The adsorption and the growth of ZnO on α-Al2O3（0001） surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials （USP） method based on density functional theory.The avera...The adsorption and the growth of ZnO on α-Al2O3（0001） surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials （USP） method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3（0001）. It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO[10^-10] is parallel with the [10^-10] of the α-Al2O3（0001）, which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃： one is the ZnO surface that has the Zn-terminated structure, and whose [10^-10] parallels the [10^-10] of the substrate surface, and the other is the ZnO[10^-10] //sapphire [11-20] with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of （substrate）-O-Zn-O has a distinct covalent character, whereas the （Zn）O-Al （substrate） shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3（0001） leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition.展开更多
Advanced integrated gasification combined cycle （IGCC） power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasif...Advanced integrated gasification combined cycle （IGCC） power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels. As a sort of effective desufurizer, such as Fe2O3, ZnO and ZnFe2O4, it will endure strong reducing atmosphere in desulfurization process. The reduced degree of desufurizer can have an effect on its desulfurization reactivity. In this paper, Fe2O3, ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH. After aging, washing and drying, the solids were calcined at 800℃. The reduction behaviors of sample were characterized by temperature-programmed reduction （TPR）. It is found that there are two reduction peaks for Fe2O3 in TPR, and whereas no reduction peaks for ZnO are found. The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3. ZnFe2O4 is easier to be reduced than Fe2O3. The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.展开更多
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 microstructure, electrical properties, and density of Dy2O3-doped ZnO-based varistor ceramics, prepared using high-energy ball milling （HEBM） and sintered at 800℃, were investigated by increasing the cooling ra...The microstructure, electrical properties, and density of Dy2O3-doped ZnO-based varistor ceramics, prepared using high-energy ball milling （HEBM） and sintered at 800℃, were investigated by increasing the cooling rate in the order of H （slow cooling in furnace） → L （cooling in furnace） → K （cooling in air）. With the increase in cooling rate, the grain size and density decreased, the breakdown voltage （VImA/mm） increased, and the nonlinear coefficient （α） and leakage current （IL） exhibited extremum. The sample with the cooling type L showed the best properties with the breakdown voltage of 2650 V/ram, o：of 20.3, IL of 5.2 laA, and density of 5.42 g/cm^3. The barrier height （ФB）, donor concentration （Nd）, density of the interface states （Nd）, and barrier width （ω） all exhibited extremum during the alteration in cooling rate. The different relative amount of Bi-rich phase and its distribution as well as the characteristic parameters of grain boundary, resulting from the alteration of cooling rate, led to the changes in the properties of varistor ceramics.展开更多
文摘The adsorption and the growth of ZnO on α-Al2O3（0001） surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials （USP） method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3（0001）. It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO[10^-10] is parallel with the [10^-10] of the α-Al2O3（0001）, which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃： one is the ZnO surface that has the Zn-terminated structure, and whose [10^-10] parallels the [10^-10] of the substrate surface, and the other is the ZnO[10^-10] //sapphire [11-20] with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of （substrate）-O-Zn-O has a distinct covalent character, whereas the （Zn）O-Al （substrate） shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3（0001） leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition.
基金the Ministry of Science and Technology of China under the Grant No. G2005CB221203the Natural Science Foundation of China(20776092)
文摘Advanced integrated gasification combined cycle （IGCC） power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels. As a sort of effective desufurizer, such as Fe2O3, ZnO and ZnFe2O4, it will endure strong reducing atmosphere in desulfurization process. The reduced degree of desufurizer can have an effect on its desulfurization reactivity. In this paper, Fe2O3, ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH. After aging, washing and drying, the solids were calcined at 800℃. The reduction behaviors of sample were characterized by temperature-programmed reduction （TPR）. It is found that there are two reduction peaks for Fe2O3 in TPR, and whereas no reduction peaks for ZnO are found. The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3. ZnFe2O4 is easier to be reduced than Fe2O3. The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.
文摘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This work is financially supported by the National Natural Science Foundation of China (No. 50471045)Shanghai Nano-technology Promotion Center (No. 0452nm026).
文摘The microstructure, electrical properties, and density of Dy2O3-doped ZnO-based varistor ceramics, prepared using high-energy ball milling （HEBM） and sintered at 800℃, were investigated by increasing the cooling rate in the order of H （slow cooling in furnace） → L （cooling in furnace） → K （cooling in air）. With the increase in cooling rate, the grain size and density decreased, the breakdown voltage （VImA/mm） increased, and the nonlinear coefficient （α） and leakage current （IL） exhibited extremum. The sample with the cooling type L showed the best properties with the breakdown voltage of 2650 V/ram, o：of 20.3, IL of 5.2 laA, and density of 5.42 g/cm^3. The barrier height （ФB）, donor concentration （Nd）, density of the interface states （Nd）, and barrier width （ω） all exhibited extremum during the alteration in cooling rate. The different relative amount of Bi-rich phase and its distribution as well as the characteristic parameters of grain boundary, resulting from the alteration of cooling rate, led to the changes in the properties of varistor ceramics.
