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1.
Hydrogen sulfide (H2S) gas is a by-product from natural gas refining, hydrodesulfurization of various fossil fuels, and syngas cleaning from pyrolysis and gasification. Catalytic pyrolysis of H2S provides an alternative and effective pathway to recover both H2 and sulfur. Catalysts from hydrotalcite of ZnAl, ZnNiAl, and ZnFeAl were employed for H2S pyrolysis and compared with TiO2 and MoS2 at atmospheric pressure and temperatures in the range of 923–1123 K. Kinetic analysis was carried out in a packed bed reactor which revealed the effect of H2S partial pressures to be of the order of 0.8–1 with respect to H2S. The developed novel catalysts showed improved performance with significantly reduced activation energy compared to TiO2 by 30 kJ/mol as well as higher H2S conversion during pyrolysis (17% at 1173 K) than with MoS2 catalyst, even at high H2S partial pressure which is necessary for viable hydrogen production. The new approach showed an alternate economical and efficient pathway of catalyst design to obtain high activity and stability for simultaneous H2 energy and pure sulfur recovery from unwanted H2S resources.  相似文献   

2.
In the present work, nanocrystalline Mg2Ni with an average size of 20–50 nm was prepared via ball milling of a 2MgH2Ni powder followed by compression under a pressure of 280 MPa. The phase component, microstructure, and hydrogen sorption properties were characterized by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-temperature (PCT) and synchronous thermal analyses (DSC/TG). Compared to the non-compressed 2MgH2Ni powder, the compressed 2MgH2Ni pellet shows lower dehydrogenation temperature (290 °C) and a single-phase Mg2Ni is obtained after hydrogen desorption. PCT measurements show that the nanocrystalline Mg2Ni obtained from dehydrogenated 2MgH2Ni pellet has a single step hydrogen absorption and desorption with fairly low absorption (?57.47 kJ/mol H2) and desorption (61.26 kJ/mol H2) enthalpies. It has very fast hydrogen absorption kinetics at 375 °C with about 3.44 wt% hydrogen absorbed in less than 5 min. The results gathered in this study show that ball milling followed by compression is an efficient method to produce Mg-based ternary hydrides.  相似文献   

3.
The synthesis of nitrogen doped orthorhombic niobium oxide nanoplates/reduced graphene oxide composites (NNb2O5/rGO) and their photocatalytic activity towards hydrogen generation from water and H2S under natural sunlight has been demonstrated, uniquely. Nanostructured NNb2O5/rGO is synthesized by in situ wet chemical method using urea as a source of nitrogen and optimized by varying percentage of graphene oxide (GO). X?ray diffraction (XRD) study reveals that NNb2O5 have orthorhombic crystal structure with crystalline size, 35 nm. Further, X?ray photoelectron spectroscopy (XPS) confirm the presence of nitrogen and rGO in NNb2O5/rGO nanocomposite. Morphological features of (NNb2O5/rGO) were examined by FE?SEM and FE?TEM showed Nb2O5 nanoplates of diameter 25–40 nm anchored on 2D rGO. Diffuse reflectance spectra depicts the extended absorbance in the visible region with band gap of 2.2 eV. Considering the band gap in the visible region, the photocatalytic hydrogen generation from water and H2S has been performed. The 1 wt % rGO hybridized NNb2O5 (S2) exhibited superior photocatalytic hydrogen generation (537 μmol/h) from water and (1385 μmol/h) from H2S under sunlight. The improved photocatalytic activity is attributed due to an extended absorbance in the visible region, modified electronic structure upon doping and formation of well defined NNb2O5/rGO interface, provides large surface area, accelerates the supression of electron and hole pairs recombination rate. In our opinion, this works may provides facile route for energy efficient and economic approach for fabrication of NNb2O5/rGO nanocomposites as a visible light active photocatalyst.  相似文献   

4.
The fatigue limit properties of a carbon steel and a low-alloy CrMo steel were investigated via fully-reversed tension-compression tests, using smooth specimens in air and in 115-MPa hydrogen gas. With respect to the CrMo steel, specimens with sharp notches were also tested in order to investigate the threshold behavior of small cracks. The obtained SN data inferred that the fatigue limit was not negatively affected by hydrogen in either of the steels. Observation of fatigue cracks in the unbroken specimens revealed that non-propagating cracks can exist even in 115-MPa hydrogen gas, and that the crack growth threshold is not degraded by hydrogen. The experimental results provide justification for the fatigue limit design of components that are to be exposed to high-pressure hydrogen gas.  相似文献   

5.
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   

6.
In order to decrease oxide growth kinetics, maintain suitable conductivity and prevent Cr-volatilization of AISI 430 stainless steels (430 SS) as the interconnect for intermediate temperature solid oxide fuel cells (SOFCs), a CoNiO spinel oxide protective coating has been successfully fabricated on the 430 SS specimen using a simple and cheap process with two steps: 1) electroplation of CoNi alloy layer and 2) pre-oxidation treatment to convert the CoNi alloy into spinel oxide. The CoNiO spinel layer on the 430 SS (CoNiO 430 SS) is dense and uniform with 8–10 μm thickness. And the CoNiO spinel oxide protective coating consists of a main face-centered-cubic (fcc) NiCo2O4 spinel phase and a minor fcc NiO phase. Compared with bare 430 SS, the oxidation resistance and the conductivity of the CoNiO 430 SS have been improved remarkably under simulated typical SOFC operating cathode conditions (at 800 °C in air). After an isothermal oxidation test at 800 °C, the area specific resistance (ASR) of CoNiO 430 SS is much lower and stable (0.1 Ω cm2 for 100 h and 0.9 Ω cm2 for 600 h) than that of bare 430 SS (1.2 Ω cm2 for 100 h and 2.4 Ω cm2 for 600 h). These performances of CoNiO 430 SS imply that it can be a promising candidate interconnect for solid oxide fuel cell.  相似文献   

7.
The nanoscaled Ni-based compounds (Ni3C, Ni3N, NiO and Ni2P) are synthesized by chemical methods. The MgH2-X (X = Ni3C, Ni3N, NiO and Ni2P) composites are prepared by mechanical ball-milling. The dehydrogenation properties of Mg-based composites are systematically studied using isothermal dehydrogenation apparatus, temperature-programmed desorption system and differential scanning calorimetry. It is experimentally confirmed that the dehydrogenation performance of the Mg-based materials ranks as following: MgH2Ni3C, MgH2Ni3N, MgH2NiO and MgH2Ni2P. The onset dehydrogenation temperatures of MgH2Ni3C, MgH2Ni3N, MgH2NiO and MgH2Ni2P are 160 °C, 180 °C, 205 °C and 248 °C, respectively. The four Mg-based composites respectively release 6.2, 4.9, 4.1 and 3.5 wt% H2 within 20 min at 300 °C. The activation energies of MgH2Ni3C, MgH2Ni3N, MgH2NiO and MgH2Ni2P are 97.8, 100.0, 119.7 and 132.5 kJ mol?1, respectively. It' found that the MgH2Ni3C composites exhibit the best hydrogen storage properties. Moreover, the catalytic mechanism of the Ni-based compounds is also discussed. It is found that Ni binding with low electron-negativity element is favorable for the dehydrogenation of the Mg-based composites.  相似文献   

8.
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   

9.
Investigations on the catalytic effects of a non-reactive and stable additive, SrTiO3, on the hydrogen storage properties of the 4MgH2Na3AlH6 destabilized system were carried out for the first time. The Na3AlH6 compound and the destabilized systems used in the investigations are prepared using ball milling method. The doped system, 4MgH2Na3AlH6SrTiO3, had an initial dehydrogenation temperature of 145 °C, which 25 °C lower as compared to the un-doped system. The isothermal absorption and desorption capacity at 320 °C has increased by 1.2 wt% and 1.6 wt% with the addition of SrTiO3 as compared to the 4MgH2Na3AlH6 destabilized system. The decomposition activation energy of the doped system is estimated to be 117.1 kJ/mol. As for the XRD analyses at different decomposition stages, SrTiO3 is found to be stable and inert. In addition to SrTiO3, similar phases are found in the doped and the un-doped system during the decomposition and dehydrogenation processes. Therefore, the catalytic effect of the SrTiO3 is speculated owing to its ability to modify the physical structure of the 4MgH2Na3AlH6 particles through pulverization effect.  相似文献   

10.
We successfully synthesized mesocrystalline Ta2O5 nanosheets supported bimetallic PdPt nanoparticles by the photo-reduction method. The as-prepared mesocrystalline Ta2O5 nanosheets in this work showed amazing visible-light absorption, mainly because of the formation of oxygen vacancy defects. And the as-prepared bimetallic PdPt/mesocrystalline Ta2O5 nanaosheets also showed highly enhanced UV–Vis light absorption and highly improved photocatalytic activity for hydrogen production in comparison to that of commercial Ta2O5, mesocrystalline Ta2O5 nanosheets, Pd/mesocrystalline Ta2O5 nanosheets and Pt/mesocrystalline Ta2O5 nanosheets. The highest photocatalytic hydrogen production rate of PdPt/mesocrystalline Ta2O5 nanaosheets was 21529.52 g?1 h?1, which was about 21.2 times of commercial Ta2O5, and the apparent quantum efficiency of PdPt/mesocrystalline Ta2O5 nanaosheets for hydrogen production was about 16.5% at 254 nm. The highly enhanced photocatalytic activity was mainly because of the significant roles of PdPt nanoparticles for accelerating the charge separation and transport upon illumination. The as-prepared PdPt/mesocrystalline Ta2O5 nanaosheets in this work could serve as an efficient photocatalyst for green energy production.  相似文献   

11.
High cost and poor stability of catalysts remain major obstacles for the commercialization of direct ethanol fuel cells (DEFCs). In this work, a Pt9Rh/TiO2C nanostructured catalyst is synthesized via an impregnation-reduction method followed by thermal annealing in N2 at ambient pressure. X-ray powder diffraction (XRD) and scanning transmission electron microscopy (STEM) are used to characterize the corresponding physico-chemical properties of the as-prepared catalysts. The results reveal that PtRh nanoparticles are uniformly distributed on the TiO2C hybrid support material. Cyclic voltammetry, linear scan voltammetry, CO-stripping voltammograms, chronoamperometry and chronopotentiometry methods are employed to investigate their catalytic performance for ethanol oxidation. The results show that the Pt9Rh/TiO2C produced a current density of 1039.5 mA mgPt?1, which are 3.98, 8.31 and 2.43 times higher than Pt/TiO2C, Pt/C and Pt9Rh/C, respectively. Furthermore, the Pt9Rh/TiO2C also has greater resistance to CO-poisoning and displays better stability for ethanol oxidation than other catalysts. Pt9Rh/TiO2C therefore provides a promising material for ethanol oxidation in direct ethanol fuel cells.  相似文献   

12.
In this research, the activity and selectivity of a platinum-based catalyst for H2 production through aqueous phase reforming (APR) in a fixed-bed reactor (FBR) as well as, a structured catalyst microreactor (MR) were investigated. In this venue, first, an in-house designed MR was fabricated and the catalytic material was deposited on the channel walls of this steel made reactor. After verification of the stability of the coated layer, the prepared reactor was employed to investigate the APR reaction. In this regard, APR of the ethylene glycol and glycerol over Pt/Al2O3 and Pt/CeO2Al2O3 catalyst were conducted in an MR and FBR. Obtained results demonstrated that employing Pt/CeO2Al2O3 as a highly active catalyst in an FBR, slightly reduced the H2 selectivity for the APR reaction of the ethylene glycol. Moreover, this effect appeared even more pronounced in reforming of glycerol. On the other hand, utilization of an MR for the APR of glycerol improved the H2 selectivity due to the more active Pt/CeO2Al2O3 catalyst, for this process. Comparison of the results revealed that the highly active catalyst alongside a reactor alleviating mass transfer limitations were two complementary factors leading to better performance of such chemical systems. Moreover, this research emphasized that obtained values of the APR conversion and H2 selectivity in an MR coated with the Pt/CeO2Al2O3 catalyst was superior to those obtained from an FBR. Ultimately, the best results obtained for the aforementioned catalytic species indicated that the APR of glycerol in a structured catalyst MR led to 75.3% conversion of glycerol and 92.4% selectivity to hydrogen production both of which were considerably better than results determined in an FBR.  相似文献   

13.
To overcome the hydrogen-induced amorphization and phase disproportionation in the fast de-/hydrogenation of YFe2, the alloying of partial substituting Y with Zr was carried out to obtain Y1?xZrxFe2 (x = 0.1, 0.2, 0.3, 0.5) alloys. All YZrFe alloys remained single C15 Laves phase structure at states of as-annealed, hydrogenated and dehydrogenated. With the increasing of Zr content, the YZrFe alloys showed the decrease in the lattice constants and hydrogenation capacity, but the increase in the dehydrogenation capacity and dehydriding equilibrium pressure. The alloy Y0.9Zr0.1Fe2 showed maximum initial hydrogenation capacity of 1.87 wt% H, while the alloy Y0.5Zr0.5Fe2 showed highest desorption capacity of 1.26 wt% with obvious dehydriding plateau. Based on experiment analysis and first principle calculation of binding energy, the great improvement in the dehydriding thermodynamics for YZrFe alloys is attributed to the change in the unit cell volume, electron concentration and stability of hydrides due to the Zr substitution.  相似文献   

14.
Pt/CeMgAl layered double hydroxides with different Ce contents were prepared by one-step co-precipitation method, which underwent calcination and reduction with hydrogen and were finally converted into Pt/CeMgAlO catalysts. These catalysts were tested in the dehydrogenation of methylcyclohexane (MCH) into toluene to produce hydrogen. The addition of CeO2 promoted the dispersion of Pt and decreased the Pt particle size. During the dehydrogenation reaction, toluene was the only liquid product and its selectivity was higher than 99.9%. MCH conversion increased with the reaction temperature rising. The conversion and hydrogen evolution rate on Pt/Ce14MgAlO350 reached up to 98.5% and 1358.6 mmol/gPt/min at 350 °C. Moreover, Pt/CeMgAlO catalysts exhibited no acidity and presented a high anti-coking ability and good stability. These results suggest that Pt/CeMgAlO catalysts have potential industrial application for hydrogen energy utilization.  相似文献   

15.
Porous silica coated Ni/CeO2ZrO2 catalysts were synthesized for steam reforming of acetic acid. The silica coated Ni/CeO2ZrO2 catalyst showed a significantly enhanced activity (95% acetic acid conversion) than the Ni/CeO2ZrO2 catalysts (62% acetic acid conversion) at a low temperature (550 °C). Interaction between Ni/CeO2ZrO2 and silica layer was proved to be a crucial role on enhancing of catalytic activities. Further characterization (XPS, H2-TPR) indicates this interaction facilitates the steam reforming reaction and raises the selectivity of CO by modifying the surface Ni electronic structure. In addition, the coated catalyst also exhibited a good stability and no obvious deactivation was detected at 550 °C and 600 °C within 30 h.  相似文献   

16.
With the combination of experiment and first-principles theory, we have evaluated and explored the catalytic effects of graphitic nanofibres for hydrogen desorption behaviour in magnesium hydride. Helical form of graphene nanofibres (HGNF) have larger surface area, curved configuration and high density of graphene layers resulting in large quantity of exposed carbon sheet edges. Therefore they are found to considerably improve hydrogen desorption from MgH2 at lower temperatures compared to graphene (onset desorption temperature of MgH2 catalyzed by HGNF is 45 °C lower as compared to MgH2 catalyzed by graphene). Using density functional theory, we find that graphene sheet edges, both the zigzag and armchair type, can weaken MgH bonds in magnesium hydride. When the MgH2 is catalyzed with higher electronegative and reactive graphene edge of graphene, the electron transfer occurs from Mg to carbon, due to which MgH2 is dissociated into hydrogen and MgH component. The Mg gets bonded with the graphene edge carbon atoms in the form of CMgH and CH bonds. In the as formed CMgH, the graphene edges “grab” more electronic charge as compared to the normal charge donation of Mg to H. This leads to the weakening of the MgH bond, causing hydrogen to desorbs at lower temperatures.  相似文献   

17.
To improve the hydrogen storage properties of YZrFe alloys, the alloying with Ti was carried out to obtain Y0.7Zr(0.3-x)TixFe2 (x = 0.03, 0.09, 0.1, 0.2) alloys by different processes. It was expected that Ti would substitute Zr and decrease the lattice constant of YFe2-based C15 Laves phase. All YZrTiFe quaternary alloys consist of the main Y(Zr)Fe2 phase and the minor YFe3 phase. Despite the large solubility of Ti in Zr or Zr in Y, the Ti incorporation into YZrFe alloys results in the inhomogeneity of Y and the segregation of Ti, and thus decreases the hydrogen storage capacity. Only the alloy Y0.7Zr0.27Ti0.03Fe2 containing very few Ti shows the substitution of Ti to Zr and the resultant improvement in the dehydriding equilibrium pressure.  相似文献   

18.
In this work, bimetallic NiPd hollow nanoporous (HNiPd) catalysts are prepared by in-situ deposition of Pd nanoparticles (Pd NPs) on hollow Ni (HNi) microspheres. Scanning electron microscope (SEM) and transmission electron microscopy (TEM) reveal the hollow nanoporous essence of HNiPd catalysts. Meanwhile, using high-angle annular dark-field scanning TEM (HAADF-STEM) and elemental mapping, it is found that tiny dendritic-like NiPd nanocomposites attach on the exterior of microspheres. The content of Pd is easily tailored to constitute HNiPd catalysts with different Ni/Pd atomic ratios. Further electrochemical evaluation vindicates that the as-prepared HNiPd catalysts have a good catalytic activity and stability toward ethanol oxidation reaction (EOR) in alkaline medium. Notably, the peak current density of HNi3.1Pd catalyst and the chronoamperometric current density of HNi4.6Pd catalyst are 4 and 2 times of Pd/C (JM) catalyst, respectively, which show that HNiPd catalysts hold great potential in application of alkaline direct ethanol fuel cells (DEFCs).  相似文献   

19.
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   

20.
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   

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