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1.
We demonstrate Schottky diode type hydrogen (H2) sensors both on a planar GaN film grown by Metal Organic Chemical Vapor Deposition and on a honeycomb GaN nanonetwork grown by Molecular Beam Epitaxy. The metal-semiconductor Pt/planar GaN film Schottky diode was fabricated and used as a H2 sensor element with response time τ   of 80 s (10,000 ppm) and 2000 ppm limit of detection for hydrogen gas (LODH2)(LODH2) at 373 K. A significant improvement in H2 detection is observed for the honeycomb GaN nanonetwork. The characteristics of the H2 sensor on the honeycomb GaN nanonetwork are quantitatively studied in comparison with that on the planar GaN film. The response time τ is shortened by a factor of 27 (3 s versus   80 s) and the LODH2LODH2 is lowered by two orders of magnitude, from 2000 to 50 ppm. Moreover, the operating temperature could be reduced to room temperature. Through analyzing the transient-state, we observed a reduction of activation energy Ea from 6.22 to 2.4 kcal/mol. The reduced activation energyEa is regarded as the reason that leads to a superior H2 detection of the honeycomb GaN nanonetwork in terms of response time τ and operating temperature.  相似文献   

2.
The effect of H2S on the performance of La0.7Ce0.2FeO3 perovskite catalyst was investigated for the production of hydrogen from simulated coal-derived syngas via the water–gas shift reaction at 600 °C and 1 atm. The results show that the catalyst activity decreases with increasing concentrations of H2S up to 1100 ppm, but the negative effect of H2S on its activity is reversible. However, even at the high H2S concentrations catalyst activity is still greater than that measured with sour shift catalyst. Overall, the results indicate that La0.7Ce0.2FeO3 perovskite catalyst has a high degree of H2S tolerance, particularly in the low H2S concentration regime.  相似文献   

3.
M2BiSbO7 (M = Ga, Fe, Gd) were synthesized by solid state reaction process for the first time as novel photocatalysts. The structural and photocatalytic properties of M2BiSbO7 (M = Ga, Fe, Gd) were reported. The results showed that Ga2BiSbO7, Fe2BiSbO7 and Gd2BiSbO7 crystallized with the pyrochlore-type structure, cubic crystal system and space group Fd3m. The lattice parameter for Ga2BiSbO7, Fe2BiSbO7 or Gd2BiSbO7 was 10.34804 Å, 10.41030 Å or 10.70353 Å respectively. In addition, the band gaps of Ga2BiSbO7 and Gd2BiSbO7 were separately estimated to be 1.955 eV and 2.081 eV. For the photocatalytic water splitting reaction, H2 or O2 evolved abundantly with Ga2BiSbO7, Fe2BiSbO7 or Gd2BiSbO7 as photocatalyst from CH3OH/H2O or AgNO3/H2O solution respectively under visible light irradiation (Wavelength > 420 nm). The results indicated that the activities of three photocatalysts followed the order of Ga2BiSbO7 > Fe2BiSbO7 > Gd2BiSbO7. Moreover, photocatalytic H2 evolution from aqueous methanol solution was observed with Ga2BiSbO7, Fe2BiSbO7 or Gd2BiSbO7 as photocatalyst under different light irradiation (λ > 390 nm and λ > 0 nm). The results showed that the photocatalytic activity decreased with increasing incident wavelength (λ). The photocatalytic activity was further enhanced under visible light irradiation with Ga2BiSbO7, Fe2BiSbO7 or Gd2BiSbO7 loaded by Pt, NiO or RuO2 (λ > 420 nm). The effect of Pt was better than that of NiO or RuO2 for improving the photocatalytic activity of Ga2BiSbO7, Fe2BiSbO7 or Gd2BiSbO7.  相似文献   

4.
This paper presents results of thermodynamic analysis and experimental evaluation of hydrogen production by steam reforming of ethanol (SRE) combined with CO2 absorption using a mixture of a solid absorbent (CaO, CaO*MgO and Na2ZrO3) and a Ni/Al2O3 catalyst. Thermodynamic analysis results indicate that a maximum of 69.5% H2 (dry basis) is feasible at 1 atm, H2O/C2H5OH = 6 (molar ratio) and T = 600 °C. whereas, the addition of a CO2 absorbent at 1 atm, T = 600 °C and H2O/C2H5OH/Absorbent = 6:1:2.5, produced a H2 concentration of 96.6, 94.1, and 92.2% using CaO, CaO*MgO, and Na2ZrO3, respectively. SRE experimental evaluation achieved a maximum of 60% H2. While combining SRE and a CO2 absorbent exhibited a concentration of 96, 94, and 90% employing CaO, CaO*MgO, and Na2ZrO3, respectively at 1 atm, T = 600 °C, SV = 414 h−1 and H2O/C2H5OH/absorbent = 6:1:2.5 (molar ratio).  相似文献   

5.
La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) has been applied as hydrogen electrode (cathode) material in solid oxide electrolysis cells operating with different steam concentrations (20, 40, 60 and 80 vol.% absolute humidity (AH)) using 40 sccm H2 carrier gas at 800, 850 and 900 °C, respectively. Impedance spectra and voltage-current curves were measured as a function of cell electrolysis current density and steam concentration to characterize the cell performance. The cell resistance decreased with the increase in electrolysis current density while increased with the increase in steam concentration under the same electrolysis current density. At 1.6 V applied electrolysis voltage, the maximum consumed current density increased from 431 mA cm−2 for 20 vol.% AH to 593 mA cm−2 for 80 vol.% AH at 850 °C. Polarization and impedance spectra experiments revealed that LSCM-YSZ hydrogen electrode played a major role in the electrolysis reaction.  相似文献   

6.
In this work, the hydriding–dehydriding properties of the LiBH4–NbF5 mixtures were investigated. It was found that the dehydrogenation and reversibility properties of LiBH4 were significantly improved by NbF5. Temperature-programed dehydrogenation (TPD) showed that 5LiBH4–NbF5 sample started releasing hydrogen from as low as 60 °C, and 4 wt.% hydrogen could be obtained below 255 °C. Meanwhile, ∼7 wt.% H2 could be reached at 400 °C in 20LiBH4–NbF5 sample, whereas pristine LiBH4 only released ∼0.7 wt.% H2. In addition, reversibility measurement demonstrated that over 4.4 wt.% H2 could still be released even during the fifth dehydrogenation in 20LiBH4–NbF5 sample. The experimental results suggested that a new borohydride possibly formed during ball milling the LiBH4–NbF5 mixtures might be the source of the active effect of NbF5 on LiBH4.  相似文献   

7.
Lithium aluminum hydride (LiAlH4) is considered as an attractive candidate for hydrogen storage owing to its favorable thermodynamics and high hydrogen storage capacity. However, its reaction kinetics and thermodynamics have to be improved for the practical application. In our present work, we have systematically investigated the effect of NiCo2O4 (NCO) additive on the dehydrogenation properties and microstructure refinement in LiAlH4. The dehydrogenation kinetics of LiAlH4 can be significantly increased with the increase of NiCo2O4 content and dehydrogenation temperature. The 2 mol% NiCo2O4-doped LiAlH4 (2% NCO–LiAlH4) exhibits the superior dehydrogenation performances, which releases 4.95 wt% H2 at 130 °C and 6.47 wt% H2 at 150 °C within 150 min. In contrast, the undoped LiAlH4 sample just releases <1 wt% H2 after 150 min. About 3.7 wt.% of hydrogen can be released from 2% NCO–LiAlH4 at 90 °C, where total 7.10 wt% of hydrogen is released at 150 °C. Moreover, 2% NCO–LiAlH4 displayed remarkably reduced activation energy for the dehydrogenation of LiAlH4.  相似文献   

8.
In this experimental study, a membrane reactor housing a composite membrane constituted by a thin Pd-layer supported onto Al2O3 is utilized to perform methanol steam reforming reaction to produce high-grade hydrogen for PEM fuel cell applications. The influence of various parameters such as temperature, from 280 to 330 °C, and pressure, from 1.5 to 2.5 bar, is analyzed. A commercial Cu/Zn-based catalyst is packed in the annulus of the membrane reactor and the experimental tests are performed at space velocity equal to 18,500 h−1 and H2O:CH3OH feed molar ratio equal to 2.5:1. Results in terms of methanol conversion, hydrogen recovery, hydrogen yield and products selectivities are given. As a best result of this work, 85% of methanol conversion and a highly pure hydrogen stream permeated through the membrane with a CO content lower than 10 ppm were reached at 330 °C and 2.5 bar. Furthermore, a comparison between the experimental results obtained in this work and literature data is proposed and discussed.  相似文献   

9.
Much progress has been made in the development of novel visible light photocatalysts that split water into hydrogen (H2) and oxygen (O2). In this study, we examine the impact of initial solution pH on H2 production using an Ru/(CuAg)0.15In0.3Zn1.4S2 photocatalyst under visible light irradiation. In addition, the reaction mechanism was analyzed by examining the oxidation products of the electron donor (I‾) at different solution pH values. The results show that the initial pH significantly influenced the rate of H2 production and quantum yield (QY). In particular, the photocatalyst yielded the highest apparent QY (∼12.8%) at 420 ± 5 nm and highest H2 production rate (∼525 μmol h−1) at pH 2; with increasing pH, the H2 production and QY decreased significantly. The oxidation product of I‾ at pH < 6 was mainly I3‾, whereas at pH > 6 water splitting did not occur at all, so no IO3‾ or I2 were observed.  相似文献   

10.
N-doped In2Ga2ZnO7 photocatalysts were fabricated by solid state reaction route. All the prepared photocatalysts were successfully characterised by PXRD, optical absorption spectra, SEM, TEM, XPS, BET surface area and photoresponse studies. The formation of In2Ga2ZnO7 was confirmed by the PXRD pattern. Optical absorption spectra showed that the visible light absorption of all the photocatalysts were enhanced by nitrogen doping. Among all the prepared photocatalysts, 1 wt% Pt loaded N-GaInZn-500 showed enhanced photocatalytic activity towards hydrogen evolution under visible light irradiation in presence of 10 vol% methanol solution as sacrificial agent. The excellent photocatalytic activity of N-GaInZn-500 is in agreement with N-content, bandgap energy, PL intensity and Surface area.  相似文献   

11.
The mutual destabilization of LiAlH4 and MgH2 in the reactive hydride composite LiAlH4-MgH2 is attributed to the formation of intermediate compounds, including Li-Mg and Mg-Al alloys, upon dehydrogenation. TiF3 was doped into the composite for promoting this interaction and thus enhancing the hydrogen sorption properties. Experimental analysis on the LiAlH4-MgH2-TiF3 composite was performed via temperature-programmed desorption (TPD), differential scanning calorimetry (DSC), isothermal sorption, pressure-composition isotherms (PCI), and powder X-ray diffraction (XRD). For LiAlH4-MgH2-TiF3 composite (mole ratio 1:1:0.05), the dehydrogenation temperature range starts from about 60 °C, which is 100 °C lower than for LiAlH4-MgH2. At 300 °C, the LiAlH4-MgH2-TiF3 composite can desorb 2.48 wt% hydrogen in 10 min during its second stage dehydrogenation, corresponding to the decomposition of MgH2. In contrast, 20 min was required for the LiAlH4-MgH2 sample to release so much hydrogen capacity under the same conditions. The hydrogen absorption properties of the LiAlH4-MgH2-TiF3 composite were also improved significantly as compared to the LiAlH4-MgH2 composite. A hydrogen absorption capacity of 2.68 wt% under 300 °C and 20 atm H2 pressure was reached after 5 min in the LiAlH4-MgH2-TiF3 composite, which is larger than that of LiAlH4-MgH2 (1.75 wt%). XRD results show that the MgH2 and LiH were reformed after rehydrogenation.  相似文献   

12.
An integrated reactor system which combines oxygen permeable La0.6Sr0.4Co0.8Ni0.2O3−δ (LSCN) perovskite ceramic hollow fiber membrane with Ni based catalyst has been successfully developed to produce hydrogen through oxy-CO2 reforming of methane (OCRM). Dense La0.6Sr0.4Co0.8Ni0.2O3−δ hollow fiber membrane was prepared using phase inversion-sintering method. OCRM reaction was tested from 650 °C to 800 °C with a quartz reactor packed with 0.5 g Ni/Al2O3 catalyst around the LSCN hollow fiber membrane. CH4 and CO2 were used as reactants and air as the oxygen source was fed through the bore side of the hollow fiber membrane. In order to gauge the effectiveness of this membrane reactor system, air flow was closed at 800 °C and dry reforming of methane (DRM) was tested for comparison. The results show that the oxygen fluxes of LSCN membrane swept by helium are nearly 3 times less than those swept by OCRM reactants. With increasing temperature and oxygen supply, methane conversion in the OCRM reactor reaches 100%, but CO2 conversion decreases from 87% to 72% due to the competition reaction with POM. CO selectivity is as high as nearly 100% at reaction temperatures of 700 °C–800 °C while H2 selectivity reaches a maximum of 88% at 700 °C. At 800 °C, when air supply was closed and DRM was conducted for comparison, CO selectivity decreased to 91%, resulting in carbon deposition which was around 4 times more than those obtained under OCRM reaction and H2/CO ratio decreased from 0.93 to 0.74, showing better carbon resistance and higher H2 selectivity of the Ni-based catalyst over the integrated oxygen separation-OCRM reaction across the LSCN hollow fiber membrane reactor.  相似文献   

13.
The Polyaniline (PANI) and Titanium dioxide (TiO2)/PANI composite thin film based chemiresistor type gas sensors for hydrogen (H2) gas sensing application are presented in this paper. Pure PANI and TiO2/PANI composites with different wt% of TiO2 were synthesized by chemical oxidative polymerization of aniline using ammonium persulfate in acidic medium at 0-5 °C. Thin films of PANI and TiO2/PANI composites were deposited on copper (Cu) interdigited electrodes (IDE) by spin coating method to prepare the chemiresistor sensor. Finally, the response of these chemiresistor sensors for H2 gas was evaluated by monitoring the change in electrical resistance at room temperature. It was observed that the TiO2/PANI composite thin film based chemiresistor sensors show a higher response as compared to pure PANI sensor. The structural and optical properties of these composite films have been characterized by X-ray diffraction (XRD) and UV-Visible (UV-Vis) spectroscopy respectively. Morphological and structural properties of these composites have also been characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) respectively.  相似文献   

14.
The hydrogen storage properties of 5LiBH4 + Mg2FeH6 reactive hydride composites for reversible hydrogen storage were investigated by comparing with the 2LiBH4 + MgH2 composite in the present work. The dehydrogenation pathway and reaction mechanism of 5LiBH4 + Mg2FeH6 composite were also investigated and elucidated. The self-decomposition of Mg2FeH6 leads to the in situ formation of Mg and Fe particles on the surface of LiBH4, resulting in a well dispersion between different reacting phases. The formation of FeB is observed during the dehydrogenation of 5LiBH4 + Mg2FeH6 composite, which might supplies nucleation sites of MgB2 during the dehydrogenation process, but is not an ascendant catalyst for the self-decomposition of LiBH4. And FeB can also transform to the LiBH4 and Fe by reacting with LiH and H2 during the rehydrogenation process. The dehydrogenation capacity for 5LiBH4 + Mg2FeH6 composite still gets to 6.5 wt% even after four cycles. The X-ray diffraction analyses reveal the phase transitions during the hydriding and dehydriding cycle. The formed FeB in the composite maintains a nanostructure after four hydriding-dehydriding cycles. The loss of hydrogen storage capacity and de-/rehydrogenation kinetics can be attributed to the incomplete generation of Mg2FeH6 during the rehydrogenation process.  相似文献   

15.
Carbon dispersed Pd5Cu4Pt nanocatalyst synthesized by chemical reduction with NaBH4 for the oxygen reduction reaction (ORR) in acid media is investigated. Nanocatalyst is physically characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (DRX). Results demonstrate the formation of conglomerate nanometric particles ranging from 2 to 10 nm in size. Electrochemical activity is demonstrated by cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The results show that the onset potential for the ORR on Pd5Cu4Pt is shifted by ca. 50 mV to more positive values and enhanced catalytic current densities are observed in comparison to carbon dispersed PdCu and Pd catalysts. The Pd5Cu4Pt tested as cathode electrode in a membrane-electrode assembly (MEA) shows a power density of 330 mW cm−2 at 0.5 V and 80 °C, resulting an attractive low Pt content cathode nanocatalyst for PEM fuel cells.  相似文献   

16.
A highly selective hydrogen (H2) sensor has been successfully developed by using an yttria-stabilized zirconia (YSZ)-based mixed-potential-type sensor utilizing SnO2 (+30 wt.% YSZ) sensing electrode (SE) with an intermediate Al2O3 barrier layer which was coated with a catalyst layer of Cr2O3. The sensor utilizing SnO2 (+30 wt.% YSZ)-SE was found to be capable of detecting H2 and propene (C3H6) sensitively at 550 °C. In order to enhance the selectivity towards H2, a selective C3H6 oxidation catalyst was employed to minimize unwanted responses caused by interfering gases. Among the examined metal oxides, Cr2O3 facilitated the selective oxidation of C3H6. However, the addition or lamination of Cr2O3 to SnO2 (+30 wt.% YSZ)-SE was found to diminish the sensing responses to all examined gases. Therefore, an intermediate layer of Al2O3 was sandwiched between the SE layer and the catalyst layer to prevent the penetration of Cr2O3 particles into the SE layer. The sensor using SnO2 (+30 wt.% YSZ)-SE coated with a catalyst layer of Cr2O3 as well as an intermediate layer of Al2O3 exhibited a sensitive response toward H2, with only minor responses toward other examined gases at 550 °C under humid conditions (21 vol.% O2 and 1.35 vol.% H2O in N2 balance). A linear relationship was observed between sensitivity and H2 concentration in the range of 20–800 ppm on a logarithmic scale. The results of sensing performance evaluation and polarization curve measurements indicate that the sensing mechanism is based on the mixed-potential model.  相似文献   

17.
The Mg17Al12 intermetallic compound is brittle and easily pulverized and hydrogenated, which holds the promise as a hydrogen source because the theoretical hydrogen generation capacity by hydrolysis of Mg17Al12 hydride (MHA) is as high as 13.6 wt.%. However, it was found that the hydrolysis reaction of MHA without any additives would be rapidly interrupted because of the formation of a passive layer on the surface of the particles. The influence of CaH2 on the hydrogen generation performances of the MHA + CaH2 mixtures by hydrolysis was investigated in this paper. The result showed that the addition of CaH2 by ball-milling is effective to improve the hydrolysis reactivity of the mixtures. The best was obtained by MHA+10wt.% CaH2 mixture ball-milled for 1 h, which produces 1389 ml H2/g at 70 °C after 1 h of hydrolysis in pure water, namely the hydrogen generation yield reaches 94.8%. In this paper, the reasons of the improvement and the reaction mechanism have also been discussed respectively.  相似文献   

18.
Catalysts of nano-sized nickel oxide particles based on flowerlike lanthanum oxide microspheres with high disperse were prepared to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, SEM, 77K N2 adsorption were used to analyze and observe the catalysts’ structure, morphology and porosity. Catalytic parameters with respect to yield of H2, activity, selectivity towards gaseous products and stability with time-on-stream and time-on-off-stream were all determined. This special morphology NiO/La2O3 catalyst represented more than 1000 h time-on-stream stability test and 500 h time-on-off-stream stability test for hydrogen fuel production from ethanol steam reforming at 300 °C without any deactivation. During the 1000 h time-on-stream stability test, ethanol–water mixtures could be converted into H2, CO, and CH4 with average selectivity values of 57.0, 20.1, 19.6 and little CO2 of 3.2 mol%, respectively, and average ethanol conversion values of 96.7 mol%, with H2 yield of 1.61 mol H2/mol C2H5OH. During the 500 h time-on-off-stream stability test, ethanol–water mixtures could be converted into H2, CO, CH4 and CO2 with average selectivity values of 65.1, 17.3, 15.1 and 2.5 mol%, respectively, and average ethanol conversion values of 80.0 mol%. For the ethanol-H2 and petrolic hybrid vehicle (EH–HV), the combustion value is the most important factor. So, it was very suitable for the EH–HV application that the low temperature ethanol steam reforming products’ distribution was with high H2, CO, CH4 and very low CO2 selectivity over the special NiO/La2O3 flowerlike microspheres.  相似文献   

19.
Zigzag-shaped pure-Pd thin film and Pd–SiO2 thin-film mixture as resistive-type hydrogen sensors were deposited on cover-glass substrates through a multiple-boat thermal evaporator. Temperature dependence of the resistance of the pure-Pd resistive-type sensor showed a relative sensitivity of 3.2% at 80 °C with a temperature coefficient of the resistance (TCR) of 0.058%/°C. Sensing properties of the Pd–SiO2 resistive-type sensor responding to the presence of 1% H2/N2 are much better than those of the pure-Pd one, including a higher relative sensitivity (9%–7.7%), a faster response time (10 s–30 s), and a lower detection concentration limit (50 ppm–100 ppm). A higher dissociation rate and a faster diffusion rate due to porous-like properties and more hydrogen atoms caught due to oxygen associated with the Pd–SiO2 thin-film mixture explain why the Pd–SiO2 resistive-type sensor has a higher relative sensitivity with a shorter response time.  相似文献   

20.
Both kinetics and thermodynamics properties of MgH2 are significantly improved by the addition of Mg(AlH4)2. The as-prepared MgH2–Mg(AlH4)2 composite displays superior hydrogen desorption performances, which starts to desorb hydrogen at 90 °C, and a total amount of 7.76 wt% hydrogen is released during its decomposition. The enthalpy of MgH2-relevant desorption is 32.3 kJ mol−1 H2 in the MgH2–Mg(AlH4)2 composite, obviously decreased than that of pure MgH2. The dehydriding mechanism of MgH2–Mg(AlH4)2 composite is systematically investigated by using x-ray diffraction and differential scanning calorimetry. Firstly, Mg(AlH4)2 decomposes and produces active Al. Subsequently, the in-situ formed Al reacts with MgH2 and forms Mg–Al alloys. For its reversibility, the products are fully re-hydrogenated into MgH2 and Al, under 3 MPa H2 pressure at 300 °C for 5 h.  相似文献   

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