In order to achieve effective, economic, and easily achievable photocatalyst for the degradation of dye methyl orange(MeO), ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanocomposites were prepared by simple chemical synthetic...In order to achieve effective, economic, and easily achievable photocatalyst for the degradation of dye methyl orange(MeO), ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanocomposites were prepared by simple chemical synthetic route in the aqueous medium. Phase, crystallinity, surface structure and surface behavior of the synthesized materials were determined by X-ray diffraction(XRD) and Brunauer-Emmett-Teller analysis(BET) techniques. XRD study established formation of good crystalline ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanomaterials. By using intensity of constituent peaks in the XRD pattern, the compositions of nanocomposites were determined. From the BET analysis, the prepared materials show mesoporous behavior, type Ⅳ curves along with H4 hysteresis. The ZnO/ZnS/α-Fe2O3 composite shows the largest surface area among three materials. From the UV-visible spectra, the band gap energy of the materials was determined. Photoluminescence spectra(PL) were used to determine the emission behavior and surface defects in the materials. In PL spectra, the intensity of UV peak of ZnO/ZnS is lowered than that of ZnO while in case of ZnO/ZnS/α-Fe2O3, the intensity further decreased. The visible emission spectra of ZnO/ZnS increased compared with ZnO while in ZnO/ZnS/α-Fe2O3 it is further increased compared with ZnO/ZnS. The as-synthesized materials were used as photocatalysts for the degradation of dye MeO. The photo-degradation data revealed that the ZnO/ZnS/α-Fe2O3 is the best photocatalyst among three specimens for the degradation of dye MeO. The decrease of intensity of UV emission peak and the increase of intensity of visible emission cause the decrease of recombination of electrons and holes which are ultimately responsible for the highest photocatalytic activity of ZnO/ZnS/α-Fe2O3.展开更多
The distributions of traps and electron density in the interfaces between polyimide (PI) matrix and Al2O3 nanoparticles are researched using the isothermal decay current and the small-angle x-ray scattering (SAXS)...The distributions of traps and electron density in the interfaces between polyimide (PI) matrix and Al2O3 nanoparticles are researched using the isothermal decay current and the small-angle x-ray scattering (SAXS) tests. According to the electron density distribution for quasi two-phase mixture doped by spherical nanoparticles, the electron densities in the interfaces of PI/Al2O3 nanocomposite films are evaluated. The trap level density and carrier mobility in the interface are studied. The experimental results show that the distribution and the change rate of the electron density in the three layers of interface are different, indicating different trap distributions in the interface layers. There is a maximum trap level density in the second layer, where the maximum trap level density for the nanocomposite film doped by 25 wt% is 1.054 × 10^22 eV·m^-3 at 1.324eV, resulting in the carrier mobility reducing. In addition, both the thickness and the electron density of the nanocomposite film interface increase with the addition of the doped Al2O3 contents. Through the study on the trap level distribution in the interface, it is possible to further analyze the insulation mechanism and to improve the performance of nano-dielectric materials.展开更多
采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(...采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。展开更多
The effects of Mg addition on mechanical thermo-electrical properties of Al.Mg/5%Al2O3 nanocomposite with differentMg contents (0, 5%, 10% and 20%) produced by mechanical alloying were studied. Scanning electron mic...The effects of Mg addition on mechanical thermo-electrical properties of Al.Mg/5%Al2O3 nanocomposite with differentMg contents (0, 5%, 10% and 20%) produced by mechanical alloying were studied. Scanning electron microscopy analysis (SEM),X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) were used to characterize the produced powder. Theresults show that addition of Mg forms a predominant phase (Al.Mg solid solution). By increasing the mass fraction of Mg, thecrystallite size decreases and the lattice strain increases which results from the atomic penetration of Mg atoms into the substitutionalsites of Al lattice. The microhardness of the composite increases with the increase of the Mg content. The thermal and electricalconductivities increase linearly with the temperature increase in the inspected temperature range. Moreover, the thermalconductivity increases with the increase of Mg content.展开更多
The soft magnetic nanocomposites with equiatomic FeCo particles dispersed in Al2O3 matrix were synthesized via a sol-gel technique combined with H2 reduction method. The samples were characterized by X-ray diffraction...The soft magnetic nanocomposites with equiatomic FeCo particles dispersed in Al2O3 matrix were synthesized via a sol-gel technique combined with H2 reduction method. The samples were characterized by X-ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The FeCo nanoparticles in all the samples have the typical bcc structure. With the decreasing of Al2O3 content, the mean grain size of FeCo in the nanocomposites and the saturation magnetization of the samples increase, while the coercivity of samples increases firstly and then decreases due to different magnetic mechanisms.展开更多
A series of nanosized CeO2-Fe2O3 mixed-oxide nanocomposites with different Ce4+/Fe3+molar ratios were successfully prepared by a co-precipitation technique.The surface area increased with Fe2O3 content increasing up t...A series of nanosized CeO2-Fe2O3 mixed-oxide nanocomposites with different Ce4+/Fe3+molar ratios were successfully prepared by a co-precipitation technique.The surface area increased with Fe2O3 content increasing up to 60 wt%in the composite.However,with further increase in Fe2O3 content,the surface area began to decrease.The reduction processes of the CeO2-Fe2O3 nanocomposites were studied in a hydrogen atmosphere at 300-600℃.The reduction rates increased by increasing both the temperature and Fe2O3 content in the nanocomposites.The microstructure of the reduced composites at 500℃illustrated the presence of a considerable number of macro-and micro-pores.The activation energy values were calculated which were in the range of 3.56-5.37 kJ mol-1 at the initial stages(up to 35%reduction)and 5.21-10.2 kJ·mol-1 at the final stages(up to 80%reduction)of reduction.The rate-controlling mechanisms in both the initial and final reduction stages were determined,and the initial reaction stage was controlled by combined gaseous diffusion and interfacial chemical reaction mechanisms for all the composites except for pure CeO2,which was controlled by a chemical reaction mechanism.The final reaction stage was controlled by a gaseous diffusion mechanism for some composites,while for the others it was controlled by combined gaseous diffusion and interfacial chemical reaction mechanisms.The hydrogen sorption properties of the nanocomposites were studied by pressure composition isotherms using a volumetric method.Hydrogen storage in the nanocomposites increased by increasing the temperature because of the formation of oxygen vacancies which enhance atomic H adsorption and function as strong adsorption sites forming more metal hydride covalent bonds.展开更多
In this study,an Al2O3/MoS2 nanocomposite coating was created on an aluminum 1050 substrate using the plasma electrolytic oxidation method.The zeta potential measurements showed that small MoS2 particles have negative...In this study,an Al2O3/MoS2 nanocomposite coating was created on an aluminum 1050 substrate using the plasma electrolytic oxidation method.The zeta potential measurements showed that small MoS2 particles have negative potential and move toward the anode electrode.The nanoparticles of MoS2 were found to have a zeta potential of-25 mV,which prevents suspension in the solution.Thus,to produce an Al2O3/MoS2 nanocomposite,one has to use the microparticles of MoS2.The X-ray diffraction analyses showed that the produced coatings containedα-Al2O3,γ-Al2O3,and MoS2,and that the size of MoS2 particles can be reduced to 30 nm.It was observed that prolonged suspension in the electrolyte results in an enhanced formation of an Al2O3/MoS2 nanocomposite.Using the results,it was hypothesized that the mechanism of the formation of the Al2O3/MoS2 nanocomposite coating on the aluminum 1050 substrate is based on electrical energy discharge.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
In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for met...In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.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
摘要In order to achieve effective, economic, and easily achievable photocatalyst for the degradation of dye methyl orange(MeO), ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanocomposites were prepared by simple chemical synthetic route in the aqueous medium. Phase, crystallinity, surface structure and surface behavior of the synthesized materials were determined by X-ray diffraction(XRD) and Brunauer-Emmett-Teller analysis(BET) techniques. XRD study established formation of good crystalline ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanomaterials. By using intensity of constituent peaks in the XRD pattern, the compositions of nanocomposites were determined. From the BET analysis, the prepared materials show mesoporous behavior, type Ⅳ curves along with H4 hysteresis. The ZnO/ZnS/α-Fe2O3 composite shows the largest surface area among three materials. From the UV-visible spectra, the band gap energy of the materials was determined. Photoluminescence spectra(PL) were used to determine the emission behavior and surface defects in the materials. In PL spectra, the intensity of UV peak of ZnO/ZnS is lowered than that of ZnO while in case of ZnO/ZnS/α-Fe2O3, the intensity further decreased. The visible emission spectra of ZnO/ZnS increased compared with ZnO while in ZnO/ZnS/α-Fe2O3 it is further increased compared with ZnO/ZnS. The as-synthesized materials were used as photocatalysts for the degradation of dye MeO. The photo-degradation data revealed that the ZnO/ZnS/α-Fe2O3 is the best photocatalyst among three specimens for the degradation of dye MeO. The decrease of intensity of UV emission peak and the increase of intensity of visible emission cause the decrease of recombination of electrons and holes which are ultimately responsible for the highest photocatalytic activity of ZnO/ZnS/α-Fe2O3.
基金Supported by the National Natural Science Foundation of China under Grant Nos 51337002,51077028,51502063 and 51307046the Foundation of Harbin Science and Technology Bureau of Heilongjiang Province under Grant No RC2014QN017034
摘要The distributions of traps and electron density in the interfaces between polyimide (PI) matrix and Al2O3 nanoparticles are researched using the isothermal decay current and the small-angle x-ray scattering (SAXS) tests. According to the electron density distribution for quasi two-phase mixture doped by spherical nanoparticles, the electron densities in the interfaces of PI/Al2O3 nanocomposite films are evaluated. The trap level density and carrier mobility in the interface are studied. The experimental results show that the distribution and the change rate of the electron density in the three layers of interface are different, indicating different trap distributions in the interface layers. There is a maximum trap level density in the second layer, where the maximum trap level density for the nanocomposite film doped by 25 wt% is 1.054 × 10^22 eV·m^-3 at 1.324eV, resulting in the carrier mobility reducing. In addition, both the thickness and the electron density of the nanocomposite film interface increase with the addition of the doped Al2O3 contents. Through the study on the trap level distribution in the interface, it is possible to further analyze the insulation mechanism and to improve the performance of nano-dielectric materials.
摘要采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。
摘要The effects of Mg addition on mechanical thermo-electrical properties of Al.Mg/5%Al2O3 nanocomposite with differentMg contents (0, 5%, 10% and 20%) produced by mechanical alloying were studied. Scanning electron microscopy analysis (SEM),X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) were used to characterize the produced powder. Theresults show that addition of Mg forms a predominant phase (Al.Mg solid solution). By increasing the mass fraction of Mg, thecrystallite size decreases and the lattice strain increases which results from the atomic penetration of Mg atoms into the substitutionalsites of Al lattice. The microhardness of the composite increases with the increase of the Mg content. The thermal and electricalconductivities increase linearly with the temperature increase in the inspected temperature range. Moreover, the thermalconductivity increases with the increase of Mg content.
基金Supported by the Development Project of Science and Technology of Jilin Province, China(No.20090144)
摘要The soft magnetic nanocomposites with equiatomic FeCo particles dispersed in Al2O3 matrix were synthesized via a sol-gel technique combined with H2 reduction method. The samples were characterized by X-ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The FeCo nanoparticles in all the samples have the typical bcc structure. With the decreasing of Al2O3 content, the mean grain size of FeCo in the nanocomposites and the saturation magnetization of the samples increase, while the coercivity of samples increases firstly and then decreases due to different magnetic mechanisms.
摘要A series of nanosized CeO2-Fe2O3 mixed-oxide nanocomposites with different Ce4+/Fe3+molar ratios were successfully prepared by a co-precipitation technique.The surface area increased with Fe2O3 content increasing up to 60 wt%in the composite.However,with further increase in Fe2O3 content,the surface area began to decrease.The reduction processes of the CeO2-Fe2O3 nanocomposites were studied in a hydrogen atmosphere at 300-600℃.The reduction rates increased by increasing both the temperature and Fe2O3 content in the nanocomposites.The microstructure of the reduced composites at 500℃illustrated the presence of a considerable number of macro-and micro-pores.The activation energy values were calculated which were in the range of 3.56-5.37 kJ mol-1 at the initial stages(up to 35%reduction)and 5.21-10.2 kJ·mol-1 at the final stages(up to 80%reduction)of reduction.The rate-controlling mechanisms in both the initial and final reduction stages were determined,and the initial reaction stage was controlled by combined gaseous diffusion and interfacial chemical reaction mechanisms for all the composites except for pure CeO2,which was controlled by a chemical reaction mechanism.The final reaction stage was controlled by a gaseous diffusion mechanism for some composites,while for the others it was controlled by combined gaseous diffusion and interfacial chemical reaction mechanisms.The hydrogen sorption properties of the nanocomposites were studied by pressure composition isotherms using a volumetric method.Hydrogen storage in the nanocomposites increased by increasing the temperature because of the formation of oxygen vacancies which enhance atomic H adsorption and function as strong adsorption sites forming more metal hydride covalent bonds.
摘要In this study,an Al2O3/MoS2 nanocomposite coating was created on an aluminum 1050 substrate using the plasma electrolytic oxidation method.The zeta potential measurements showed that small MoS2 particles have negative potential and move toward the anode electrode.The nanoparticles of MoS2 were found to have a zeta potential of-25 mV,which prevents suspension in the solution.Thus,to produce an Al2O3/MoS2 nanocomposite,one has to use the microparticles of MoS2.The X-ray diffraction analyses showed that the produced coatings containedα-Al2O3,γ-Al2O3,and MoS2,and that the size of MoS2 particles can be reduced to 30 nm.It was observed that prolonged suspension in the electrolyte results in an enhanced formation of an Al2O3/MoS2 nanocomposite.Using the results,it was hypothesized that the mechanism of the formation of the Al2O3/MoS2 nanocomposite coating on the aluminum 1050 substrate is based on electrical energy discharge.
摘要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.
基金supported by the National Basic Research Program of China(973 Program,2013CB933104)the National Natural Science Foundation of China(Nos.11275258 and 11135008)
摘要In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.
摘要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.