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1.
A highly active and stable catalyst for hydrogen-iodide decomposition reaction in sulfur-iodine (SI) cycle has been prepared in the form of PdCeO2 nanocatalyst by sol-gel method with different calcination temperatures (300 °C, 500 °C, and 700 °C). XRD and TEM confirmed a size around 6–8 nm for PdCeO2 particles calcined at 300 °C. Raman study revealed large number oxygen vacancies in PdCeO2-300 when compared to PdCeO2-500 and PdCeO2-700. With increase in calcination temperature, the average particle size increased whereas the specific surface area and number of oxygen vacancies decreased. Hydrogen-iodide catalytic-decomposition was carried out in the temperature range of 400°C–550 °C in a quartz-tube, vertical, fixed-bed reactor with 55 wt % aqueous hydrogen-iodide feed over PdCeO2 catalyst using nitrogen as a carrier gas. PdCeO2-300 showed hydrogen-iodide conversion of 23.3%, which is close to the theoretical equilibrium conversion of 24%, at 550 °C. It also showed a reasonable stability with a time-on-stream of 5 h.  相似文献   

2.
By surface-decorating PtTiO2 hybrid catalyst with MoS2 nanosheets, we prepared a new MoS2/PtTiO2 ternary system as high-performance photocatalysts. The ternary MoS2/PtTiO2 outperforms both the binary MoS2TiO2 and PtTiO2 systems in photocatalytic hydrogen evolution with an AQY (apparent quantum yield) value of 12.54% at 420 nm, owing to the unique ternary design that creates more efficient electron transport path and electron-hole separation mechanism. Electrochemical characterization showed that the MoS2/PtTiO2 ternary electrode afford an efficient pathway of photo-excited electrons from TiO2 to surface-decorated Pt nanoparticles using MoS2 and internal Pt nanoparticles as bridges, thus significantly promoting electron transfer, reducing the system overpotential and leading to the activation of more reactive sites. This internal electron transfer pathway (TiO2 → Pt (internal) → MoS2 → Pt (surface)) eliminates the need of other metal cocatalysts because the Pt nanoparticles play two roles of storing the conduction band electrons of TiO2 and acting as co-catalyst for reduction of protons to hydrogen. This unique ternary metal-semiconductor heterojunction for efficient photocatalytic hydrogen evolution provides a meaningful reference for reasonable design of other hybrid photocatalysts.  相似文献   

3.
A one-pot synthesis method is utilized for the fabrication of ultrasmall platinum-silver nanoparticles decorated on graphene (PtAg/G) catalyst. This method has several advantages such as inexpensiveness, simplicity, low temperature, surfactant free, reductant free, being environmentally friendly and greenness. In this work, graphene and silver formate were dispersed in ultrapure water in an ultrasonic bath at 25 °C followed by through a galvanic displacement reaction; to prepare PtAg/G, PtCl2 was added to the suspension under mild stirring condition. The morphology, crystal structure and chemical compositions of the as-fabricated PtAg/G and Pt/C catalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Energy dispersive X-ray spectroscopy (EDS) techniques. Electrochemical techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical activity of the PtAg/G and Pt/C catalysts. The TEM images illustrate the uniform distribution of ultrasmall PtAg nanoparticles with the average size of 2–3 nm on the graphene nanosheets. The PtAg/G promoted the current density 2.46 times as much as Pt/C with a negative shift in onset oxidation potential and peak potential for oxidation reaction of methanol. Besides, the novel PtAg/G catalyst shows large electrochemically active surface area, lower apparent activation energy, and higher levels of durability in comparison to the Pt/C catalyst for the oxidation of methanol. The PtAg/G catalyst depicts extraordinary catalytic performance and stability to those of the Pt/C catalyst toward methanol oxidation in alkaline media.  相似文献   

4.
In this paper, sulfonated nitrogen sulfur co-doped graphene (S-NS-GR) nanocomposite, i.e., nitrogen sulfur co-doped graphene functionalized with SO3H group as a novel catalyst support material was prepared. PtPd nanoparticles (PtPd NPs) were deposited on the surface of S-NS-GR by a facile electrochemical approach. The morphology and structure of Pd-PtNPs/S-NS-GR were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and electrochemical impedance spectroscopy (EIS), respectively. In addition, the electrocatalytic performance of catalyst for methanol oxidation reaction (MOR) was systematically studied by cyclic voltammetry and chronoamperometry in alkaline media. Compared with PtPd NPs supported on nitrogen sulfur co-doped graphene (Pt-PdNPs/NS-GR), the excellent performance of Pd-PtNPs/S-NS-GR is mainly ascribed to the embedding of abundant functional groups (SO3H) into the NS-GR layers, which not only facilitate the homogeneous distribution of metal NPs, but also strengthen the interaction between metals and support material, thus improve the stability of catalyst in MOR.  相似文献   

5.
This work first reports AuCu alloys deposited on the surface of TiO2 nanosheets (TiNs) to form heterojunction. A simple deposition-precipitation method was used to construct a new type of AuCu/TiNs heterostructures through gradually depositing Au and Cu nanoparticles on TiNs. Such structures served the dual advantage of constructing a heterostructure which can improve visible light absorption, and the formation of a Schottky barrier between AuCu alloys (lower Fermi level) and TiNs (higher Fermi level) which can suppress the recombination of photo-generated charge carriers to improve the overall photocatalytic activity. The mass ratio of Au and Cu in the AuCu/TiNs heterostructures and the sequence and method of their deposition are found to be the important factors which affect the photocatalytic performance. When the mass ratio of Au to Cu was determined to be 1: 1, the AuCu/TiNs heterostructure exhibited the best photocatalytic performance for hydrogen production from water splitting (over 9 times than TiNs, 1.47 times than Au/TiNs, and 1.75 times than Cu/TiNs).  相似文献   

6.
A novel photocatalyst comprises of ZrO2TiO2 immobilized on reduced graphene oxide (rGO) – a ternary heterojunction (ZrO2TiO2/rGO) was synthesized by using facile chemical method. The nanocomposite was prepared with a strategy to achieve better utilization of excitons for catalytic reactions by channelizing from metal oxide surfaces to rGO support. TEM and XRD analysis results revealed the heterojunction formed between ZrO2 and single crystalline anatase TiO2. The mesoporous structure of ZrO2TiO2 was confirmed using BET analysis. The red shift in absorption edge position of ZrO2TiO2/rGO photocatalyst was characterized by using diffuse reflectance UV–Visible spectra. ZrO2TiO2/rGO showed greater interfacial charge transfer efficiency than ZrO2TiO2, which was evidenced by well suppressed PL intensity and high photocurrent of ZrO2TiO2/rGO. The suitable band gap of 1.0 wt% ZrO2TiO2/rGO facilitated the utilization of solar light in a wide range by responding to the light of energy equal to as well as greater than 2.95 eV by the additional formation of excited high-energy electrons (HEEs). ZrO2TiO2/rGO showed the enhanced H2 production than TiO2/rGO, which revealed the role of ZrO2 for the effective charge separation at the heterojunction and the solar light response. The optimum loading of 1.0 wt% of ZrO2 and rGO on TiO2 showed the highest photocatalytic performance (7773 μmolh?1gcat?1) for hydrogen (H2) production under direct solar light irradiation.  相似文献   

7.
Zeolitic Imidazolate Frameworks (ZIF) is one of the potential candidates as highly conducting networks with large surface area with a possibility to be used as catalyst support for low temperature fuel cells. In the present study, highly active state-of-the-art PtCo@NCNTs (Nitrogen Doped Carbon Nanotube) catalyst was synthesized by pyrolyzing ZIF-67 along with Pt precursor under flowing ArH2 atmosphere. The multi-walled NCNTs were densely grown on the surface of ZIF particles after pyrolysis. The high resolution TEM examination was employed to examine the nature of the PtCo particles as well as multi-walled NCNTs. Rotating disk electrode study was used for measuring oxygen reduction reaction performance for PtCo@NCNTs in 0.1 M HClO4 and compared with commercial Pt/C catalyst. Fuel cell performance with PtCo@NCNT and commercial Pt/C catalysts was evaluated at 70 °C using Nafion-212 electrolyte using H2 and O2 gases (100% RH) and the observed peak power density of 630 and 560 mW cm?2, respectively.  相似文献   

8.
In recent years, biomass has been introduced as a promising solution for environmental crisis. Biomass steam gasification is a valuable process for hydrogen production. Main problem of this process is low conversion and low partial pressure of hydrogen in product stream. PdAg membrane reactor (MR) can be used in biomass steam gasification to improve the process efficiency. Hence, Computational fluid dynamic (CFD) method was used in this study for a detail modeling and analyzing the biomass steam gasification in a two-dimensional PdAg MR. After good agreement of CFD model results with literature experimental data, simulation results was indicated that the PdAg MR has better efficiency compared with traditional reactor (TR). Biomass conversion of near 100%, CO selectivity in the range 0–14 and H2 recovery of 70% in the best condition were achieved. In addition, different flow patterns (cocurrent and counter-current modules) were compared for MR and overall efficiency (biomass conversion) of counter-current model was obtained higher than co-current model. In summary, for all operating conditions and modules, PdAg MR was showed better efficiency compared with TR.  相似文献   

9.
Carbonaceous materials containing non-precious metal atoms and doped with nitrogen have enthralled stunning attention in the field of electrochemical energy conversion systems. Herein, we demonstrated a facile method to fabricate iron and nitrogen doped carbon nanofiber (FeN-CNFs) catalyst material from ferric chloride and interfacial synthesized polyaniline (PANI) nanofibers, by carbonization process in an inert atmosphere at 800 °C. Further, synthesized material was characterized by elemental analysis and X-ray photoelectron spectroscopy (XPS) that confirms the presence of FeN bonds. The structural and morphological features are studied using various microscopy and spectroscopy techniques. The oxygen reduction reaction (ORR) activity of synthesized catalyst materials was examined by rotating disk electrode experiments in 0.1 M KOH. Among all these synthesized materials FeN-CNFs material showed enhanced ORR activity regarding current density and onset potential. Also, FeN-CNFs catalyst exhibited tolerance to methanol and durability in comparison to commercial Pt/C catalyst. The superior performance of FeN-CNFs may be attributed due to the introduction of Fe and formation of FeN bond in catalyst material.  相似文献   

10.
In this paper, Pt/TiO2 and PtGa/TiO2 catalysts with similar Pt dispersion and similar structural and morphological characteristics were compared in the H2 production from the phototransformation of aqueous solutions of ethanol. Catalysts were characterized by means of N2 adsorption-desorption, XRD, Raman, H2-TPR, UV–Vis diffuse reflectance spectroscopy, XPS and CO chemisorption. The photocatalytic reaction was carried out in liquid and vapour phase. The photocatalytic transformation of ethanol(aq) vapour over Pt/TiO2 and PtGa/TiO2 catalysts was studied by in situ DRIFTS-MS. Differences in the photocatalytic transformation of ethanol(aq) over Pt/TiO2 and PtGa/TiO2 were determined. The effect of Ga is analysed in the light of the evolution of surface species under photocatalytic reaction conditions.  相似文献   

11.
Bimetallic nanoparticles of Au and Ni in the form of alloy nanostructures with varying Ni content are synthesized on reduced graphene oxide (rGO) sheets via a simple solution chemistry route and tested as electrocatalysts towards the hydrogen evolution (HE) and oxygen reduction (OR) reactions using polarization and impedance studies. The AuNi alloy NPs/rGO nanocomposites display excellent electrocatalytic activity which is found to improve with increasing Ni content in the AuNi/rGO alloy nanocomposites. For HER, the best AuNi alloy NPs/rGO electrocatalyst, the one with the highest Ni content, exhibits high activity with an onset overpotential approaching zero versus the reversible hydrogen electrode and an overpotential of only 37 mV at 10 mA cm?2. Additionally, a low Tafel slope of 33 mV dec?1 and a high exchange current density of 0.6 mA cm?2 are measured which are very close to those of commercial Pt/C catalyst. Also, in the ORR tests, this electrocatalyst displays comparable activity to Pt/C. The Koutecky–Levich plots referred to a 4-electron mechanism for the reduction of dissolved O2 on the AuNi alloy NPs/rGO catalyst. The electrocatalyst thus demonstrates excellent activity towards HER and ORR. Additionally, it exhibits outstanding operational durability and activation after 10,000th cycles assuring its practical applicability.  相似文献   

12.
The mechanism of tandem dimethylamine-borane (NHMe2BH3, DMAB) dehydrogenation and alkene hydrogenation catalyzed by [Pd(NHC)(PMe3)] are investigated by density functional theory (DFT) calculations [NHC = N,N′-bis(2,6-diisopropylphenyl) imidazole-2-ylidene]. Four possible DMAB dehydrogenation mechanisms have been carefully investigated involving concerted BH/NH activation, sequential BH/NH activation, sequential NH/BH activation, and proton transfer mechanism. DFT studies show that the NH proton transfers to ligated carbene carbon and sequential CH/BH activation is the most kinetically favorable pathway with the lowest activation barrier of 23.8 kcal/mol. For hydrogenation, it was found that a trans-dihydride Pd(II) complex, [Pd(H)2(NHC)(PMe3)], formed in the dehydrogenation process, serves as an effective catalyst for reduction of trans-stilbene.  相似文献   

13.
Methanol is one of the chemical compounds utilized in fuel cells. The direct methanol fuel cell (DMFC) can be applied in many devices such as light electric vehicles and field equipment. Such a fuel cell is characterized by its high fuel energy density and low pollution. Despite many advantages of DMFCs, they are not commercially available, as the most efficient catalyst, which can be used in this process, has not been developed yet. Traditionally, it was platinum that was used in these fuel cells which is expensive and susceptible to CO poisoning. The solution to this is the use of bimetallic catalysts such as a NiPt system. In this study, we used a sintered NiPt electrode as the anode for the electrocatalytic oxidation of methanol. Based on our results, the sintered NiPt electrodes exhibited much higher activity in the oxidation of methanol, when compared with some conventional anodes.  相似文献   

14.
Vanadium trichloride (VCl3) is one of the best catalysts for the hydrogenation-dehydrogenation MgMgH2 system. X-ray photoelectron spectroscopy (XPS) has shown that VCl3 reduced to metallic vanadium during ball milling along with MgH2. The in-situ-formed metallic vanadium doped over the MgH2 surface which has shown an excellent catalytic effect on hydrogenation-dehydrogenation of the MgMgH2 system. The catalyzed surface reduced the activation energies of hydrogenation-dehydrogenation reactions and correspondingly on-set hydrogenation-dehydrogenation temperatures. The microstructural analysis has also shown an excellent grain refinement property of VCl3 which reduced the crystallite size of MgH2. The decreased crystallite size decreases the diffusion path length of hydrogen and increases the active surface area which eventually enhances the hydrogenation-dehydrogenation kinetics of MgMgH2.  相似文献   

15.
Through electrodeposition, controlling hydrogen evolution reaction and selective electrochemical dealloying of copper from NiCu porous foam, highly nanoporous nickel and nickel oxide is fabricated on the copper surface. Electrochemically reduced graphene oxide (ERGO) is loaded on the NiNiO foam as high-performance electrodes for supercapacitors through pulsed galvanostatic reduction of drop casted graphene oxide nanosheets at different duty cycles and frequencies. Surface morphology and composition of fabricated ERGO/NiNiO foam composite electrodes are characterized using scanning electron microscopy (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Raman Spectroscopy. Electrochemical impedance spectroscopy (EIS) measurements, galvanostatic charge/discharge (GCD) and cyclic voltammetry (CV) are carried out to study the electrochemical behavior of ERGO/NiNiO foam electrodes. From structural and electrochemical characterizations, optimized parameters for pulse duty cycle and frequency were found to be 10% and 1000 Hz, respectively. As a result, the ERGO/NiNiO foam film (ic = ?10 mA/cm2, f = 1000 Hz and DC = 10%) provides a specific capacitance of 2298 F/g in 1 M KOH at a current density of 1 A/g. Stability study of fabricated film represents a long cycling life up to 4000 cycles with 0.7% decay in specific capacitance at the high current density of 20 A/g in the potential range of 0–0.6 V vs. saturated calomel electrode (SCE).  相似文献   

16.
[Ni,Mg,Al]-layered double hydroxide (LDH) was modified with NaOH solution to prepare the LDH-derived Ni/MgOAl2O3 catalyst and characterized by X-ray diffraction, inductively coupled plasma optical emission spectrometer, scanning electron microscope, transmission electron microscopy, temperature programmed desorption of CO2 or NH3, N2 adsorption, and thermogravimetry analysis, respectively. The resultant Ni/MgOAl2O3 catalysts were used for CO2 reforming of CH4. The results showed that the concentration of NaOH solution has an obvious effect on the structure of LDH and catalytic performances of the resultant nickel-based catalysts. Aluminum species in LDH was partly dissolved with increasing NaOH solution concentration, resulting in the increase of [M2+/M3+] molar ratio and the interlayer spacing of modified LDHs. The surface area and pore volume, especially mesoporous surface area and pore volume, were improved compared with parent [Ni,Mg,Al]-LDH, and the catalytic activity of the resultant Ni/MgOAl2O3 catalyst in CO2 reforming of CH4 was enhanced. NaOH concentration has a slight influence on CO2 conversion and stability of the resultant Ni/MgOAl2O3 catalyst. The Ni/MgOAl2O3 prepared from the modified [Ni,Mg,Al]-LDH with 0.1 mol/L NaOH exhibits the best stability and anti-coke deposit ability. CH4 and CO2 conversions retain at about 91% and 96%, respectively, along with a H2/CO ratio of about 0.90 after reaction of 28 h. High CO2/CH4 molar ratio can improve catalytic stability, resistance to coke deposit and Ni sintering of the catalyst.  相似文献   

17.
In present work, we reported an novel oxide-salt Al2O3NaAlO2 composite, which was prepared by mixing Al2O3 and Na2CO3 two phase materials in different weight ratio, and then sintering at 1100 °C. The X-ray diffraction pattern, scanning-electron microscope and impedance spectra are applied to characterize the crystal structure, morphology and electrical properties of the Al2O3NaAlO2 composite. The Al2O3NaAlO2 composite as electrolyte membrane was sandwiched by two pieces of Ni0.8Co0.15Al0.05Li-oxide (NCAL) electrode layer to construct advanced fuel cell. Optimizing the weight ratio of Al2O3 and NaAlO2, such cell delivered an highest power density of 789 mW/cm2 and an open circuit voltage (Voc) of 1.13 V at 575 °C. The superior performance is mainly due to the excellent ion-conducting of Al2O3NaAlO2 composites and the outstanding catalysis activity of the NCAL eletrodes. The EIS results revealed that the Al2O3NaAlO2 composite possessed superior ionic conductivity of 0.121 S/cm at 575 °C. The interfacial effects between oxide-salt two phase including space-charge and structural misfit at the interface region dominated the ion transport for Al2O3NaAlO2 composite.  相似文献   

18.
This work mainly aims to establish a link between Co/Ce loading ratio in CoCe/ZrO2 catalysts and their Carbon Dioxide Reforming of Methane (CDRM) performance. In this context, catalysts with different Co and Ce loadings were prepared and characterized via BET, XRD, HRTEM-EDX, XPS and Raman, and parametrically tested under different CDRM conditions. Dispersion of Co particles was nonhomogeneous on all samples. For the sample with the highest Co/Ce ratio (10%Co2%Ce/ZrO2), higher amount of lattice oxygen vacancies and lowest degree of ceria reduction were determined. Raman analysis showed that graphitic carbon coexisted with amorphous carbon on the surface of all spent samples. The extent of side reactions prevailed in determining selectivity. It was expressed that both CoCe synergistic interaction and synchronous contribution of Ce and ZrO2 were enhanced for the samples having lower Co/Ce ratio. It was confirmed that Ce is only responsible for oxygen transfer but not its formation.  相似文献   

19.
A compact and adherent CoCu spinel coating on ferritic stainless steel was developed by electroplating a CoCu alloy layer followed by oxidation. The CoCu alloy was oxidized into a three-layer structure consisted of a thinner CuO outer layer, a middle thicker Cu0.92Co2.08O4 layer and an inner Co3O4 layer after an oxidation treatment of 2 h at 800 °C in air. The three-layer oxide structure was transformed into a double-layer scale with a (Co,Cr,Cu,Mn,Fe)3O4 spinel outer layer and an inner Cr-rich oxide layer after an oxidation of 500 h at 800 °C in air. The CuCo coating enhanced the oxidation resistance of the alloy and served as a diffusion barrier against the outward migration of Cr elements. Meanwhile, the area specific resistance (ASR) of the scale for the CuCo coated alloy was significantly lower than that for the bare sample.  相似文献   

20.
A series of PtRu and PtMo bimetallic catalysts were prepared via a chemical reduction method by bubbling CO to form carbonyl compounds as metal precursors. In both cases the PtRu and PtMo bimetallic electrocatalysts achieved the maximum activity when the amount of Ru and Mo in the material was 50%wt. The physicochemical characterization of the electrocatalytic materials through X-ray diffraction (XRD) and transmission electron microscopy (TEM) has determined the presence of bimetallic structures. The electrochemical characterization using cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and polarization curves in Proton Exchange Membrane Fuel Cells (PEMFC) and Direct Methanol Fuel Cell (DMFC) allowed to systematically investigate the electrocatalytic activity of the synthesized materials for the electrooxidation of hydrogen and methanol. The PtRu/SWCNT electrocatalysts showed a higher current density at least 7-fold and 3-fold compared with Pt/SWCNT and PtMo/SWCNT electrocatalysts, respectively. Besides, the Pt50%–Ru50%/SWCNT exhibited a shifting to negative values in the onset potential reaction for the electrooxidation of methanol of 200 mV in comparison with Pt100%/SWCNT and Pt50%–Mo50%/SWCNT electrocatalysts. The experimental and simulated polarization curves obtained from DMFC show that PtRu/SWCNT and PtMo/SWCNT electrocatalysts exhibited higher power and current densities values compared with the Pt/SWCNT electrocatalyst. The membrane-electrode assembly (MEA) with Nafion® and the PtRu/SWCNT electrocatalysts showed an open-circuit voltage value of 0.730 V, significantly higher than that the values for the MEAs with Pt/SWCNT (0.663 V) and PtMo/SWCNT (0.633 V), respectively.  相似文献   

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