentrated aqueous solution. However, on noble metal electrodes ammonia oxidation is a sluggish reaction and the electrocatalyst needs to be improved for developing efficient ammonia fuel cells. In this work, ammonia electrooxidation reaction on 3–4-nm bimetallic PtMe (Ir, Rh, Pd, Ru) and on preferentially oriented Pt(1 0 0) nanoparticles is reported. PtMe nanoparticles have been prepared by using water-in-oil microemulsions to obtain a narrow size distribution whereas preferentially oriented Pt nanoparticles have been prepared through colloidal routes. Among all the bimetallic samples tested, only Pt75Ir25 and Pt75Rh25 nanoparticles show, at the low potential range, an enhancement of the oxidation density current with respect to the behaviour found for pure platinum nanoparticles prepared by the same method. In addition, two Pt(1 0 0) preferentially oriented nanoparticles of different particle size (4 and 9 nm) have been also studied. These oriented nanoparticles show higher current densities than polycrystalline Pt nanoparticles due to the sensitivity of ammonia oxidation toward the presence of surface sites with square symmetry. The reactivity of the different 4-nm nanoparticles parallels well with that expected from bulk PtMe alloys and Pt single crystal electrodes.  相似文献   

19.
The instability of carbon support materials has motivated the development of metal oxides supports which are stable under the fuel cell environment. In this study, tungsten (VI) oxide (WO3) is utilized as a secondary support and cocatalyst for the electrooxidation of methanol and ethanol. Functionalized carbon nanodots employed as primary supports were blended with WO3 nanoparticles to form a composite support onto which Pd nanoparticles were deposited by a borohydride reduction method. The synthesized Pd/fCNDs-WO3 electrocatalysts were characterized by Transmission Electron microscopy (TEM), X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy. XRD results proved that incorporating WO3 into Pd/fCNDs electrocatalyst shifts the Pd diffraction peaks to lower 2Ɵ value due to lattice relaxation. XPS results revealed that W exist in oxidised form and confirmed the strong interaction between the support material and the catalyst. The Pd/fCNDs-WO3 electrocatalysts exhibited a remarkable catalytic activity towards methanol and ethanol oxidation. High current densities of 87.24 mA cm−2 and 44.23 mA cm−2 were obtained for ethanol and methanol oxidation, respectively, using a catalyst with 2.5% Pd loading. EIS, CA and stability tests revealed that the presence of WO3 in Pd/fCNDs electrocatalyst improves the kinetics, tolerance to poisoning and long-term durability in alkaline conditions. This superior performance is attributed to the electronic coupling between Pd and WO3 nanoparticles.  相似文献   

20.
In this paper, newly graphite carbon/Prussian blue analogue/palladium (GC/PBA/Pd) synergistic-effect electrocatalyst for ethanol oxidation reaction were developed, with Co-based PBA (Co3[Co(CN)6]2) as a co-catalyst. Structural analysis shows that the Co3(Co(CN)6)2 nanoparticles were highly dispersed and inlaid on surface of GC nanosheets with outstanding structural stability. The GC/Co3(Co(CN)6)2/Pd electrocatalyst exhibits significantly enhanced electrocatalytic activity towards ethanol oxidation with a maximum mass activity of 2644 A g?1 Pd GC/Pd, which is more than double that of GC/Pd electrocatalyst (1249 A g?1). Excellent electrochemical stability is also demonstrated for this GC/Co3(Co(CN)6)2/Pd electrocatalyst. The enhanced electrocatalytic activity can be attributed to the synergistic effects of GC support and Co3(Co(CN)6)2 promoter on the Pd electrocatalysts, in which Co3(Co(CN)6)2 acts as a co-catalyst and GC acts as a conductive support.  相似文献   

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