In this work, ZnO, Ce<sup>3+</sup> doped ZnO (ZnO/Ce<sup>3+</sup>) and Cu<sup>2+</sup> + Ce<sup>3+</sup> co-doped ZnO (ZnO/Cu<sup>2+</sup> + Ce<sup>3+&...In this work, ZnO, Ce<sup>3+</sup> doped ZnO (ZnO/Ce<sup>3+</sup>) and Cu<sup>2+</sup> + Ce<sup>3+</sup> co-doped ZnO (ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup> ) solid solutions powders were synthesized by a solution combustion method maintaining the Ce<sup>3+</sup> ion concentration constant in 3%Wt while the Cu<sup>2+</sup> ion concentration was varied in 1, 2, 3, 10 and 20%Wt. After its synthesis, all the samples were annealed at 900?C by 24 h. The ZnO, ZnO/Ce<sup>3+</sup> and ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup> powders were structurally characterized using X-ray diffraction (XRD) technique, and the XRD patterns showed that for pure ZnO, Cu<sup>2+</sup> undoped ZnO/Ce<sup>3</sup><sup>+</sup> and ZnO/Ce<sup>3+</sup> doped with the Cu<sup>2+</sup> ion, the three samples exhibited the hexagonal wurtzite ZnO crystalline structure. However, the morphology and particle size of both samples were observed by means of a scanning electron microscopy (SEM);from SEM image, it is observed that the crystallites of both samples are agglomerated forming bigger amorphous particles with an approximate average size of 1 μm. In addition, the photoluminescence of the ZnO, Ce<sup>3+</sup> doped ZnO and Cu<sup>2+</sup> + Ce<sup>3+</sup> doped ZnO samples was measurement under an illumination of 209 nm wavelength (UV region): for the ZnO/Ce<sup>3+</sup> sample, your emission spectrum is in the visible region from blue color until red color;the UV band of the ZnO is suppressed. The multicolor emission visible is attributed to the Ce<sup>3+</sup> ion photoluminescence, while for the ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup>, its emission PL spectrum is quenching by the Cu<sup>2+</sup> ion, present in the ZnO crystalline.展开更多
ZnO thin films co-doped with A1 and Sb with different concentrations and a fixed molar ratio of AlCl3 to SbCl3 at 1：2, are prepared by a sol-gel spin-coating method on glass annealed at 550 ℃ for 2 h in air. The x-r...ZnO thin films co-doped with A1 and Sb with different concentrations and a fixed molar ratio of AlCl3 to SbCl3 at 1：2, are prepared by a sol-gel spin-coating method on glass annealed at 550 ℃ for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al distortion, and the biaxial stresses are 1.03× 10^8. 3.26× 10^8 and Sb are of wurtzite hexagonal ZnO with a very small 5.23 × 10^8, and 6.97× 10^8 Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5 Ω·cm.展开更多
A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to t...A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to the catalysts modified by other type of carbon materials, the ACF-promoted catalyst prepared via carbonate-coprecipitation method exhibit the highest performance in the low-temperature steam reforming of methanol. It was suggested that the intrinsic high surface area nature of ACF material may favor the generation of modified catalysts with a high surface area and improved component dispersion, thus leading to improved performance for methanol steam reforming.展开更多
A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventiona...A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventional method, the new catalysts prepared via the new method exhibit much higher BET surface area and pore size, much smaller crystallite size and higher catalytic activity and selectivity in CO 2 hydrogenation to methanol. It is also found that the molar ratio of Cu + to Cu 0 on the surface of the catalyst obtained by coprecipitation-reduction is much higher than that on the reduced catalyst obtained by the conventional method, which could be crucial for its high activity and selectivity for catalytic hydrogenation of CO 2 to methanol.展开更多
Hydrogen production by catalytic steam reforming of methanol over a series of coprecipitated Cu/ZnO/Al2O3 catalysts under atmospheric pressure in a microreactor has been studied Effects of catalyst composition...Hydrogen production by catalytic steam reforming of methanol over a series of coprecipitated Cu/ZnO/Al2O3 catalysts under atmospheric pressure in a microreactor has been studied Effects of catalyst composition, reaction temperature and activation conditions on the catalytic activity have been investigated Crystal phases of catalysts were analyzed by XRD The results showed that Cu/ZnO/Al2O3 catalysts displayed high activity and selectivity for hydrogen and stability The optimized molar ratio is Cu/Zn=10, a maximum methanol conversion of 994?mol%, hydrogen selectivity of 999?mol% and CO molar fraction of 0007% were obtained in the steam reforming reaction with the catalyst containing 45?mol% copper XRD results showed that the diffraction peaks of CuO in the catalyst were clearly lower and broaden It indicated that high dispersion of small copper crystallites on the catalyst surface was formed under the calcination conditions It is suggested that the good performance of Cu/ZnO/Al2O3 catalysts partly resulted from well dispersed展开更多
We demonstrate for the first time that a short time of microwave irradiation on the oxide precursor of a Cu/ZnO/Al2O3 catalyst can provide unique opportunity for tailoring the microstructure and activity of the cataly...We demonstrate for the first time that a short time of microwave irradiation on the oxide precursor of a Cu/ZnO/Al2O3 catalyst can provide unique opportunity for tailoring the microstructure and activity of the catalyst for methanol steam reforming. It is shown by in situ XRD that a considerable increase in the microstrain of Cu nanocrystals could be achieved in the catalysts processed by microwave irradiation for 310 min, which correlates well with the enhanced CH3OH conversion as observed on the corresponding samples. The present work also confirms that although the high specific surface area of Cu is a prerequisite for catalytic activity, it does not account for the observed changes in activity and selectivity alone without taking bulk microstructural changes into account.展开更多
In view of not uniformity in conventional coprecipitation preparation, urea was used as the precursor of precipitator to prepare Cu/ZnO/Al2O3 catalysts for methanol synthesis. In the method, urea was dissolved in nitr...In view of not uniformity in conventional coprecipitation preparation, urea was used as the precursor of precipitator to prepare Cu/ZnO/Al2O3 catalysts for methanol synthesis. In the method, urea was dissolved in nitrate solution and hydrolyzed to produce OH- as precipitator after the solution was heated to 90℃. After 6h, the precipitation was accomplished. The evaluation results of the catalyst activity showed that this catalyst had comparable catalytic activities to the industrial catalyst, and reached its maximum activity at 250℃. At reaction conditions of 250℃, 3MPa,and SV=7600h-1, the STY of methanol was 0.38g/（mL·h） with syngas compositing of H2,CO, CO2, and N2 atmolar ratio of 65.9∶27.1∶2.9∶4.1. X-ray Diffraction （XRD） revealed that the particle size of CuO and ZnO was about 200nm, and Al existed in the form of ZnAl2O4 spinel in the catalysts.展开更多
文摘In this work, ZnO, Ce<sup>3+</sup> doped ZnO (ZnO/Ce<sup>3+</sup>) and Cu<sup>2+</sup> + Ce<sup>3+</sup> co-doped ZnO (ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup> ) solid solutions powders were synthesized by a solution combustion method maintaining the Ce<sup>3+</sup> ion concentration constant in 3%Wt while the Cu<sup>2+</sup> ion concentration was varied in 1, 2, 3, 10 and 20%Wt. After its synthesis, all the samples were annealed at 900?C by 24 h. The ZnO, ZnO/Ce<sup>3+</sup> and ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup> powders were structurally characterized using X-ray diffraction (XRD) technique, and the XRD patterns showed that for pure ZnO, Cu<sup>2+</sup> undoped ZnO/Ce<sup>3</sup><sup>+</sup> and ZnO/Ce<sup>3+</sup> doped with the Cu<sup>2+</sup> ion, the three samples exhibited the hexagonal wurtzite ZnO crystalline structure. However, the morphology and particle size of both samples were observed by means of a scanning electron microscopy (SEM);from SEM image, it is observed that the crystallites of both samples are agglomerated forming bigger amorphous particles with an approximate average size of 1 μm. In addition, the photoluminescence of the ZnO, Ce<sup>3+</sup> doped ZnO and Cu<sup>2+</sup> + Ce<sup>3+</sup> doped ZnO samples was measurement under an illumination of 209 nm wavelength (UV region): for the ZnO/Ce<sup>3+</sup> sample, your emission spectrum is in the visible region from blue color until red color;the UV band of the ZnO is suppressed. The multicolor emission visible is attributed to the Ce<sup>3+</sup> ion photoluminescence, while for the ZnO/Cu<sup>2+</sup> + Ce<sup>3+</sup>, its emission PL spectrum is quenching by the Cu<sup>2+</sup> ion, present in the ZnO crystalline.
基金Project supported by the Innovation Foundation of Beijing University of Aeronautics and Astronautics for PhD Graduates, China (Grant No. 292122)the Equipment Research Foundation of China (Grant No. 373974)
文摘ZnO thin films co-doped with A1 and Sb with different concentrations and a fixed molar ratio of AlCl3 to SbCl3 at 1：2, are prepared by a sol-gel spin-coating method on glass annealed at 550 ℃ for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al distortion, and the biaxial stresses are 1.03× 10^8. 3.26× 10^8 and Sb are of wurtzite hexagonal ZnO with a very small 5.23 × 10^8, and 6.97× 10^8 Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5 Ω·cm.
文摘A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to the catalysts modified by other type of carbon materials, the ACF-promoted catalyst prepared via carbonate-coprecipitation method exhibit the highest performance in the low-temperature steam reforming of methanol. It was suggested that the intrinsic high surface area nature of ACF material may favor the generation of modified catalysts with a high surface area and improved component dispersion, thus leading to improved performance for methanol steam reforming.
文摘A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventional method, the new catalysts prepared via the new method exhibit much higher BET surface area and pore size, much smaller crystallite size and higher catalytic activity and selectivity in CO 2 hydrogenation to methanol. It is also found that the molar ratio of Cu + to Cu 0 on the surface of the catalyst obtained by coprecipitation-reduction is much higher than that on the reduced catalyst obtained by the conventional method, which could be crucial for its high activity and selectivity for catalytic hydrogenation of CO 2 to methanol.
文摘Hydrogen production by catalytic steam reforming of methanol over a series of coprecipitated Cu/ZnO/Al2O3 catalysts under atmospheric pressure in a microreactor has been studied Effects of catalyst composition, reaction temperature and activation conditions on the catalytic activity have been investigated Crystal phases of catalysts were analyzed by XRD The results showed that Cu/ZnO/Al2O3 catalysts displayed high activity and selectivity for hydrogen and stability The optimized molar ratio is Cu/Zn=10, a maximum methanol conversion of 994?mol%, hydrogen selectivity of 999?mol% and CO molar fraction of 0007% were obtained in the steam reforming reaction with the catalyst containing 45?mol% copper XRD results showed that the diffraction peaks of CuO in the catalyst were clearly lower and broaden It indicated that high dispersion of small copper crystallites on the catalyst surface was formed under the calcination conditions It is suggested that the good performance of Cu/ZnO/Al2O3 catalysts partly resulted from well dispersed
文摘We demonstrate for the first time that a short time of microwave irradiation on the oxide precursor of a Cu/ZnO/Al2O3 catalyst can provide unique opportunity for tailoring the microstructure and activity of the catalyst for methanol steam reforming. It is shown by in situ XRD that a considerable increase in the microstrain of Cu nanocrystals could be achieved in the catalysts processed by microwave irradiation for 310 min, which correlates well with the enhanced CH3OH conversion as observed on the corresponding samples. The present work also confirms that although the high specific surface area of Cu is a prerequisite for catalytic activity, it does not account for the observed changes in activity and selectivity alone without taking bulk microstructural changes into account.
文摘In view of not uniformity in conventional coprecipitation preparation, urea was used as the precursor of precipitator to prepare Cu/ZnO/Al2O3 catalysts for methanol synthesis. In the method, urea was dissolved in nitrate solution and hydrolyzed to produce OH- as precipitator after the solution was heated to 90℃. After 6h, the precipitation was accomplished. The evaluation results of the catalyst activity showed that this catalyst had comparable catalytic activities to the industrial catalyst, and reached its maximum activity at 250℃. At reaction conditions of 250℃, 3MPa,and SV=7600h-1, the STY of methanol was 0.38g/（mL·h） with syngas compositing of H2,CO, CO2, and N2 atmolar ratio of 65.9∶27.1∶2.9∶4.1. X-ray Diffraction （XRD） revealed that the particle size of CuO and ZnO was about 200nm, and Al existed in the form of ZnAl2O4 spinel in the catalysts.
