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1.
The composition (CuO/ZnO/Al2O3 = 30/60/10) of a commercial catalyst G66B was used as a reference for designing CuO/ZnO/CeO2/ZrO2/Al2O3 catalysts for the oxidative (or combined) steam reforming of methanol (OSRM). The effects of Al2O3, CeO2 and ZrO2 on the OSRM reaction were clearly identified. CeO2, ZrO2 and Al2O3 all promoted the dispersions of CuO and ZnO in CuO/ZnO/CeO2/ZrO2/Al2O3 catalysts. Aluminum oxide lowered the reducibility of the catalyst, and weakened the OSRM reaction. Cerium oxide increased the reducibility of the catalyst, but weakened the reaction. Zirconium oxide improved the reducibility of the catalyst, and promoted the reaction. A lower CuO/ZnO ratio of the catalyst was associated with greater promotion of ZrO2. The critical CuO/ZnO ratio for the promotion of ZrO2 was approximately 0.75–0.8. Introducing of ZrO2 into CuO/ZnO/Al2O3 also improved the stability of the catalyst. Although Al2O3 inhibited the OSRM reaction, a certain amount of it was required to ensure the stability and the mechanical strength of the catalysts.  相似文献   

2.
Steam reforming of methanol was investigated over Cu–ZnO–ZrO2–Al2O3 catalysts at 473 and 573 K. The Cu:Zn:(Al + Zr) molar ratio was 3:3:4; however, the Zr:Al molar ratio was varied and the catalysts were pretreated at different calcination and reduction temperatures. The synthesized catalysts were characterized by N2 physisorption, temperature-programmed reduction with H2 (H2-TPR), X-ray diffraction, oxidized surface TPR, and infrared spectroscopy after carbon monoxide chemisorption. The crystalline size of Cu decreased on increasing the calcination temperatures from 573 to 623 K and increased on increasing the reduction temperatures from 523 to 573 K. Among the tested catalysts, the Cu–ZnO–ZrO2 catalyst exhibited the highest and lowest hydrogen-formation rates at 473 and 573 K, respectively. After the reaction at 573 K, all the tested catalysts exhibited an increase in the Cu crystalline size, causing the catalyst deactivation. Among the tested catalysts, the Cu–ZnO–ZrO2–Al2O3 catalyst, where the Cu:Zn:Al:Zr molar ratio was 3:3:2:2, showed the highest and most stable catalytic activity at 573 K. Cu dispersion and catalyst composition affected the catalytic performance for steam reforming of methanol.  相似文献   

3.
Bioethanol was reformed in supercritical water (SCW) at 500 °C and 25 MPa on Ni/Al2O3 and Ni/CeZrO2/Al2O3 catalysts to produce high-pressure hydrogen. The results were compared with non-catalytic reactions. Under supercritical water and in a non-catalytic environment, ethanol was reformed to H2, CO2 and CH4 with small amounts of CO and C2 gas and liquid products. The presence of either Ni/Al2O3 or Ni/CeZrO2/Al2O3 promoted reactions of ethanol reforming, dehydrogenation and decomposition. Acetaldehyde produced from the decomposition of ethanol was completely decomposed into CH4 and CO, which underwent a further water-gas shift reaction in SCW. This led to great increases in ethanol conversion and H2 yield on the catalysts of more than 3-4 times than that of the non-catalytic condition. For the catalytic operation, adding small amounts of oxygen at oxygen to ethanol molar ratio of 0.06 into the feed improved ethanol conversion, at the expense of some H2 oxidized to water, resulting in a slightly lower H2 yield. The ceria-zirconia promoted catalyst was more active than the unpromoted catalyst. On the promoted catalyst, complete ethanol conversion was achieved and no coke formation was found. The ceria-zirconia promoter has important roles in improving the decomposition of acetaldehyde, the enhancement of the water-gas shift as well as the methanation reactions to give an extremely low CO yield and a tremendously high H2/CO ratio. The SCW environment for ethanol reforming caused the transformation of gamma-alumina towards the corundum phase of the alumina support in the Ni/Al2O3 catalyst, but this transformation was slowed down by the presence of the ceria-zirconia promoter.  相似文献   

4.
Ni/xY2O3–Al2O3 (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al2O3 catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H2-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH4 conversion increased with elevating levels of Y2O3 from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY2O3–Al2O3 catalysts maintained high activity after 24 h on stream, while Ni/Al2O3 had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.  相似文献   

5.
A novel nickel catalyst supported on Al2O3@ZrO2 core/shell nanocomposites was prepared by the impregnation method. The core/shell nanocomposites were synthesized by depositing zirconium species on boehmite nanofibres. This contribution aims to study the effects of the pore structure of supports and the zirconia dispersed on the surface of the alumina nanofibres on the CO methanation. The catalysts and supports were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR), nitrogen adsorption–desorption, and thermogravimetry and differential thermal analysis (TG-DTA). The catalytic performance of the catalysts for CO methanation was investigated at a temperature range from 300 °C to 500 °C. The results of the characterization indicate that the metastable tetragonal zirconia could be stably and evenly dispersed on the surface of alumina nanofibres. The interlaced nanorods of the Al2O3@ZrO2 core/shell nanocomposites resulted in a macropore structure and the spaces between the zirconia nanoparticles dispersed on the alumina nanofibres formed most of the mesopores. Zirconia on the surface of the support promoted the dispersion and influenced the reduction states of the nickel species on the support, so it prevented the nickel species from sintering as well as from forming a spinel phase with alumina at high temperatures, and thus reduced the carbon deposition during the reaction. With the increase of the zirconia content in the catalyst, the catalytic performance for the CO methanation was enhanced. The Ni/Al2O3@ZrO2-15 exhibited the highest CO conversion and methane selectivity at 400 °C, but they decreased dramatically above or below 400 °C due to the temperature sensitivity of the catalyst. Ni/Al2O3@ZrO2-30 exhibited a high and constant rate of methane formation between 350 °C and 450 °C. The excellent catalytic performance of this catalyst is attributed to its reasonable pore structure and good dispersion of zirconia on the support. This catalyst has great potential to be further studied for the future industrial use.  相似文献   

6.
Ni-Al2O3 composites with varying contents of nickel are synthesized via a glycine nitrate process (GNP) and an impregnation process (IMP). Their potential application as an anode functional layer for internal methane CO2 reforming in a solid oxide fuel cell is investigated. H2-TPR results show that the chemical interaction between NiO and Al2O3 decreases as the nickel content increases. Catalytic tests demonstrate that 15 wt.% Ni-Al2O3 catalysts exhibit the best catalytic activity for methane CO2 reforming. However, the carbon formation rates over Ni-Al2O3 prepared via GNP are lower than those over Ni-Al2O3 prepared via IMP using the same amounts of nickel, with the exception of the 1 wt.% Ni-Al2O3 catalyst. Raman spectroscopy and O2-TPO results indicate that the degree of graphitization and the amount of carbon deposited on the 15 wt.% Ni-Al2O3 catalyst synthesized via GNP are lower than those of the catalyst prepared via IMP following a 60 h stability test. A cell with a 15 wt.% Ni-Al2O3 catalyst layer prepared via GNP is fabricated that delivers a peak power density of 1006 mW cm−2 at 850 °C when operating on methane-CO2 gas mixtures, which is comparable to that observed when operating on hydrogen fuel.  相似文献   

7.
Highly c-axis oriented Mg:ZnO films were fabricated on Al2O3 substrate by radio frequency sputtering for different substrate temperatures. The crystal structure revealed that the Mg dopants are well integrated into ZnO wurtzite lattice. X-ray photoelectron spectroscopy measurements also confirmed the successful incorporation of Mg into ZnO. The substrate temperature exhibit significant influence on the optical absorbance and band gap of Mg:ZnO films. Scanning electron microscope images revealed the formation of Mg:ZnO nanorods with good crystalline quality. The films prepared at 1200 °C show well grown rods of Mg:ZnO due to strengthening of the preferred orientation of ZnO along the c-axis. The Mg:ZnO/Al2O3 films prepared at different temperature were tested for its sensing performance towards 200 ppm of H2 at room temperature. The Mg:ZnO sensor prepared at 1200 °C revealed fast response and recovery time of about 85 s and 70 s, respectively. The response of the sensor was linear to H2 concentration in the range of 100–500 ppm. It can be summarized that this high performance H2 sensor has potential for use as a portable room temperature gas sensor.  相似文献   

8.
The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO2, SnO/TiO2, CuO/TiO2, Al2O3/TiO2 and CuO/Al2O3/TiO2 nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al2O3/TiO2 nanocomposites. A variety of components of CuO/Al2O3/TiO2 photocatalysts were tested for the enhancement of H2 formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al2O3/TiO2. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO2. Nano-sized TiO2 photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.  相似文献   

9.
A novel composite membrane consisting of a poly(phenylene oxide) (PPO) selective layer and a CMS/Al2O3 substrate was fabricated by a spin-coating method. This new class of PPO/CMS/Al2O3 multilayer composite membranes showed an H2 permeability of 134 Barrer, two times greater than that for the corresponding self-supported PPO polymeric membrane. High selectivities for H2/CH4 and H2/N2 of 31.8 and 37.1, respectively, were also obtained with this composite membrane. According to field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) observations, using the CMS/Al2O3 material as the substrate provided a smooth surface for the support of the PPO selective layer and increased the roughness from the top to bottom surfaces. The effects of the substrate materials on the permselectivity of the resulting membrane were also investigated.  相似文献   

10.
Alumina supported nickel (Ni/Al2O3), nickel–cobalt (Ni–Co/Al2O3) and cobalt (Co/Al2O3) catalysts containing 15% metal were synthesized, characterized and tested for the reforming of CH4 with CO2 and CH4 cracking reactions. In the Ni–Co/Al2O3 catalysts Ni–Co alloys were detected and the surface metal sites decreased with decrease in Ni:Co ratio. Turnover frequencies of CH4 were determined for both reactions. The initial turnover frequencies of reforming (TOFDRM) for Ni–Co/Al2O3 were greater than that for Ni/Al2O3, which suggested a higher activity of alloy sites. The initial turnover frequencies for cracking (TOFCRK) did not follow this trend. The highest average TOFDRM, H2:CO ratio and TOFCRK were observed for a catalyst containing a Ni:Co ratio of 3:1. This catalyst also had the maximum carbon deposited during reforming and produced the maximum reactive carbon during cracking. It appeared that carbon was an intermediate product of reforming and the best catalyst was able to most effectively crack CH4 and oxidize carbon to CO by CO2.  相似文献   

11.
Ti/PbO2 + nano-Co3O4 composite electrode materials with different compositions were prepared by anodic composite electrodeposition on Ti substrate, with a SnO2-Sb2O5 intermediate layer in Pb2+ plating solution containing suspended nano-Co3O4 particles. The composition, structure, and morphology of the composite materials were investigated by XRD, XPS, and SEM analyses. The composite electrodes were studied as anodes for oxygen evolution reaction (OER) in 1 mol/L NaOH solution. The activities for the OER of the composites were explained by recording linear scanning voltammograms and Tafel plots. Results indicate that the onset potential of oxygen evolution at the composite electrode was lowered by approximately 160 mV compared to the PbO2 electrode without nano-Co3O4. The catalytic activity of the composite electrode towards OER was improved significantly.  相似文献   

12.
Dehydrogenation of organic chemical hydrides has been improved by reconstructing the catalyst in the form of hierarchical porous structure nanocatalyst, in which the economical Ni was adopted as catalytic component and nano Al2O3–TiO2 hybrid composite as support. The Al2O3–TiO2 composite was prepared by spontaneous self-assembly of nano Al2O3 and TiO2 aggregates by hydrolysis of tetra-n-butyl-titanate under continuous agitation. The multi-scaled distribution of Al2O3–TiO2 aggregates with hierarchy could be observed in dynamic light scattering spectrometer. The aggregates are comprised of nano-sized γ-Al2O3 and anatase TiO2 crystallites with sizes of about 5 and 7 nm, respectively. The surface modulation by TiO2 could be verified in FTIR Spectra. The migration of Ti species and crystallite growth were hindered by the Al2O3 skeleton and the hierarchical porous structure was sustained during the thermal related process. The multi-scaled distributed pores were confirmed by both TEM analysis and N2 adsorption results. The results of dehydrogenation experiments showed that the hierarchical porous structure nano Ni/Al2O3–TiO2 exhibited superior catalytic performance to Ni/Al2O3 with the optimum conversion of 99.9% at 400 °C, while the catalyst of Ni/Al2O3 exhibited only 16.5% under the same condition.  相似文献   

13.
LiCoO2 particles were coated with various wt.% of lanthanum aluminum garnets (3LaAlO3:Al2O3) by an in situ sol–gel process, followed by calcination at 1123 K for 12 h in air. X-ray diffraction (XRD) patterns confirmed the formation of a 3LaAlO3:Al2O3 compound and the in situ sol–gel process synthesized 3LaAlO3:Al2O3-coated LiCoO2 was a single-phase hexagonal α-NaFeO2-type structure of the core material without any modification. Scanning electron microscope (SEM) images revealed a modification of the surface of the cathode particles. Transmission electron microscope (TEM) images exposed that the surface of the core material was coated with a uniform compact layer of 3LaAlO3:Al2O3, which had an average thickness of 40 nm. Galvanostatic cycling studies demonstrated that the 1.0 wt.% 3LaAlO3:Al2O3-coated LiCoO2 cathode showed excellent cycle stability of 182 cycles, which was much higher than the 38 cycles sustained by the pristine LiCoO2 cathode material when it was charged at 4.4 V.  相似文献   

14.
Unloaded and 0.25–1.0 wt% Pt-loaded WO3 nanoparticles were synthesized by hydrothermal method using sodium tungstate dihydrate and sodium chloride as precursors in an acidic condition and impregnated using platinum acetylacetonate. Pt-loaded WO3 films on an Al2O3 substrate with interdigitated Au electrodes were prepared by spin-coating technique. The response of WO3 sensors with different Pt-loading concentrations was tested towards 0.01–1.0 vol% of H2 in air as a function of operating temperature (200–350 °C). The 1.0 wt% Pt-loaded WO3 sensing film showed the highest response of ∼2.16 × 104 to 1.0 vol% H2 at 250 °C. Therefore, an operating temperature of 250 °C was optimal for H2 detection. The responses of 1.0 wt% Pt-loaded WO3 sensing film to other flammable gases, including C2H5OH, C2H4 and CO, were considerably less, demonstrating Pt-loaded WO3 sensing film to be highly selective to H2.  相似文献   

15.
The hydrogen photo-evolution was successfully achieved in aqueous (Fe1−xCrx)2O3 suspensions (0 ≤ x ≤ 1). The solid solution has been prepared by incipient wetness impregnation and characterized by X-ray diffraction, BET, transport properties and photo-electrochemistry. The oxides crystallize in the corundum structure, they exhibit n-type conductivity with activation energy of ∼0.1 eV and the conduction occurs via adiabatic polaron hops. The characterization of the band edges has been studied by the Mott Schottky plots. The onset potential of the photo-current is ∼0.2 V cathodic with respect to the flat band potential, implying a small existence of surface states within the gap region. The absorption of visible light promotes electrons into (Fe1−xCrx)2O3-CB with a potential (∼−0.5 VSCE) sufficient to reduce water into hydrogen. As expected, the quantum yield increases with decreasing the electro affinity through the substitution of iron by the more electropositive chromium which increases the band bending at the interface and favours the charge separation. The generated photo-voltage was sufficient to promote simultaneously H2O reduction and SO32− oxidation in the energetically downhill reaction (H2O + SO32− → H2 + SO42−, ΔG = −17.68 kJ mol−1). The best activity occurs over Fe1.2Cr0.8O3 in SO32− (0.1 M) solution with H2 liberation rate of 21.7 μmol g−1 min−1 and a quantum yield 0.06% under polychromatic light. Over time, a pronounced deceleration occurs, due to the competitive reduction of the end product S2O62−.  相似文献   

16.
The effect of CeO2 loading amount of Ru/CeO2/Al2O3 on CO2 methanation activity and CH4 selectivity was studied. The CO2 reaction rate was increased by adding CeO2 to Ru/Al2O3, and the order of CO2 reaction rate at 250 °C is Ru/30%CeO2/Al2O3 > Ru/60%CeO2/Al2O3 > Ru/CeO2 > Ru/Al2O3. With a decrease in CeO2 loading of Ru/CeO2/Al2O3 from 98% to 30%, partial reduction of CeO2 surface was promoted and the specific surface area was enlarged. Furthermore, it was observed using FTIR technique that intermediates of CO2 methanation, such as formate and carbonate species, reacted with H2 faster over Ru/30%CeO2/Al2O3 and Ru/CeO2 than over Ru/Al2O3. These could result in the high CO2 reaction rate over CeO2-containing catalysts. As for the selectivity to CH4, Ru/30%CeO2/Al2O3 exhibited high CH4 selectivity compared with Ru/CeO2, due to prompt CO conversion into CH4 over Ru/30%CeO2/Al2O3.  相似文献   

17.
Composite cathodes of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) and Y2O3 stabilized ZrO2 (YSZ) are fabricated by impregnating the porous YSZ scaffold pre-formed on YSZ electrolyte substrate with a solution containing La, Sr, Co and Fe in desired composition. The performance stability of the cathodes is evaluated in air at 750 °C for up to 120 h by electrochemical impedance spectroscopy under the condition of open circuit. An insignificant small amount of resistive phase SrZrO3 is formed at 800 °C during cathode preparation; however, its volume is not further increased at 750 °C for 120 h, as indicated by the XRD results. The cathode polarization resistance (Rp) increases from 0.17 to 0.30 Ωcm2 after the 120 h test mainly due to the increase of the low frequency polarization resistance (Rp2), which characterizes the low frequency processes in the reaction of oxygen reduction. The morphology change of the well connected LSCF particles to dispersive and flattened configuration accounts for the increase of the Rp2 and in turn the degradation of cathode performance.  相似文献   

18.
The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La0.75Sr0.25Cr0.5Mn0.5O3−δ (LSCrM) anodes are modified using Ni(NO3)2 and/or Ce(NO3)3/(Sm,Ce)(NO3)x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO2 to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (Pmax) at 850 °C is 198 mW cm−2 when dry H2 and air are used as the fuel and oxidant, respectively. When H2 is changed to CH4, the value of Pmax is 32 mW cm−2. After 8.9 wt.% Ni and 5.8 wt.% CeO2 are introduced into the LSCrM anode, the cell exhibits increased values of Pmax 432, 681, 948 and 1135 mW cm−2 at 700, 750, 800 and 850 °C, respectively, with dry H2 as fuel and air as oxidant. When O2 at 50 mL min−1 is used as the oxidant, the value of Pmax increases to 1450 mW cm−2 at 850 °C. When dry CH4 is used as fuel and air as oxidant, the values of Pmax reach 95, 197, 421 and 645 mW cm−2 at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.  相似文献   

19.
A series of Au catalysts supported on CeO2–TiO2 with various CeO2 contents were prepared. CeO2–TiO2 was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO3)3 on TiO2. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO2 on Au/TiO2 catalyst could enhance CO oxidation and suppress H2 oxidation at high reaction temperature (>50 °C). Additives such as La2O3, Co3O4 and CuO were added to Au/CeO2–TiO2 catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO2–TiO2 catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO2–TiO2 with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.  相似文献   

20.
Ag promoted ZnO/Al2O3 catalysts were prepared by using the incipient wetness impregnation method. The catalytic properties of steam reforming reaction for hydrogen production on the prepared catalysts were evaluated with H2O:C2H5OH molar ratios of 3:1 at 450 °C and atmospheric pressure. Ag promoted ZnO/Al2O3 catalysts show higher SRE catalytic activity than ZnO/Al2O3 catalysts. H2 and CH3CHO are the major products on Ag promoted catalysts, and C2H4 is also produced probably due to acid sites on Al2O3. SRE mechanism on Ag promoted ZnO/Al2O3 catalysts, which contains C-C scission, is different from that on ZnO/Al2O3 catalysts. A method based on thermogravimetry (TG), differential scanning calorimetry (DSC) and mass spectrometry (MS) was used to analysis the coking behavior on catalyst surface. The surfaces of Ag promoted ZnO/Al2O3 catalysts show two different types of coking, and suffer higher coke deposition during the steam reforming reaction.  相似文献   

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