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1.
The electrodeposition of Pd on graphite felt (GF, thickness ~3 mm in uncompressed state) was studied and the resulting catalyst was compared with Pt-Ru/GF for the electro-oxidation of formic acid. A micellar solution composed of the non-ionic surfactant Triton X-102 and an aqueous phase containing PdCl2 were utilized for the galvanostatic electrodeposition of Pd nanoparticles. The presence of the surfactant during electrodeposition coupled with pretreatment of the GF surface by a Shipley-type method (PdCl2 + SnCl2 solution) creating nucleation sites had a major impact on the Pd catalyst morphology and penetration throughout the electrode thickness, affecting, therefore, the electrocatalytic activity toward formic acid oxidation. It was found that large (~1,000 nm) Pd particles with smooth surface favored the indirect COad pathway, while Pd nanoparticles (diameter <40 nm) with rough surface, formed with surfactant and pretreatment, were much more active leading to the direct non-COad pathway. Due to pretreatment the GF surface has been modified and the effective catalytic system could be described as Pd/SnO2–Pd(PdO)/GF with possible electronic interaction between support and catalyst. In direct formic acid fuel cell (DFAFC) experiments at 333 K and 1 M HCOOH, the peak power density using the Pd/GF anode reached 852 W m?2 (57 g m?2 Pd) compared to 392 W m?2 (40 g m?2 Pd) with a commercial Pd catalyst-coated membrane (CCM). The long-term stability of Pd-based anodes was poor and inferior to Pt–Ru (4:1 at. ratio) prepared and tested under identical conditions.  相似文献   

2.
Oxygen reduction electrocatalysts based on the monoethanolmine complexes {[CoEtm]2(μ-Etm)4Ni(NO3)2} and {[CoEtm]2(μ-Etm)4Ni(NO3)2} + activated carbon AG-3 have been obtained by high-temperature synthesis. The nature of active centers on the synthesized electrocatalysts was described. Using potentiostatic and cyclic potentiodynamic voltammetry, the kinetic characteristics of catalysts in the oxygen electroreduction reaction were determined. Thermal decomposition of the thermally unstable complexes was described and character of the active centers formed was discussed. The optimal synthesis temperature of electrocatalysts is 600 °C in an inert atmosphere. The calculated exchange current densities for the oxygen electroreduction reaction at the catalysts in 1 M KOH at 20 °C was j 0  = 1.01 × 10?3 A g?1–3.3 × 10?3 A g?1. The Tafel slopes of stationary polarization curves are 0.054–0.063 V for b 1 and 0.106–0.125 V for b 2 . The prepared electrocatalysts can be recommended only for electrochemical systems with alkaline electrolyte.  相似文献   

3.
Ru-MCM-41 molecular sieves were prepared (Si/Ru atomic ratio?=?50 or 100) by a hydrothermal method and impregnated with TiO2. The materials were characterized by XRD, N2 physisorption, DRS, SEM and TEM. Their potential application to hydrogen production by photolysis of water using solar light was tested in a batch reactor using mixtures of water and glycerol (0–6.85 mol L?1) at pH varying from 1 to 11. The photocatalytic efficiency under simultaneous UV (0.05 μW cm?2) and visible light (90.07 W m?2) irradiation was compared to the activity of TiO2/MCM-41 (i.e., no Ru incorporated) and commercial Degussa TiO2 P25. The most active material was 20%TiO2/Ru-MCM-41(100) whose performance (220.6 µmol gTi ?1 H2) was approximately 47 times higher than TiO2 P25. Characterization results showed the deposition of TiO2 and revealed the formation of RuO2 on the surface. Hydrogen generation was improved due to higher charge separation at the TiO2/RuO2 heterojunction and to the enhancement of visible light absorption caused by surface plasmon resonance (SPR). Hydrogen production increased with glycerol concentration, tending to stabilize around 40.3 µmol h?1 gTi ?1 above 4 mol L?1 of glycerol. Hydrogen generation reached its maximum at extreme values of pH (1 and 11).  相似文献   

4.
Nickel–copper metallic foams were electrodeposited from an acidic electrolyte, using hydrogen bubble evolution as a dynamic template. Their morphology and chemical composition was studied by scanning electron microscopy and related to the deposition parameters (applied current density and deposition time). For high currents densities (above 1 A cm?2) the nickel–copper deposits have a three-dimensional foam-like morphology with randomly distributed nearly-circular pores whose walls present an open dendritic structure. The nickel–copper foams are crystalline and composed of pure nickel and a copper-rich phase containing nickel in solid solution. The electrochemical behaviour of the material was studied by cyclic voltammetry and chronopotentiometry (charge–discharge curves) aiming at its application as a positive electrode for supercapacitors. Cyclic voltammograms showed that the Ni–Cu foams have a pseudocapacitive behaviour. The specific capacitance was calculated from charge–discharge data and the best value (105 F g?1 at 1 mA cm?2) was obtained for nickel–copper foams deposited at 1.8 A cm?2 for 180 s. Cycling stability of these foams was also assessed and they present a 90 % capacitance retention after 10,000 cycles at 10 mA cm?2.  相似文献   

5.
A small quantity of palladium metal (Pd, 5 wt%) nanoparticles supported by a polypyrrole/manganese oxyhydroxide (PPy/MOH) nanocomposite was developed and investigated as an electrocatalyst for the alcohol electrooxidation reaction in alkaline media. In voltammetric studies, the PPy/MOH/Pd catalyst, compared to C/Pd, exhibited improved electrocatalytic activity for methanol electrooxidation. The peak current density ratios (j f/j b) for the C/Pd and PPy/MOH/Pd nanocomposite electrodes were 0.67 and 2.43, respectively, indicating that the PPy/MOH/Pd nanocomposite electrode was much more resistant to catalytic poisoning. The electrooxidation of ethylene glycol (EG), glycerol, and xylitol was also tested using the PPy/MOH/Pd nanocomposite electrode. Among these alcohol electrooxidations, that of EG exhibited the maximum power density of 430 mA cm?2. The intermediates formed during the electrooxidation reactions were removed by increasing the upper sweep potential from +0.2 to +1.0 V. The catalytic performance of the PPy/MOH nanocomposite is discussed in detail. The study results demonstrate that PPy/MOH acts as a superior catalytic supporting material for alcohol electrooxidation reactions in alkaline media.  相似文献   

6.
Nitrogen-doped carbon (CNx) nanotubes were synthesized by thermal decomposition of ferrocene/ethylenediamine mixture at 600–900 °C. The effect of the temperature on the growth and structure of CNx nanotubes was studied by transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. With increasing growth temperature, the total nitrogen content of CNx nanotubes was decreased from 8.93 to 6.01 at.%. The N configurations were changed from pyrrolic-N to quaternary-N when increasing the temperature. Examination of the catalytic activities of the nanotubes for oxygen reduction reaction by rotating disk electrode measurements and single-cell tests shows that the onset potential for oxygen reduction in 0.5 M H2SO4 of the most effective catalyst (CNx nanotubes synthesized at 900 °C) was 0.83 V versus the normal hydrogen electrode. A current density of 0.07 A cm?2 at 0.6 V was obtained in an H2/O2 proton-exchange membrane fuel cell at a cathode catalyst loading of 2 mg cm?2.  相似文献   

7.
Sodium-ion batteries (SIBs) is considered as a promising alternative to lithium-ion batteries. Supercapacitors (SCs) are receiving great attention for their significantly higher power density than batteries and prolonged cycle life. Herein, SIBs and SCs based on N-doped amorphous multi-size pores dominated polymeric frameworks were fabricated and examined. The enlarged interlayer spacing and multi-size-pore dominated interconnected architecture with high specific surface area, high pore volume and high N content optimize the electrochemical performance of N-PPF-20. As an anode material, N-PPF-20 exhibited a sodium ion storage capacity of 432.2 mAh g?1 at a current density of 0.05 A g?1, while maintaining a reversible capacity of 61.1 mAh g?1 at an ultrahigh current density of 20 A g?1. Additionally, a specific capacity of 158.3 mAh g?1 at 1 A g?1 was obtained after 1000 cycles, indicating an excellent cycling stability. When tested as an electrode material for SCs, N-PPF-20 delivered a high specific capacitance of 438.7 F g?1 at 0.1 A g?1, and a specific capacitance of 111.2 F g?1 was achieved even at a high current density of 10 A g?1. Meanwhile, a long-term cycling life test demonstrated a specific capacitance of 120 F g?1 at an ultrahigh current density of 10 A g?1 after 10,000 cycles.  相似文献   

8.
Methyl paraben is commonly employed as a preservative in pharmaceutical preparations, personal care products and some processed foods. However, the ester constitutes a potential pollutant in aquatic environments and has been classified as an endocrine disruptor. This study describes the degradation of methyl paraben (100 mg L?1 in 0.05 mol L?1 aqueous potassium sulfate at pH 5.7) by means of an electrochemical process (employing a boron-doped diamond anode) either alone or coupled with sonolysis. Electrolyses were performed at 25, 30 and 35 ± 1 °C during 120 min using applied constant current densities of 10.8 and 21.6 mA cm?2. The hybrid sonoelectrochemical processes were conducted under similar conditions with the application of ultrasound at a frequency of 20 kHz and a power intensity of 523 W cm?2. Although mineralization of methyl paraben could be achieved using either process, in comparison with the electrochemical method, the hybrid technique showed a higher mineralization efficiency (around 60 %) with approximately 50 % removal of total organic carbon, thereby confirming the synergistic effect of sonolysis.  相似文献   

9.
A polyaniline/titanium nitride (PANI/TiN) nanotube hybrid was prepared and used for an electrochemical supercapacitor application. Firstly, the well-aligned TiN nanotube array was prepared by anodization of titanium foil and subsequent nitridation through ammonia annealing. Then, PANI was deposited into TiN nanotube through the electrochemical polymerization process. The obtained PANI/TiN nanotube hybrid had an ordered porous structure. A high specific capacitance of 1,066 F g?1 was obtained at the charge–discharge current density of 1 A g?1 when only the mass of PANI was considered. The specific capacitance can even achieve 864 F g?1 at 10 A g?1 and still keep 93 % of the initial capacity after 200 cycles. An aqueous supercapacitor, consisting of two symmetric PANI/TiN nanotube hybrid electrodes and 1.0 M H2SO4 electrolyte solution, showed the specific capacitance of 194.8 F g?1, energy density of 9.74 Wh kg?1, and power density of 0.3 kW kg?1.  相似文献   

10.
Carbon nanofiber paper was prepared by electrospinning from thermosetting phenolic resin, followed by activation via KOH-containing molten salt at high temperature. By adding a small dosage of KOH in the molten salt the porous volume and specific surface area could be greatly improved. The obtained porous carbon nanofibers had a specific surface area of 1007 m2 g?1, total pore volume of 0.363 cm3 g?1, micropore volume of 0.247 cm3 g?1. The electrochemical measurements in 6 M KOH aqueous solution showed that the porous carbon nanofibers possessed high specific capacitance and considerable rate performance. The maximal specific capacitance of 288 F g?1 was achieved at 0.2 A g?1 and the specific capacitance could still remain 204 F g??1 at 20 A g?1 with the retention of 71%. In the molten salt system, the reaction between activating agent and carbon could be more efficient, hence, such molten salt-assisted activation method was considered as a general activation method for the high-specific-surface-areaed carbons.  相似文献   

11.
A series of Pd/γ-Al2O3 catalysts was prepared from [Pd(hfac)2] (hfac = hexafluoroacetylacetonate) in liquid carbon dioxide using the method reported by Kim et al. [Chem Mater 18:4710 (2006)]. The catalysts were characterized using CO pulse chemisorption, diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray absorption fine structure (XAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron microscopy. The catalysts were reduced initially in the high-pressure CO2 reaction cell using H2 at 75 °C. Samples were removed, stored in a desiccator, and re-reduced in situ at 250 °C prior to pulse chemisorption, DRIFTS and XAFS. CO pulse chemisorption evidenced that the Pd dispersion decreased from 55% to 5% as the Pd loading increased from 0.58 to 3.94 wt.%. The as-prepared 0.58 and 1.77 wt.% Pd/γ-Al2O3 catalysts (after air exposure) contained oxidized Pd species that were converted after in situ reduction to supported Pd particles. The average Pd particle sizes of these two catalysts (16 and 23 Å, respectively) estimated from the first-shell Pd–Pd coordination numbers are in good agreement with the CO chemisorption results. DRIFTS evidenced a prevalence of weakly bound linear CO (νCO = 2083 cm?1) adsorbed on the 0.58 wt.% Pd catalyst. A 2.95 wt% Pd catalyst (49 Å average particle size) also exhibited a strong linear CO band (νCO = 2093 cm?1). In contrast, CO chemisorption on a commercial 1 wt.% Pd/Al2O3 catalyst (37 Å average particle size) gave predominantly 2-fold bridging CO species. We infer that the supported Pd particles prepared from [Pd(hfac)2] are rougher on the atomic scale (with a higher percentage of edge and corner atoms) than equivalently sized particles in conventionally prepared Pd/γ-Al2O3 catalysts.  相似文献   

12.
In this study zirconium incorporated Cr3C2-(NiCr) coating has been sprayed on three superalloys viz. Superni 718, Superni 600 and Superco 605 using D-gun technique. A comparative study has been carried out to check the cyclic oxidation in air and hot corrosion in simulated incinerator environment (40%Na2SO4-40%K2SO4-10%NaCl-10%KCl) for the coated specimens at 900 °C for 100 cycles. Oxidation kinetics has been established for all the specimens using weight change measurements. Corrosion products have been characterized using X-ray diffractometer (XRD) and scanning electron microscopy/energy-dispersive analysis (SEM/EDAX). Cr3C2-(NiCr) + 0.2%wtZr coating provides very good corrosion resistance in air oxidation for all the three coated superalloys. As all the three coated superalloys shows parabolic behaviour with parabolic rate constant as 0.07 × 10?10 (g2 cm?4 s?1) for Superni 718, 0.43 × 10?10 (g2 cm?4 s?1) for Superni 600 and 0.3 × 10?10 (g2 cm?4 s?1) for Superco 605 This coating is also effective in the molten salt environment but coating on Co-based superalloy Superco 605 did not perform satisfactorily. The parabolic rate constants for coated Superni 718 is 0.61 × 10?10 (g2 cm?4 s?1), for coated Superni 600 is 6.72 × 10?10 (g2 cm?4 s?1) and for coated Superco 605 is 17.5 × 10?10 (g2 cm?4 s?1).  相似文献   

13.
Carbon-supported Pd-based binary alloy electrocatalysts (Pd–Co and Pd–Ni) with different particle sizes for polymer electrolyte fuel cells were prepared by a NaBH4 reduction method and investigated to examine effects of the size and lattice constant of the Pd alloy nanoparticles on the oxygen reduction reaction (ORR) activity. The particle size and lattice constant were controlled in the wide ranges 4.2–12.1 and 0.3802–0.3948 nm, respectively by heating the catalysts in specific atmospheres. The alloy structures were characterized by X-ray diffraction, transmission electron microscopy and X-ray absorption fine structure. The electrochemical tests of the Pd–Co/C and Pd–Ni/C catalysts were performed by cyclic voltammetry and rotating disk electrode in 0.1 M HClO4. Nearly linear relationship between the lattice constant and nanoparticle size was observed with the Pd–Co and Pd–Ni nanoparticles. The nanoparticle sizes and lattice constants of the Pd–Co/C and Pd–Ni/C electrocatalysts, which influence the Pd d-band center, showed positive and inverse relations with the ORR specific activities, respectively. The mass activities of the Pd–Co/C and Pd–Ni/C electrocatalysts showed an increasing trend with the lattice expansion.  相似文献   

14.
Mesoporous nickel cobaltite (NiCo2O4) nanoparticles were synthesized via a hydrothermal and soft-templating method through quasi-reverse-micelle mechanism. The physicochemical properties of the NiCo2O4 materials were characterized via X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectra, and nitrogen sorption isotherms measurements. The electrochemical performances of the NiCo2O4 electrode were investigated by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy tests. The obtained NiCo2O4 materials exhibit typical mesoporous structures, with an average particle size of about 200 nm, a specific surface area of 88.63 m2 g?1, and a total pore volume of 0.337 cm3 g?1. The facile electrolytes penetration for the mesoporous structures favors high-performance of the NiCo2O4 electrode. The NiCo2O4 electrode shows a high specific capacitance (591 F g?1 at 1 A g?1), high-rate capability (248 F g?1 at 20 A g?1), and a good cycling behavior for tested 3,000 cycles, indicating a promising application for electrochemical capacitors.  相似文献   

15.
Lithium transition metal phosphates have the capability of improving cathode energy densities up to 800 Wh kg?1, a 27 % increase over conventional cathode active material energy densities. In this study, the effect of base-to-acid (NH4OH:H3PO4) stoichiometric conditions on the intrinsic reversible capacity of lithium cobalt phosphate (LiCoPO4) active material are investigated through microwave synthesis and electrochemical testing. Variation in solution pH results in an increase of 69 mAh g?1 in achievable capacity. X-ray diffraction results show highly crystalline LiCoPO4, with particle sizes ranging from 200 nm to greater than 1 μm based upon scanning electron microscopy. Electrochemical analysis with 1 M LiPF6 EC:EMC (1:2 v/v) provides the highest capacity over multiple cycles. A discharge capacity of 128 mAh g?1 (78 % of theoretical capacity) is achievable for intrinsic LiCoPO4 without further treatment (e.g., carbon coating) at an effective 0.1 C rate with a proper constant current–constant voltage step. Analysis of reported synthesis techniques shows that microwave synthesis yields the highest capacity for the intrinsic LiCoPO4 material to date.  相似文献   

16.
Titanium dioxide (TiO2) nanotubes were fabricated by anodisation of titanium foil in 0.15 M ammonium fluoride in an aqueous solution of glycerol (90 % v/v). Electropolymerisation of pyrrole and deposition of gold nanoparticles on to the TiO2 nanotube array electrode were carried out by cyclic voltammetry (CV). Electrochemical characterization of the sensor was performed by CV and electrochemical impedance spectroscopy. The morphology of the electrode was studied after every step of modification using field emission scanning electron microscope and atomic force microscope. The sensor was tested for AA and other biomolecules in phosphate buffered saline solution of pH 7 using CV, differential pulse voltammetry and amperometry. The sensor exhibited very high sensitivity of 63.912 μA mM?1 cm?2 and excellent selectivity to ascorbic acid (AA) in the presence of other biomolecules such as uric acid, dopamine, glucose and para-acetaminophen. It also showed very good linearity (R = 0.9995) over a wide range (1 μM–5 mM) of detection. The sensor was tested for AA in lemon and found its concentration to be 339 mg ml?1.  相似文献   

17.
Ordered mesoporous carbon is synthesized by the organic–organic self-assembly method with novolac as carbon precursor and two kinds of triblock copolymers (Pluronic F127 and P123) as template. The hexagonal structure and a worm-hole structure are observed by TEM. The carbonization temperature is determined by TG and FT-IR. Characterization of physical properties of mesoporous carbon is executed by N2 absorption–desorption isotherms and XRD. The mass ratios of carbon precursor/template affect the textural properties of mesoporous carbon. The mesoporous carbon with F127/PF of 1/1 has lager surface area (670 m2 g?1), pore size (3.2 nm), pore volume (0.40 cm3 g?1), smaller microporous surface area (368 m2 g?1) and wall thickness (3.7 nm) compare to that with F127/PF of 0.5/1 (576 m2 g?1, 2.7 nm, 0.29 cm3 g?1, 409 m2 g?1 and 4.3 nm, respectively). The mesoporous carbon prepared by carbonization at high temperature (700 °C) exhibits lager surface area, lower pore size and pore volume than the corresponding one obtained at 500 °C. The structure and order of the resulting materials are notably affected with types of templates. The mesoporous carbon with P123 as template exhibits worm-hole structure compare to that with F127 as template with hexagonal structure. In general, the pore size of mesoporous carbon with novolac as precursor is smaller than that with resorcinol–formaldehyde as precursor.  相似文献   

18.
A microbial fuel cell using manganese oxide oxygen reduction catalysts   总被引:1,自引:0,他引:1  
Microbial fuel cells (MFCs) are a potential method for enhanced water and waste treatment, which offer the additional benefit of energy generation. Manganese oxide was prepared by a simple chemical oxidation using potassium permanganate. Carbon-supported manganese oxide nanoparticles were successfully characterised as cathode materials for MFCs. The manganese oxide particles when used in a two-chamber MFC, using inoculum from an anaerobically digested sewage sludge, were found to exhibit similar oxygen reduction performance to that in separate electrochemical tests. MFC tests were conducted in a simple two chamber cell using aqueous air-saturated catholytes separated from the anode chamber by a Nafion membrane. MFC peak power densities were ca. 161 mW m?2 for MnO x /C compared to 193 mW m?2 for a benchmark Pt/C, in neutral solution at room temperature. The catalyst materials demonstrated good stability in the 7.0–10.0 pH range. Theoretical (IR free) peak power densities were 937 mW m?2 for MnO x /C compared with 1037 mW m?2 for Pt/C in the same experimental conditions: showing the MFCs performances can easily be improved by using more favourable conditions (more conductive electrolyte, improved cathode catalyst etc.). Our studies indicated that the use of our low cost MnO x /C catalysts is of potential interest for the future application of MFC systems.  相似文献   

19.
The antecedent effect of lime on the gaseous products of denitrification (N2O and N2) was examined in a laboratory study using a clay loam soil (Soil 1) with a starting pH of 5.4, and a sandy loam soil (Soil 2) with a starting pH of 5.3. The soils were amended with 0, 2.3, 5.7 and 18.9 g CaCO3 kg?1, and were incubated for a period of 3 years at 4 °C during which time the soil equilibrated at pH values of 4.7, 5.8, 7.3 and 7.7 (Soil 1) and pH 4.7, 5.2, 6.6 and 7.6 (Soil 2). Ammonium nitrate, labelled with 15N (15NH4NO3, NH4 15NO3 and 15NH4 15NO3) was added to each incubation jar at a rate of 7.14 μmol N g?1 oven dried (OD) soil. Headspace gas samples were extracted daily over a 5 days incubation period at 20 °C. The amount of N2O and N2, and 15N enrichment of N2O-N in the headspace, was determined using continuous-flow isotope-ratio mass spectrometry. As pH increased, the quantity of N2 and N2O emitted significantly increased in both soils (P < 0.001), with a peak N2 flux of 0.179 μmol N g?1 OD soil h?1, and a peak N2O flux of 0.002 μmol N g?1 OD soil h?1 occurring at pH 7.6, 2 days after the addition of NH4NO3. The loss as N2 far exceeded the loss of N2O, which remained at less than 1 % of the total mineral N content of the soil. Lime generally lowered the N2O:N2 ratio, however the results from this study suggest that it is not a mitigation strategy for GHG emissions.  相似文献   

20.
Li2S is coated with carbon to improve the electrical conductivity of the composite cathode in all-solid-state lithium-sulfur batteries. Carbon is applied by thermal evaporation from a polyacrylonitrile (PAN) source at 600 °C for 5 h. It is shown that the carbon coating is impurity free, and the crystallinity of Li2S is well maintained. The electronic conductivity of Li2S is dramatically improved from 9.21 × 10?9 S cm?1 to 2.39 × 10?2 S cm?1 upon carbon coating. An all-solid-state battery prepared with the carbon-coated Li2S shows a high initial capacity of 585 mAh g?1 (g of Li2S) that increases up to 730 mAh g?1 (g of carbon-coated Li2S) by the 10th cycle. This high capacity is stable throughout the 25 cycles tested, with an excellent coulombic efficiency of 99%. Carbon-coated Li2S is advantageous for all-solid-state batteries due to the increased electrical conductivity, while allowing a reduction of the total carbon content present in the composite cathode.  相似文献   

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