The development of blue semiconductor light-emitting diodes(LEDs)has produced potential applications for Prdoped materials that can absorb blue light,especially crystals,and we now report structure and optical propert...The development of blue semiconductor light-emitting diodes(LEDs)has produced potential applications for Prdoped materials that can absorb blue light,especially crystals,and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia(YSZ)grown by the optical floating zone(FZ)method.X-ray diffraction(XRD)and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase,whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases.X-ray photoelectron spectroscopy(XPS)and electron paramagnetic resonance(EPR)spectroscopy showed that Pr was present as the Pr^(3+)ion in ceramic rods and single crystals after heating to high temperatures.The absorption and photoluminescence excitation(PLE)spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light,while their photoluminescence(PL)spectra showed five emission peaks at 565 nm,588 nm,614 nm,638 nm,and 716 nm under450 nm excitation.The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol%Pr_(6)O_(11),and those with higher concentrations showed evidence of quenching of the luminescence properties.In addition,the color purity of Pr-doped YSZ single crystal reached 98.9%in the orange–red region.展开更多
The influences of adding sodium to zirconia on the acid-base properties of the surface and on the catalytic conversion of ethanol and acetone were investigated. The rates of ethanol dehydration, dehydrogenation and co...The influences of adding sodium to zirconia on the acid-base properties of the surface and on the catalytic conversion of ethanol and acetone were investigated. The rates of ethanol dehydration, dehydrogenation and coupling were evaluated in a fixed-bed flow reactor operating at temperatures from 613 to 673 K. The rate of acetone condensation was evaluated in the same reactor operating at 473-573 K. Addition of 1.0 wt% Na to ZrO2 decreased the rate of ethanol dehydration by more than an order of magnitude, which was consistent with a neutralization of acid sites evaluated by ammonia adsorption microcalorimetry. Addition of 1.0 wt% Na to ZrO2 also increased the base site density quantified by carbon dioxide adsorption microcalorimetry and the rate of acetone condensation. Although the rate of ethanol coupling was not increased by the addition of Na, the overall selectivity of ethanol to butanol was improved over the 1.0 wt% Na/ZrO2 sample because of the significant inhibition of ethanol dehydration.展开更多
A novel method to prepare mesoporous nano-zirconia was developed. Thesynthesis was carried out in the presence of PEO surfactants via a solid-state reaction. Thematerials exhibit a strong diffraction peak at low 2θ a...A novel method to prepare mesoporous nano-zirconia was developed. Thesynthesis was carried out in the presence of PEO surfactants via a solid-state reaction. Thematerials exhibit a strong diffraction peak at low 2θ angle and their nitrogenadsorption/desorption isotherms are typical of type IV with H1 hysteresis loops. The pore structureimaged by TEM can be described as wormhole domains. The tetragonal zirconia nanocrystals are uniformin size (around 1.5 nm) and their mesopores focus on around 4.6 nm. The zirconia nanocrystal growthis tentatively postulated to be the result of an aggregation mechanism. This study also revealsthat the PEO surfactants can interact with the Zr-O-Zr framework to reinforce the thermal stabilityof zirconia. The ratio of NaOH to ZrOCl_2, crystallization and calcination temperature play animportant role in the synthesis of mesoporous nano-zirconia.展开更多
An efficient ZrO2-doped Cu/SiO2 catalyst was fabricated through hydrolysis precipitation method(HP)and used to produce ethylene glycol(EG)through dimethyl oxalate(DMO)hydrogenation.The states for zirconia on copper ca...An efficient ZrO2-doped Cu/SiO2 catalyst was fabricated through hydrolysis precipitation method(HP)and used to produce ethylene glycol(EG)through dimethyl oxalate(DMO)hydrogenation.The states for zirconia on copper catalyst and roles in DMO hydrogenation were investigated through various characterization tools,including N2 physical adsorption,XRD,H2-TPR,Methyl glycolate-TPD-MS,XPS,XAES as well.Compared with common ammonia evaporation and co-precipitation methods used in catalyst preparation,this HP method is found to effectively suppress the agglomeration and further size growth of copper nanoparticles by enhancing the interactions between copper and zirconia species.More importantly,uniform distribution of ZrO2 dopant is achieved due to the pseudo-homogeneous reactions in the mixing step of catalyst preparation.A proper amount of zirconium dopant helps achieve the desirable proportion of Cu+/(Cu++CuO)for surface copper species,especially promotes the production of Cu+species originated from Cu-ZrO2 species at the interface of copper and zirconia particles.In comparison with Cu+species formed from copper phyllosilicates reduction,the Cu+sites derived from Cu-ZrO2 species show higher adsorption ability of MG,an important intermediate species in ethylene glycol production.These adsorbed MG molecules further react with atomic hydrogen shifted from adjacent metallic copper surface,leading to a higher catalytic behavior.For the EG production via DMO hydrogenation,the turnover frequency(TOF)normalized by CuO species on CuZr/SiO2 catalyst is 1.8 times than that of traditional Cu/SiO2 counterpart.Due to the enhanced synergy effect between Cu+and Cuo active sites,a lower activation energy of ester hydrogenation on this ZrO2-doped Cu/SiO2 catalyst is believed to be responsible for the significant improvement.展开更多
The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low tem...The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.展开更多
Objective:To assess the biomechanical properties of a new design configuration for zirconia dental implants. Methods: The new design has a cylindrical shape that is partially hollow and porous in the bottom, which per...Objective:To assess the biomechanical properties of a new design configuration for zirconia dental implants. Methods: The new design has a cylindrical shape that is partially hollow and porous in the bottom, which permits the implants to be locked into the alveolar bone over time. It also utilizes bioactive glass coatings to increase adhesion to surrounding bone structure. Samples of the new design were fabricated in the laboratory and their material strength, hardness, and fracture toughness were evaluated. In addition, biocompatibility of the new design was evaluated through testing in dogs. Results: Results of mechanical tests indicate that structural properties of the new design exceed the usual requirements for implants. Moreover, animal tests suggest that there is appreciable improvement in lock-in strength and osteointegration. Conclusion: The new design configuration is biomechanically feasible and further research is warranted to improve the design for human use.展开更多
The surface morphology of buffer layer yttrium-stabilized zirconia （YSZ） of YBa2CuaO7-σ （YBCO） high temperature superconducting films relies on a series of controllable experimental parameters. In this work, we f...The surface morphology of buffer layer yttrium-stabilized zirconia （YSZ） of YBa2CuaO7-σ （YBCO） high temperature superconducting films relies on a series of controllable experimental parameters. In this work, we focus on the influence of pulsed laser frequency and target crystalline type on surface morphology of YSZ films deposited by pulsed laser deposition （PLD） on rolling assisted biaxially textured substrate tapes. Usually two kinds of particles are observed in the YSZ layer： randomly distributed ones on the whole film and self-assembled ones along grain boundaries. SEM images are used to prove that particles can be partly removed when choosing dense targets of single crystalline. Lower frequency of pulsed laser also contributes to a smoother film surface. TEM images are used to view the crystalline structure of thin film. Thus we can obtain a basic understanding of how to prepare a particle-free YSZ buffer layer for YBCO in optimized conditions using PLD. The YBCO layer with nice structure and critical current density of around 5 MA/cm2 can be reached on smooth YSZ samples.展开更多
Zirconia-loaded sulfuric acid （SO2-/ZrO2） catalysts were prepared by impregnation method, molded by punch tablet machine and characterized by X-ray diffraction. SO4^2-/ZrO2 catalyst was used to obtain glycerol triac...Zirconia-loaded sulfuric acid （SO2-/ZrO2） catalysts were prepared by impregnation method, molded by punch tablet machine and characterized by X-ray diffraction. SO4^2-/ZrO2 catalyst was used to obtain glycerol triacetate （GTA） directly from glycerin. The effect of some factors, such as different temperatures of calcination and catalysts molded or not, on the reusable times of catalysts and the yield of GTA were investigated. The optimum reaction conditions were shown as follows： the reaction temperature was 403 K; the reaction time continued for 8 h; the amount of molded catalysts was 5 wt% of glycerin and the molar ratio of glycerin to acetic acid was 1 ： 8. The yield of GTA was 97.93% under the optimum condition.展开更多
基金the National Natural Science Foundation of China(Grant No.11975004)the Key Research and Development Plan Project of Guangxi,China(Grant No.Guike AB18281007)。
文摘The development of blue semiconductor light-emitting diodes(LEDs)has produced potential applications for Prdoped materials that can absorb blue light,especially crystals,and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia(YSZ)grown by the optical floating zone(FZ)method.X-ray diffraction(XRD)and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase,whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases.X-ray photoelectron spectroscopy(XPS)and electron paramagnetic resonance(EPR)spectroscopy showed that Pr was present as the Pr^(3+)ion in ceramic rods and single crystals after heating to high temperatures.The absorption and photoluminescence excitation(PLE)spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light,while their photoluminescence(PL)spectra showed five emission peaks at 565 nm,588 nm,614 nm,638 nm,and 716 nm under450 nm excitation.The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol%Pr_(6)O_(11),and those with higher concentrations showed evidence of quenching of the luminescence properties.In addition,the color purity of Pr-doped YSZ single crystal reached 98.9%in the orange–red region.
基金the Chemical Sciences,Geosciences and Biosciences Division,Office of Basic Energy Sciences,Office of Science,U.S.Department of Energy,grant no.DEFG0295ER14549
文摘The influences of adding sodium to zirconia on the acid-base properties of the surface and on the catalytic conversion of ethanol and acetone were investigated. The rates of ethanol dehydration, dehydrogenation and coupling were evaluated in a fixed-bed flow reactor operating at temperatures from 613 to 673 K. The rate of acetone condensation was evaluated in the same reactor operating at 473-573 K. Addition of 1.0 wt% Na to ZrO2 decreased the rate of ethanol dehydration by more than an order of magnitude, which was consistent with a neutralization of acid sites evaluated by ammonia adsorption microcalorimetry. Addition of 1.0 wt% Na to ZrO2 also increased the base site density quantified by carbon dioxide adsorption microcalorimetry and the rate of acetone condensation. Although the rate of ethanol coupling was not increased by the addition of Na, the overall selectivity of ethanol to butanol was improved over the 1.0 wt% Na/ZrO2 sample because of the significant inhibition of ethanol dehydration.
文摘A novel method to prepare mesoporous nano-zirconia was developed. Thesynthesis was carried out in the presence of PEO surfactants via a solid-state reaction. Thematerials exhibit a strong diffraction peak at low 2θ angle and their nitrogenadsorption/desorption isotherms are typical of type IV with H1 hysteresis loops. The pore structureimaged by TEM can be described as wormhole domains. The tetragonal zirconia nanocrystals are uniformin size (around 1.5 nm) and their mesopores focus on around 4.6 nm. The zirconia nanocrystal growthis tentatively postulated to be the result of an aggregation mechanism. This study also revealsthat the PEO surfactants can interact with the Zr-O-Zr framework to reinforce the thermal stabilityof zirconia. The ratio of NaOH to ZrOCl_2, crystallization and calcination temperature play animportant role in the synthesis of mesoporous nano-zirconia.
基金financial support from the National Natural Science Foundation of China(21878227,U1510203)。
文摘An efficient ZrO2-doped Cu/SiO2 catalyst was fabricated through hydrolysis precipitation method(HP)and used to produce ethylene glycol(EG)through dimethyl oxalate(DMO)hydrogenation.The states for zirconia on copper catalyst and roles in DMO hydrogenation were investigated through various characterization tools,including N2 physical adsorption,XRD,H2-TPR,Methyl glycolate-TPD-MS,XPS,XAES as well.Compared with common ammonia evaporation and co-precipitation methods used in catalyst preparation,this HP method is found to effectively suppress the agglomeration and further size growth of copper nanoparticles by enhancing the interactions between copper and zirconia species.More importantly,uniform distribution of ZrO2 dopant is achieved due to the pseudo-homogeneous reactions in the mixing step of catalyst preparation.A proper amount of zirconium dopant helps achieve the desirable proportion of Cu+/(Cu++CuO)for surface copper species,especially promotes the production of Cu+species originated from Cu-ZrO2 species at the interface of copper and zirconia particles.In comparison with Cu+species formed from copper phyllosilicates reduction,the Cu+sites derived from Cu-ZrO2 species show higher adsorption ability of MG,an important intermediate species in ethylene glycol production.These adsorbed MG molecules further react with atomic hydrogen shifted from adjacent metallic copper surface,leading to a higher catalytic behavior.For the EG production via DMO hydrogenation,the turnover frequency(TOF)normalized by CuO species on CuZr/SiO2 catalyst is 1.8 times than that of traditional Cu/SiO2 counterpart.Due to the enhanced synergy effect between Cu+and Cuo active sites,a lower activation energy of ester hydrogenation on this ZrO2-doped Cu/SiO2 catalyst is believed to be responsible for the significant improvement.
基金supported by the National Natural Science Foundation of China(20825310 and 20973011)National Basic Research Project of China (2011CB201400 and 2011CB808700)
文摘The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.
文摘Objective:To assess the biomechanical properties of a new design configuration for zirconia dental implants. Methods: The new design has a cylindrical shape that is partially hollow and porous in the bottom, which permits the implants to be locked into the alveolar bone over time. It also utilizes bioactive glass coatings to increase adhesion to surrounding bone structure. Samples of the new design were fabricated in the laboratory and their material strength, hardness, and fracture toughness were evaluated. In addition, biocompatibility of the new design was evaluated through testing in dogs. Results: Results of mechanical tests indicate that structural properties of the new design exceed the usual requirements for implants. Moreover, animal tests suggest that there is appreciable improvement in lock-in strength and osteointegration. Conclusion: The new design configuration is biomechanically feasible and further research is warranted to improve the design for human use.
基金Supported by the ITER Project of the Ministry of Science and Technology of China under Grant No 2011GB113004the Shanghai Commission of Science and Technology under Grant No 11DZ1100402the Youth Fund of the National Natural Science Foundation of China under Grant No 11204174
文摘The surface morphology of buffer layer yttrium-stabilized zirconia （YSZ） of YBa2CuaO7-σ （YBCO） high temperature superconducting films relies on a series of controllable experimental parameters. In this work, we focus on the influence of pulsed laser frequency and target crystalline type on surface morphology of YSZ films deposited by pulsed laser deposition （PLD） on rolling assisted biaxially textured substrate tapes. Usually two kinds of particles are observed in the YSZ layer： randomly distributed ones on the whole film and self-assembled ones along grain boundaries. SEM images are used to prove that particles can be partly removed when choosing dense targets of single crystalline. Lower frequency of pulsed laser also contributes to a smoother film surface. TEM images are used to view the crystalline structure of thin film. Thus we can obtain a basic understanding of how to prepare a particle-free YSZ buffer layer for YBCO in optimized conditions using PLD. The YBCO layer with nice structure and critical current density of around 5 MA/cm2 can be reached on smooth YSZ samples.
基金supported by the National High Technology Research and Development Program of China (No. 2009AA03Z222 and No. 2009AA05Z437)the "Six Talents Pinnacle Program" of Jiangsu Province of China (No. 2008028)
文摘Zirconia-loaded sulfuric acid （SO2-/ZrO2） catalysts were prepared by impregnation method, molded by punch tablet machine and characterized by X-ray diffraction. SO4^2-/ZrO2 catalyst was used to obtain glycerol triacetate （GTA） directly from glycerin. The effect of some factors, such as different temperatures of calcination and catalysts molded or not, on the reusable times of catalysts and the yield of GTA were investigated. The optimum reaction conditions were shown as follows： the reaction temperature was 403 K; the reaction time continued for 8 h; the amount of molded catalysts was 5 wt% of glycerin and the molar ratio of glycerin to acetic acid was 1 ： 8. The yield of GTA was 97.93% under the optimum condition.
