Flower-like ZnO microstructures were successfully produced using a hydrothermal method employing ZnSO_(4)/(NH_(4))_(2)SO_(4) as a raw material.The effect of the operating parameters of the hydrothermal temperature, OH...Flower-like ZnO microstructures were successfully produced using a hydrothermal method employing ZnSO_(4)/(NH_(4))_(2)SO_(4) as a raw material.The effect of the operating parameters of the hydrothermal temperature, OH^(-)/Zn^(2+) molar ratio, time, and amount of dispersant on the phase structure and micromorphology of the ZnO particles were investigated.The synthesis conditions of the flower-like ZnO microstructures were: hydrothermal temperature of 160℃, OH^(-)/Zn^(2+) molar ratio of 5:1, reaction time of 4 h, and 4 mL of dispersant.The flower-like ZnO microstructures were comprised of hexagon-shaped ZnO rods arranged in a radiatively.Degradation experiments of Rhodamine B with the flower-like ZnO microstructures demonstrated a degradation efficiency of 97.6% after 4 h of exposure to sunshine, indicating excellent photocatalytic capacity.The growth mechanism of the flower-like ZnO microstructures was presented.展开更多
In this paper we investigated the optical properties of ZnO and Mn doped ZnO nanocrystals that were fabricated by a vapor phase transport growth process, using zinc acetate dihydrate with or without Mn in a constant O...In this paper we investigated the optical properties of ZnO and Mn doped ZnO nanocrystals that were fabricated by a vapor phase transport growth process, using zinc acetate dihydrate with or without Mn in a constant O2/Ar mixture gas flowing through the furnace at 400600℃, respectively. The as grown ZnO nanocrystals are homogeneous with a mean size of 19 nm observed by scanning electron microscope（SEM）. The optical characteristics were analyzed by absorption spectra and photoluminescence（PL） spectra at room-temperature. For ZnO nanocrystals, a strong and predominant UV emission peaked at 377 nm was found in the PL spectra. For Mn doped ZnO nanocrystals, in addition to the strong UV emission, a strong blue emission peaked at 435 nm was observed as well. By doping Mn ions, the major UV emission shifts from 377 nm to 408 nm, showing that Mn ions were not only incorporated into ZnO Ncs, but also introduced an impurity level in the bandgap. Moreover, with the concentration of Mn increasing, the relative intensities of the two emissions change largely, and the photoluminescence mechanism of them is discussed.展开更多
Due to the high specific capacity and energy density, lithium–sulfur battery is regarded as a potential energy storage conversion system. However, the serious shuttle effect and the sluggish electrochemical reaction ...Due to the high specific capacity and energy density, lithium–sulfur battery is regarded as a potential energy storage conversion system. However, the serious shuttle effect and the sluggish electrochemical reaction kinetics impede the practical use of lithium–sulfur battery. In the interests of breaking through the above knotty problems, herein we propose to use the polar flower-like Zn O modified by Bi OI nanoparticles as bifunctional host with catalytic and adsorption ability for polysulfides in lithium–sulfur battery.It can be found that this adsorption/catalytic host integrates the functions of adsorption and mutual catalytic conversion of polysulfides, in which the polar flower-like Zn O can effectively capture the polysulfides through strong polar-polar interaction, simultaneously the BiOI nanoparticles can accelerate the mutual conversion of polysulfides to Li2 S through reducing the activation energy and conversion energy barrier required for the electrochemical reaction. As a result, under a sulfur loading of 2.5 mg cm^(-2), the lithium–sulfur battery with Zn O/Bi OI/CNT/S as cathode reveals a considerable initial specific capacity of1267 mAh g^(-1) at a current density of 0.1 C. Even the current density increased to 1 C, the capacity can reach as 873.4 mAh g^(-1), together with a good capacity retention of 67.1% after 400 cycles. Therefore,after systematically study the positive effects of the flower-like ZnO modified by catalytic BiOI nanoparticles on the adsorption and catalytic conversion of polysulfides, this work provides a new idea for the development and application of high-performance lithium–sulfur batteries.展开更多
Ag modified ZnO （Ag/ZnO） nanocrystals were prepared by a facile and low temperature wet chemical method. The phase structures, morphologies, and optical properties of the as-prepared samples were characterized by X-...Ag modified ZnO （Ag/ZnO） nanocrystals were prepared by a facile and low temperature wet chemical method. The phase structures, morphologies, and optical properties of the as-prepared samples were characterized by X-ray powder diffraction （XRD）, field-emission scanning electron microscopy （FESEM）, high-resolution transmission electron microscopy （HRTEM）, the Brumauer-Emmett-Teller （BET） surface area, UV-vis diffuse reflectance spectroscopy and photoluminescence （PL） spectra, respectively. The photocatalytic performance of Ag/ZnO with diffent Ag contents was measured with the degradation of methyl orange （MO） at room temperature under UV light irradiation. The experimental results indicated that the well-crystalline ZnO nanopaticles with a size of ca. 4.5 nm exhibited a high photocatalytic activity for the degradation of MO with the apparent rate constant （k） of 1.57 ×10-2 min-1, and the photocatalytic activities of ZnO were further enhanced by modification with silver. When the Ag loading was 3mol%, Ag/ZnO showed the highest photocatalytic acitivity with a k value of 5.452×10-2 min-1, which is 3.5 and 2.5 time more than that of ZnO and commercial P25, respectively.展开更多
A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission elec...A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission electron microscopy and UV-visible absorption spectroscopy. The results indicate that modulating the adding ways of water has a significant effect on the shape of the obtained nanocrystals. The addition of small quantity of water can increase the growth rate of crystals and leads to the formation of different shapes. The resulting shapes of the novel structures are diverse, including spheres, cones, and teardrops, all of which are obtained without any additional surfactants. These studies concerning the shape evolution of nanocrystals should be valuable for further design and for greater understanding of advanced nanoscale building-block architectures.展开更多
In this article, we report the results of our detailed investigations of the growth kinetics of zero-dimensional nanocrystals as well as one-dimensional nanorods by the combined use of small angel X-ray scattering （S...In this article, we report the results of our detailed investigations of the growth kinetics of zero-dimensional nanocrystals as well as one-dimensional nanorods by the combined use of small angel X-ray scattering （SAXS）, transmission electron microscopy （TEM） along with other physical techniques. The study includes growth kinetics of gold nanocrystals formed by the reduction of HAuCl4 by tetrakis（hydroxymethyl） phosphonium chloride in aqueous solution, of CdSe nanocrystals formed by the reaction of cadmium stearate and selenium under solvothermal conditions, and of ZnO nanorods formed by the reaction of zinc acetate with sodium hydroxide under solvothermal conditions in the absence and presence of capping agents. The growth of gold nanocrystals does not follow the diffusion-limited Ostwald ripening, and instead follows a Sigmoidal rate curve. The heat change associated with the growth determined by isothermal titration calorimetry is about 10 kcal·mol^-1 per I nm increase in the diameter of the nanocrystals. In the case of CdSe nanocrystals also, the growth mechanism deviates from diffusion-limited growth and follows a combined model containing both diffusion and surface reaction terms. Our study of the growth kinetics of uncapped and poly（vinyl pyrollidone） （PVP）-capped ZnO nanorods has yielded interesting insights. We observe small nanocrystals next to the ZnO nanorods after a lapse of time in addition to periodic focusing and defocusing of the width of the length distribution. These observations lend support to the diffusion-limited growth model for the growth of uncapped ZnO nanorods. Accordingly, the time dependence on the length of uncapped nanorods follows the L3 law as required for diffusion-limited Ostwald ripening. The PVP-capped nanorods, however, show a time dependence, which is best described by a combination of diffusion （L^3） and surface reaction （L^2） terms.展开更多
利用热分解法制备了结构明确的负载型纳米晶催化剂。在纳米晶成核和生长过程中加入一维ZnO纳米棒作为晶种,调控不同组分的纳米晶在ZnO纳米棒表面均匀生长,从而获得了结构明确的MnO/ZnO、Co_(3)O_(4)/ZnO、Co_(3)Mn_(1)/ZnO催化剂。透射...利用热分解法制备了结构明确的负载型纳米晶催化剂。在纳米晶成核和生长过程中加入一维ZnO纳米棒作为晶种,调控不同组分的纳米晶在ZnO纳米棒表面均匀生长,从而获得了结构明确的MnO/ZnO、Co_(3)O_(4)/ZnO、Co_(3)Mn_(1)/ZnO催化剂。透射电子显微镜(TEM)与X射线粉末衍射(XRD)结果显示,不同组分纳米颗粒都均匀分散在ZnO纳米棒表面。相对于MnO/ZnO和Co_(3)O_(4)/ZnO催化剂,Co_(3)Mn_(1)/ZnO催化剂在CO氧化反应中具有最佳的催化性能。在200 L·g_(cat)^(-1)·h^(-1)的气时空速下,Co_(3)Mn_(1)/ZnO催化剂起活温度为50℃,其T100(CO转化率达到100%时的温度)为200℃;利用X射线光电子能谱(XPS)对不同催化剂进行了分析,结果显示,Co_(3)Mn_(1)/ZnO催化剂的氧空位比MnO/ZnO催化剂提高了30%以上,从而使其具有较高的CO氧化催化性能。更为重要的是,Co_(3)Mn_(1)/ZnO复合纳米晶催化剂的活化能(39.4 k J·mol^(-1))远低于其它负载型纳米晶催化剂。展开更多
基金financially supported by the Funding of Shenyang Ligong University’s Research Support Program for High-level Talents (No.1010147000802)the National Natural Science Foundation of China (Nos.52004165 and 51774070)。
文摘Flower-like ZnO microstructures were successfully produced using a hydrothermal method employing ZnSO_(4)/(NH_(4))_(2)SO_(4) as a raw material.The effect of the operating parameters of the hydrothermal temperature, OH^(-)/Zn^(2+) molar ratio, time, and amount of dispersant on the phase structure and micromorphology of the ZnO particles were investigated.The synthesis conditions of the flower-like ZnO microstructures were: hydrothermal temperature of 160℃, OH^(-)/Zn^(2+) molar ratio of 5:1, reaction time of 4 h, and 4 mL of dispersant.The flower-like ZnO microstructures were comprised of hexagon-shaped ZnO rods arranged in a radiatively.Degradation experiments of Rhodamine B with the flower-like ZnO microstructures demonstrated a degradation efficiency of 97.6% after 4 h of exposure to sunshine, indicating excellent photocatalytic capacity.The growth mechanism of the flower-like ZnO microstructures was presented.
基金supported in parts by the National Natural Science Foundation of China(No.60776004,60976071)the Laboratory for Thin Film Microfabrication of the Ministry of Education
文摘In this paper we investigated the optical properties of ZnO and Mn doped ZnO nanocrystals that were fabricated by a vapor phase transport growth process, using zinc acetate dihydrate with or without Mn in a constant O2/Ar mixture gas flowing through the furnace at 400600℃, respectively. The as grown ZnO nanocrystals are homogeneous with a mean size of 19 nm observed by scanning electron microscope（SEM）. The optical characteristics were analyzed by absorption spectra and photoluminescence（PL） spectra at room-temperature. For ZnO nanocrystals, a strong and predominant UV emission peaked at 377 nm was found in the PL spectra. For Mn doped ZnO nanocrystals, in addition to the strong UV emission, a strong blue emission peaked at 435 nm was observed as well. By doping Mn ions, the major UV emission shifts from 377 nm to 408 nm, showing that Mn ions were not only incorporated into ZnO Ncs, but also introduced an impurity level in the bandgap. Moreover, with the concentration of Mn increasing, the relative intensities of the two emissions change largely, and the photoluminescence mechanism of them is discussed.
基金supported financially by the National Key Research and Development Program of China (2018YFB0104200)the Key Project of Strategic New Industry of Hunan Province (No. 2019GK2032)。
文摘Due to the high specific capacity and energy density, lithium–sulfur battery is regarded as a potential energy storage conversion system. However, the serious shuttle effect and the sluggish electrochemical reaction kinetics impede the practical use of lithium–sulfur battery. In the interests of breaking through the above knotty problems, herein we propose to use the polar flower-like Zn O modified by Bi OI nanoparticles as bifunctional host with catalytic and adsorption ability for polysulfides in lithium–sulfur battery.It can be found that this adsorption/catalytic host integrates the functions of adsorption and mutual catalytic conversion of polysulfides, in which the polar flower-like Zn O can effectively capture the polysulfides through strong polar-polar interaction, simultaneously the BiOI nanoparticles can accelerate the mutual conversion of polysulfides to Li2 S through reducing the activation energy and conversion energy barrier required for the electrochemical reaction. As a result, under a sulfur loading of 2.5 mg cm^(-2), the lithium–sulfur battery with Zn O/Bi OI/CNT/S as cathode reveals a considerable initial specific capacity of1267 mAh g^(-1) at a current density of 0.1 C. Even the current density increased to 1 C, the capacity can reach as 873.4 mAh g^(-1), together with a good capacity retention of 67.1% after 400 cycles. Therefore,after systematically study the positive effects of the flower-like ZnO modified by catalytic BiOI nanoparticles on the adsorption and catalytic conversion of polysulfides, this work provides a new idea for the development and application of high-performance lithium–sulfur batteries.
基金Funded by the National Natural Science Foundation of China (No. 20803055)the Fundamental Research Funds for the Central Universities (2010-1a-008,2011-1a-39,2011-1a-16)
文摘Ag modified ZnO （Ag/ZnO） nanocrystals were prepared by a facile and low temperature wet chemical method. The phase structures, morphologies, and optical properties of the as-prepared samples were characterized by X-ray powder diffraction （XRD）, field-emission scanning electron microscopy （FESEM）, high-resolution transmission electron microscopy （HRTEM）, the Brumauer-Emmett-Teller （BET） surface area, UV-vis diffuse reflectance spectroscopy and photoluminescence （PL） spectra, respectively. The photocatalytic performance of Ag/ZnO with diffent Ag contents was measured with the degradation of methyl orange （MO） at room temperature under UV light irradiation. The experimental results indicated that the well-crystalline ZnO nanopaticles with a size of ca. 4.5 nm exhibited a high photocatalytic activity for the degradation of MO with the apparent rate constant （k） of 1.57 ×10-2 min-1, and the photocatalytic activities of ZnO were further enhanced by modification with silver. When the Ag loading was 3mol%, Ag/ZnO showed the highest photocatalytic acitivity with a k value of 5.452×10-2 min-1, which is 3.5 and 2.5 time more than that of ZnO and commercial P25, respectively.
基金Funded by the National Natural Science Foundation of China (No.50572039)the Postdoctoral Foundation of China (No. 20060390284)Jiangsu Planned Projects for Postdoctoral Research Funds
文摘A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission electron microscopy and UV-visible absorption spectroscopy. The results indicate that modulating the adding ways of water has a significant effect on the shape of the obtained nanocrystals. The addition of small quantity of water can increase the growth rate of crystals and leads to the formation of different shapes. The resulting shapes of the novel structures are diverse, including spheres, cones, and teardrops, all of which are obtained without any additional surfactants. These studies concerning the shape evolution of nanocrystals should be valuable for further design and for greater understanding of advanced nanoscale building-block architectures.
文摘In this article, we report the results of our detailed investigations of the growth kinetics of zero-dimensional nanocrystals as well as one-dimensional nanorods by the combined use of small angel X-ray scattering （SAXS）, transmission electron microscopy （TEM） along with other physical techniques. The study includes growth kinetics of gold nanocrystals formed by the reduction of HAuCl4 by tetrakis（hydroxymethyl） phosphonium chloride in aqueous solution, of CdSe nanocrystals formed by the reaction of cadmium stearate and selenium under solvothermal conditions, and of ZnO nanorods formed by the reaction of zinc acetate with sodium hydroxide under solvothermal conditions in the absence and presence of capping agents. The growth of gold nanocrystals does not follow the diffusion-limited Ostwald ripening, and instead follows a Sigmoidal rate curve. The heat change associated with the growth determined by isothermal titration calorimetry is about 10 kcal·mol^-1 per I nm increase in the diameter of the nanocrystals. In the case of CdSe nanocrystals also, the growth mechanism deviates from diffusion-limited growth and follows a combined model containing both diffusion and surface reaction terms. Our study of the growth kinetics of uncapped and poly（vinyl pyrollidone） （PVP）-capped ZnO nanorods has yielded interesting insights. We observe small nanocrystals next to the ZnO nanorods after a lapse of time in addition to periodic focusing and defocusing of the width of the length distribution. These observations lend support to the diffusion-limited growth model for the growth of uncapped ZnO nanorods. Accordingly, the time dependence on the length of uncapped nanorods follows the L3 law as required for diffusion-limited Ostwald ripening. The PVP-capped nanorods, however, show a time dependence, which is best described by a combination of diffusion （L^3） and surface reaction （L^2） terms.
文摘利用热分解法制备了结构明确的负载型纳米晶催化剂。在纳米晶成核和生长过程中加入一维ZnO纳米棒作为晶种,调控不同组分的纳米晶在ZnO纳米棒表面均匀生长,从而获得了结构明确的MnO/ZnO、Co_(3)O_(4)/ZnO、Co_(3)Mn_(1)/ZnO催化剂。透射电子显微镜(TEM)与X射线粉末衍射(XRD)结果显示,不同组分纳米颗粒都均匀分散在ZnO纳米棒表面。相对于MnO/ZnO和Co_(3)O_(4)/ZnO催化剂,Co_(3)Mn_(1)/ZnO催化剂在CO氧化反应中具有最佳的催化性能。在200 L·g_(cat)^(-1)·h^(-1)的气时空速下,Co_(3)Mn_(1)/ZnO催化剂起活温度为50℃,其T100(CO转化率达到100%时的温度)为200℃;利用X射线光电子能谱(XPS)对不同催化剂进行了分析,结果显示,Co_(3)Mn_(1)/ZnO催化剂的氧空位比MnO/ZnO催化剂提高了30%以上,从而使其具有较高的CO氧化催化性能。更为重要的是,Co_(3)Mn_(1)/ZnO复合纳米晶催化剂的活化能(39.4 k J·mol^(-1))远低于其它负载型纳米晶催化剂。
