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1.
At present, a novel and active catalyst, RuW/MWCNT catalyst, was successfully synthesized to complete the hydrolysis reaction of sodium borohydride (NaBH4). The activity of Ru catalyst was increased by adding tungsten (W) to ruthenium (Ru) on multi-walled carbon nanotube (MWCNT) support. Surface characterization of the catalyst was performed with scanning electron microscope (SEM-EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmissing electron microscope (TEM) analysis methods. SEM-EDX revealed that RuW (95:5) catalyst metal ratio was obtained at desired nominal ratio. XRD characterization revealed that W addittion to the Ru structure increased its activity by forming an alloy. W addition Ru altered the electronic structure of the Ru. Parameters affecting the hydrolysis performance of RuW/MWCNT catalyst such as temperature, amount of catalyst, NaBH4 concentration and sodium hydroxide (NaOH) concentration were investigated. Adding NaOH to the reaction vessel reduced the activity of the RuW/MWCNT catalyst. From the hydrolysis measurements, the activation energy of RuW(95–5)/MWCNT catalyst was found to be 16.327 kjmol?1, the reaction order as 0.61 and the initial rate as 95,841,4 mL H2gcatmin?1. The stability of the RuW/MWCNT catalyst was tested using 5 times and it was observed that this novel RuW/MWCNT catalyst could complete the hydrolysis reaction despite repeated use.  相似文献   

2.
Cyclic voltammetry (CV), amperometric i − t experiments, and electrochemical impedance spectroscopy (EIS) measurements were carried out by using glassy carbon disk electrode covered with the Pt/C catalyst powder in solutions of 0.5 mol L−1 H2SO4 containing 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 containing 0.5 mol L−1 HCOOH at 25 °C, respectively. Electrochemical measurements show that the activity of Pt/C for formic acid electrooxidation is prominently higher than for methanol electrooxidation. EIS information also discloses that the electrooxidation of methanol and formic acid on the Pt/C catalyst at various polarization potentials show different impedance behaviors. The mechanisms and the rate-determining steps of formic acid electrooxidation are also changed with the increase of the potential. Simultaneously, the effects of the electrode potentials on the impedance patterns were revealed.  相似文献   

3.
The kinetics of the methanol electrooxidation needs to be improved to increase the power density using a lower amount of noble metal catalysts (i.e., Pt and Ru) in direct methanol fuel cells (DMFC). PtRu nanoparticles (∼5 nm) supported on TiO2-nanoparticle (∼4 nm)-coated carbon nanofibers were proposed as an alternative active catalyst for the DMFC. The nano-sized TiO2 can provide a short distance of electron transport from PtRu (reaction site) to the carbon (current collector). At the composite catalyst, the activity enhancement by the PtRu-TiO2 interaction suggested the sufficient electron conductivity at the electrode. The maximized specific activity of the proposed catalyst was 3 times higher compared to that of the commercial PtRu/C. The pore structure of the catalyst was changed by the oxidation conditions due to gasification of the carbon, and the higher activity was obtained by the catalyst with the higher surface area of the micropores (>800 m2 g−1). However, the contribution of micropore would be a secondary effect to the activity. The maximized specific activity was obtained when the volumes of PtRu and TiO2 were similar for the almost same size (around 5 nm) of these particles suggesting that the number of contact points between the PtRu and TiO2 were optimized and the interaction between them was maximized. The PtRu-TiO2-carbon nano-composite catalyst has a high potential as an alternative catalyst as the anode of DMFC.  相似文献   

4.
The anodic Pt–Ru–Ni/C and the Pt–Ru/C catalysts for potential application in direct methanol fuel cell (DMFC) were prepared by chemical reduction method. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements were carried out by using a glassy carbon working electrode covered with the catalyst powder in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 at 25 °C. EIS information discloses that the methanol electrooxidation on the Pt–Ru–Ni/C catalyst at various potentials shows different impedance behaviors. The mechanism and the rate-determining step of methanol electrooxidation are changed with increasing potential. Its rate-determining steps are the methanol dehydrogenation and the oxidation reaction of adsorbed intermediate COads and OHads in low (400–500 mV) and high (600–800 mV) potentials, respectively. The catalytic activity of the Pt–Ru–Ni/C catalyst is higher for methanol electrooxidation than that of the Pt–Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol dehydrogenation is also better than that of the Pt–Ru/C catalyst.  相似文献   

5.
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   

6.
This research aims to improve the activity of Pt-Ru nanoparticle electrocatalysts and thus, to lower the catalyst loading in anodes for methanol electrooxidation. The direct methanol fuel cell (DMFC) anodic Pt-Ru/C nanoparticle electrocatalysts were prepared using a chemical reduction method. The pH values of the reductive solutions were adjusted by different buffer solutions of CH3COONa–NaOH, C6H5Na3O7–NaOH, and Na2CO3–NaHCO3, respectively. The performance of the nanoparticle electrocatalysts were examined by cyclic voltammetry, chronoamperometry, and amperometric it curves using a glassy carbon working electrode in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. The structures and micro-morphology of the Pt-Ru/C nanoparticles were determined and observed by X-ray diffraction (XRD) and transmission electron microscopy. XRD analysis showed that all of catalysts exhibited face-centered cubic (fcc) structures. No diffraction peaks indicated the presence of either pure Ru or Ru-rich hexagonal close packed (hcp) phase. The size of the Pt-Ru/C nanoparticles prepared with a C6H5Na3O7–NaOH solution was relatively small ∼4.3 nm. Its size distribution in carbon was more homogeneous. The electrochemical active measurements results showed that the catalytic activity and the stability of Pt-Ru/C nanoparticle electrocatalyst prepared with a C6H5Na3O7–NaOH solution for methanol electrooxidation was higher than that from the other solutions due to the citrate complexation stabilizing effect and a competing adsorption effect.  相似文献   

7.
In this work, a facile Fe- and N-containing porous carbon derived from sewage sludge was prepared and served as the support of Pt nanoparticles for the electrooxidation of methanol. Both the sludge-derived carbon (denoted as SC) and the resultant Pt/SC catalyst was physically characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrocatalytic performance for methanol oxidation reaction (MOR) of the Pt/SC was examined by cyclic voltammetry (CV) and chronoamperometric method. The results showed that the Pt/SC possessed slightly larger Pt particle size (5.5 nm) and lower electrochemical active surface area (ECA) compared to common Pt/C catalyst. However, the mass activity of Pt/SC for MOR was up to 201 mA mg−1, which was much higher than that of Pt/C (93 mA mg−1), indicating the synergistic effect of the sewage sludge-derived carbon with Fe and N species on methanol electrooxidation. Furthermore, Pt/SC showed enhanced durability towards MOR compared to common Pt/C, implying its potential for using in direct methanol fuel cell (DMFC) for energy conversion, which also demonstrated a promising solution for the utilization of sewage sludge resources.  相似文献   

8.
The electrooxidation of methanol and ethanol was investigated in acidic media on the platinum–nickel nanoparticles carbon-ceramic modified electrode (Pt–Ni/CCE) via cyclic voltammetric analysis in the mixed 0.5 M methanol (or 0.15 M ethanol) and 0.1 M H2SO4 solutions. The Pt–Ni/CCE catalyst, which has excellent electrocatalytic activity for methanol and ethanol oxidation than the Pt–Ni particles glassy carbon modified electrode (Pt–Ni/GCE), Pt nanoparticles carbon-ceramic modified electrode (Pt/CCE) and smooth Pt electrode, shows great potential as less expensive electrocatalyst for these fuels oxidation. These results showed that the presence of Ni in the structure of catalyst and application of CCE as a substrate greatly enhance the electrocatalytic activity of Pt towards the oxidation of methanol and ethanol. Moreover, the presence of Ni contributes to reduce the amount of Pt in the anodic material of direct methanol or ethanol fuel cells, which remains one of the challenges to make the technology of direct alcohol fuel cells possible. On the other hand, the Pt–Ni/CCE catalyst has satisfactory stability and reproducibility for electrooxidation of methanol and ethanol when stored in ambient conditions or continues cycling making it more attractive for fuel cell applications.  相似文献   

9.
In this work, PdO/TiO2 and Eu2O3/TiO2 nanocomposites (NCs) were synthesized using a new facile, template‐free, and one‐step solvothermal approach and characterized by several instrumentation techniques. X‐ray photoelectron spectroscopy studies revealed the presence of oxidized form of the Pd and Eu nanoparticles within the NC materials (PdO and Eu2O3). The two catalysts exhibited remarkable activity for the hydrogen evaluation reaction (HER) in a strong alkaline solution (4.0 M NaOH) with PdO/TiO2 catalyst being the best, which recorded an exchange current density (jo) of 0.26 mA cm?2 and a Tafel slope (βc) of 125 mV dec?1. Such parameters are not far from those recorded for a commercial Pt/C catalyst (0.71 mA cm?2 and 120 mV dec?1) performed here under the same operating conditions. Eu2O3/TiO2 catalyst recorded jo and βc values of 0.05 mA cm?2 and 135 mV dec?1. The Tafel slopes 125 and 135 mV dec?1 calculated on the PdO/TiO2 and Eu2O3/TiO2 catalysts suggest a HER kinetics controlled by the Volmer step. PdO/TiO2 catalyzed the HER with a high turnover frequency of 2.3 H2/s at 0.2 V versus the reversible hydrogen electrode, while Eu2O3/TiO2 catalyst only measured a turnover frequency value of 1.25 H2/s at the same overpotential. The two catalysts exhibited excellent stability and durability after 10 000 cycles and 72 hours of controlled potential electrolysis at a high cathodic overpotential, reflecting their practical applicability. Scanning electron microscope and X‐ray photoelectron spectroscopy examinations revealed that the morphology and chemistry of both catalysts were not altered as a result of the performed long‐term stability and durability tests.  相似文献   

10.
This study reports a novel strategy by using polyaniline nanofibers (PANFs) to modify membrane-electrode assembly (MEA) for improving direct methanol fuel cell (DMFC) performance. First of all, a series of PANFs emeraldine salt was synthesized and characterized. Then, we investigated the effect of PANFs layout in MEA on DMFC performance. Three different placements to incorporate the as-synthesized PANFs in anodes include (1) placing a layer of PANFs between catalyst layer (CL) and proton exchange membrane (PEM), (2) mixing with catalyst slurry and coating onto gas diffusion layer (GDL), and (3) placing a layer of PANFs between CL and GDL. Polarization curves indicate that the third method is superior to the others and is adopted as the incorporation layout thereafter. Both methanol transport resistance and methanol crossover of the PANFs-modified MEA are studied further. The DMFC incorporated with H2SO4-doped PANFs obtained after the re-doping process with 2 mol L−1 H2SO4 performs a power density as high as 53 mW cm−2, about 20% higher than that of the pristine one without PANFs incorporation. However, an excessive doping level may result in a higher methanol transport resistance due to PANFs aggregation and thus deteriorate DMFC performance. This study provides a simple and effective way by placing a layer of PANFs between CL and GDL in anode to act as methanol transport regulator and improve DMFC performance consequently.  相似文献   

11.
The development of highly efficient catalysts using inexpensive and earth-abundant metals is a crucial factor in a large-scale commercialization of direct methanol fuel cells (DMFCs). In this study, we explored a new catalyst based on copper nanodendrites (CuNDs) supported on carbon nanofibers/poly (para-phenylenediamine) (CNF/PpPD) nanocomposite for methanol oxidation reaction (MOR). The catalyst support was prepared on a carbon paste electrode by electropolymerization of para-phenylenediamine monomer on a drop-cast carbon nanofibers network. Afterwards, CuNDs were electrodeposited on the nanocomposite through a potentiostatic method. The morphology and the structure of the prepared nanomaterials were characterized by transmission electron microscope, scanning electron microscope, energy dispersive X-ray, X-ray diffraction, and X-ray photoelectron spectroscope. The results suggested that a three-dimensional nanodendritic structure consisting of Cu2O and Cu(OH)2 formed on the hybrid CNF/PpPD nanocomposite. The catalytic performance of CuNDs supported on CNF, PpPD and CNF/PpPD was evaluated for MOR under alkaline conditions. The CNF/PpPD/CuNDs exhibits a highest activity (50 mA cm?2) and stability toward MOR over 6 h, with respect to CNF/CuNDs (40 mA cm?2) and PpPD/CuNDs (36 mA cm?2). This inexpensive catalyst with high catalytic activity and stability is a promising anode catalyst for alkaline DMFC applications.  相似文献   

12.
The effect of Nafion® ionomer aggregation in solution on the structure of the cathode catalyst layer of a direct methanol fuel cell (DMFC) was investigated by dynamic light scattering (DLS), laser particle sizer, electron probe microanalysis (EPMA) and scanning electron microscopy (SEM). The results showed that large aggregation particles were suppressed by the addition of NaOH to aqueous solutions of Nafion®, which led to a smaller agglomerate particle size distribution in the catalyst ink. The cathode catalyst layer made from the catalyst ink with NaOH addition showed a more uniform distribution of sulfur and Pt elements, a higher electrochemical active surface area (48% increase) and achieved a better performance in the DMFC than one made from the catalyst ink without NaOH addition.  相似文献   

13.
A mesoporous carbon‐confined cobalt (Co@C) catalyst was fabricated by pyrolysis of macroscale Co‐metal–organic framework (MOF) crystals and used to catalyze NaBH4 hydrolysis for hydrogen production. To reveal the structural changes of cobalt nanoparticles, we characterized the fresh and used Co@C catalysts using X‐ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and N2 adsorption. This MOF‐derived Co@C exhibits high and stable activity toward NaBH4 hydrolysis. No obvious agglomeration of Co nanoparticles occurred after five consecutive runs, implying good resistance of Co@C composite to metal aggregation. The kinetics of NaBH4 hydrolysis was experimentally studied by changing initial NaBH4 concentration, NaOH concentration, and catalyst dosage, respectively. It was found that the hydrogen generation rate follows a power law: r = A exp (?45.0/RT)[NaBH4]0.985[cat]1.169[NaOH]?0.451 .  相似文献   

14.
We reported the direct reduction of H2PtCl6 and RuCl3 solution containing acetylene black powder by Na2S2O4 to make Pt–Ru (20–10 wt%) supported on acetylene black (Pt–Ru/AB) as a nanocatalyst for methanol electrooxidation in acidic media. The electrochemical activity of catalyst was studied by electrochemical impedance spectroscopy, linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Structural aspects of the Pt–Ru (20–10 wt%)/AB were studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The analysis of electrochemical results indicated lower charge transfer resistance, higher peak current for Pt–Ru (20–10 wt%)/AB compared to the commercial catalyst, Pt–Ru (20–10 wt%)/carbon Vulcan. XRD spectra verified a face centered cubic structure for the synthesized Pt–Ru/AB and its particle size was mostly 10 nm according to TEM and XRD images. In DMFC, Pt–Ru/AB had superior performance compared to the commercial catalyst in all current densities, which could be attributed to enhancement of the methanol oxidation kinetics, higher conductivity, and more uniform distribution of the ionomer in anode catalyst layer.  相似文献   

15.
In this study, the effect of multiwalled carbon nanotube and graphene nanoplatelet‐based catalyst supports on the performance of reformate gas‐fed polybenzimidazole (PBI)‐based high‐temperature proton exchange membrane fuel cell (HT‐PEMFC) was investigated. In addition, the effect of several microwave conditions on the performance of the Pt‐Ru/multiwalled carbon nanotube (MWCNT)–graphene nanoplatelet (GNP) catalyst was assessed. Through X‐ray diffraction, thermal gravimetric analysis, transmission electron microscopy, scanning electron microscopy, and energy dispersive spectroscopy, the catalysts' chemical structure and morphology were characterized. Cyclic voltammetry analysis was used for the electrochemical characterization of catalysts through an electrochemical cell with three electrodes connected to a potentiostat. The results showed that the best performing catalyst is the catalyst produced using 800‐W power for 40 seconds. The electrochemically active surface area values of this catalyst ranged from 54 to 45 m2/g. Single‐cell performance tests of the HT‐PEMFC were then carried out. In these tests, reformate gas mixture, consisting of H2, CO2, and CO, was fed to the anode side at 160°C without humidification. These tests for the best performing catalyst yielded peak power density of 0.280 W/cm2 and current density (at 0.6 V) of 0.180 A/cm2 in the H2/air environment and peak power density of 0.266 W/cm2 and current density (at 0.6 V) of 0.171 A/cm2 in the reformate gas/air environment. As a result of the experiments, it was found that Pt‐Ru/MWCNT‐GNP hybrid material is a suitable catalyst for HT‐PEMFC.  相似文献   

16.
In this study, a thermodynamic model of an active direct methanol fuel cell (DMFC) system, which couples in‐house experimental data for the DMFC with the mass and energy balances for the system components (condenser, mixing vessel, blower, and pumps), is formed. The modeling equations are solved using the Engineering Equation Solver (EES) program. This model gives the mass fluxes and thermodynamic properties of fluids for each state, heat and work transfer between the components and their surroundings, and electrical efficiency of the system. The effect of the methanol concentration (between 0.5 and 1.25 M) and air flow rate (between 20 and 30 mL cm?2 min?1) on the net power output and electrical efficiency of the system and the condenser outlet temperature is investigated. The results essentially showed that the highest value for the electrical efficiency of the system is 23.6% when the current density, methanol concentration, and air flow rate are taken as 0.2 A cm?2, 0.75 M, and 20 mL cm?2 min?1, respectively. In addition, the air flow rate was found to be the most significant parameter affecting the condenser outlet temperature.  相似文献   

17.
Glassy carbon electrode (GCE) modified by reduced graphene oxide Cu–Pd nano-dendrimer (Pd-CuNDs-RGO/GCE) was prepared using electro-deposition and spontaneous displacement methods. Graphene oxide was put on the surface of GCE by drop-casting, then a thin film of reduced graphene oxide (RGO) was formed by electro-reduction at ?0.9 V. The copper nano-dendrimers (CuNDs) were electro-plated on RGO/GCE surface. Finally, Pd-CuNDs-RGO/GCE was prepared by the spontaneous replacement of CuNDs with palladium nanoparticles (PdNPs) in a dilute solution of palladium. The electrode surface was characterized using field-emission scanning electron microscopy (FESEM), X-ray energy diffraction (EDX) spectroscopy, and electrochemical techniques. The electrochemical behavior of the modified electrode in the oxidation of alkaline solution of methanol was investigated. The experimental conditions affecting the performance of the modified electrode in the methanol oxidation were studied and optimized. Finally, the proposed electrode has the onset potential of ?0.5 V and the ratio of if/ib equal to 2.2, which confirms the high catalytic activity. The electrode has appropriate stability and shows about 86% of initial activity after 100 times testing.  相似文献   

18.
A Co/HTNT catalyst is developed by immobilizing Co on the surface of titanate nanotubes. The microstructure and composition of the catalyst are investigated with atomic absorption spectroscopy (AAS), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR) and X-ray photoelectron spectroscopy (XPS). The developed Co/HTNT catalyst shows great performance in catalyzing NaBH4 hydrolysis. The hydrolysis of 25 mg NaBH4 catalyzed by 50 mg Co/HTNT in 10 g NaOH solution (12.5 wt%) provides a hydrogen production rate of 1.04 L min?1 gCo?1 at 30 °C, and the activation energy of the reaction is 29.68 kJ mol?1. The high catalytic activity and economical property make this catalyst a promising choice for on-site hydrogen production from NaBH4 hydrolysis.  相似文献   

19.
A PtCo catalyst with an ordered cubic primitive structure was synthesized and investigated for the application as a cathode in direct methanol fuel cells. The synthesis involved the preparation of an amorphous PtOx/C precursor by the sulfite complex route, an impregnation with Co(NO3)2, a high temperature (800 °C) carbothermal reduction and, finally, a leaching procedure. This method led to the occurrence of a Pt3Co/C catalyst with a primitive cubic ordered (L12) phase and a mean crystallite size of 3.3 nm, as well as a suitable degree of alloying. This electrocatalyst was investigated for the oxygen reduction reaction in a direct methanol fuel cell (DMFC) operating in the range 30–90 °C. At 60 °C, under atmospheric pressure, a maximum power density of 40 mW cm−2 was obtained with the new PtCo catalyst formulation at low noble metal loading on the electrode (1 mg cm−2). This performance was 2.3 times higher than a benchmark Pt catalyst used for comparison.  相似文献   

20.
The design and synthesis of novel electrode catalysts is an applicable strategy to improve the performance of direct methanol fuel cells (DMFCs). The catalyst is composed of molybdenum disulfide as the shell and nickel silicide-doped sodalite (MoS2/NiSi@SOD) as the core. A series of characterization results indicate that NiSi is highly dispersed in the nanosized SOD cage on the surface of the SOD zeolite at the crystal faces of (011), (102), and (201). A thin conductive protective cover is formed by MoS2 on the surface of the zeolite. By the cyclic voltammetry (CV), the catalyst performs a maximum current density of 46.9 mA cm−2 (1250.1 A gNi−1) with 10 M methanol while no remarkable catalyst poisoning and catalyst deactivation are observed. It is revealed that MoS2/NiSi@SOD under high catalysis activity protects the Ni from the drain in the alkaline electrolyte, leading to a broad application prospect as a noble-metals-free DMFC catalyst.  相似文献   

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