In a previous greenhouse experiment, we showed that there was an interaction between Cu and Zn, which affected growth and metal uptake by young barley plants grown on soil to which Cd, Cu, Pb, and Zn had been added. W...In a previous greenhouse experiment, we showed that there was an interaction between Cu and Zn, which affected growth and metal uptake by young barley plants grown on soil to which Cd, Cu, Pb, and Zn had been added. We suggested that the underlying mechanism was the control of the amount of plant-available Zn by competitive adsorption between Cu and Zn. In order to test this hypothesis, the adsorption of Zn alone, and in the presence of added Cd, Cu and Pb, has been measured using the same soil. Following adsorption, the extractability of the Zn in CaCl2 solution was measured. The adsorption isotherms showed that of the added metals only Cu had a large effect on Zn adsorption. The effect of Cu was to reduce Zn adsorption and to increase the amount of CaCl2-extractable (i.e. plant-available) Zn, in agreement with the conclusions from the greenhouse experiment. The magnitude of the effect of Cu on plant-available Zn was similar in both experiments.展开更多
The global demand for resource sustainability is growing. Thus, the development of single-source, environment-friendly colloidal semiconductor nanocrystal (NC) phosphors with broadband emission spectra is highly des...The global demand for resource sustainability is growing. Thus, the development of single-source, environment-friendly colloidal semiconductor nanocrystal (NC) phosphors with broadband emission spectra is highly desirable for use as color converters in white light-emitting diodes (WLEDs). We report herein the gram-scale synthesis of single-source, cadmium-free, dual-emissive Mn-doped Zn-Cu-In-S NCs (d-dots) by a simple, non-injection, low-cost, one-pot approach. This synthesis method led to the formation of NCs with continuously varying compositions in a radial direction because each precursor had a different reactivity. Consequently, the d-dots exhibited two emission bands, one that could be attributed to Mn emission and a second that could be ascribed to the band edge of the Zn-Cu-In-S NCs. The emission peaks assigned to band edge were tunable by modifying the particle size and composition. The prepared d-dots also exhibited the characteristic zero self-absorption, a quantum yield of 46%, and good thermal stability. Combining a commercial blue light-emitting diode (LED) chip with optimized d-dots as color converters gave a high color rendering index of up to 90, Commission Internationale de l'eclairage color coordinates of (0.332, 0.321), and a correlated color temperature of 5,680 K. These results suggest that cadmium-free, thermally stable, single-phase d-dot phosphors have potential applications in WLEDs.展开更多
Zinc(Zn) and its alloys have been proposed as biodegradable implant materials due to their unique combination of biodegradability, biocompatibility, and biofunctionality. However, the insufficient mechanical propertie...Zinc(Zn) and its alloys have been proposed as biodegradable implant materials due to their unique combination of biodegradability, biocompatibility, and biofunctionality. However, the insufficient mechanical properties of pure Zn greatly limit its clinical application. Here, we report on the microstructure, mechanical properties, friction and wear behavior, corrosion and degradation properties, hemocompatibility, and cytocompatibility of Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys under three different conditions of as-cast(AC),hot-rolling(HR), and hot-rolling plus cold-rolling(HR + CR). The HR + CR Zn–3 Cu–0.2 Ti exhibited the best set of comprehensive properties among all the alloy samples, with yield strength of 211.0 MPa, ultimate strength of 271.1 MPa, and elongation of 72.1 %. Immersion tests of the Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys in Hanks’ solution for 3 months indicated that the AC samples showed the lowest degradation rate,followed by the HR samples, and then the HR + CR samples, while the HR + CR Zn–3 Cu exhibited the highest degradation rate of 23.9 m/a. Friction and wear testing of the Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys in Hanks’ solution indicated that the AC samples showed the highest wear resistance, followed by the HR samples, and then the HR + CR samples, while the AC Zn–3 Cu–0.2 Ti showed the highest wear resistance.The diluted extracts of HR + CR Zn–3 Cu and Zn–3 Cu–0.2 Ti at a concentration of ≤25 % exhibited noncytotoxicity. Furthermore, both the HR + CR Zn–3 Cu and Zn–3 Cu–0.2 Ti exhibited effective antibacterial properties against S. aureus.展开更多
In this work,trace Li was introduced to strengthen Zn–4Cu alloys.The results indicated that trace amounts of Li contributed to a significant increase in strength,resulting in an acceptable loss of elongation at fract...In this work,trace Li was introduced to strengthen Zn–4Cu alloys.The results indicated that trace amounts of Li contributed to a significant increase in strength,resulting in an acceptable loss of elongation at fracture.Additionally,Li in the form of LiZn_(4) led to more intensive galvanic corrosion,which accelerated the early corrosion rate.The release of a large amount of Zn^(2+),caused by the addition of Li,affected the phase composition of the main Zn-containing corrosion products.Moreover,the inhibition effect of the alloy on Staphylococcus aureus(S.aureus)was enhanced by the addition of 0.02 wt.%Li.展开更多
An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 7...An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 717 resins based on the coordination difference between Zn^(2+)/Cu^(2+)and Cl^(-).The theoretical calculation and spectroscopic analyses suggested that the coordination between Zn^(2+)and Cl^(-)is much stronger than that between Cu^(2+)and Cl^(-),and the Cl-concentration significantly affects Zn(Ⅱ)and Cu(Ⅱ)species.The factors involving Cl-concentration,resin dosage,shaking speed,and temperature were investigated to determine the optimal condition,and the maximum separation factor of Zn/Cu reached as high as 479.2.The results of the adsorption isotherms,adsorption kinetics,SEM,FTIR,and XPS analyses indicated that the process followed the monolayer uniform chemisorption.Through the continuous adsorption experiments,Zn(Ⅱ)and Cu(Ⅱ)in the high-chlorine raffinate were separately recovered,allowing the reuse of residual waste acid and germanium.展开更多
This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- ...This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability (HGAS) of the η phase. This indicates that HGAS was successfully achieved in the present experiments.展开更多
Zn-Cu-codoped SnO2 nanoparticles have been synthesized by chemical precipitation method. All nanoparticles are crystalline, with the average size increases from 2.55 nm to 4.13 nm as the calcination temperature increa...Zn-Cu-codoped SnO2 nanoparticles have been synthesized by chemical precipitation method. All nanoparticles are crystalline, with the average size increases from 2.55 nm to 4.13 nm as the calcination temperature increases from 400℃ to 600℃. The high calcination temperature can enhance the crystalline quality and grain growth. The oxygen content decreases with decreasing calcination temperature; at a low temperature of 400℃, Zn-Cu-codoped SnO2 nanoparticles are in a rather oxygen-poor state having many oxygen vacancies. The optical band gap energies of Zn-Cu-codoped SnO2 nanoparticles calcined at 400℃ and 600℃ are decreased from 3.93 eV to 3.62 eV due to quantum confinement effects. Both samples exhibit room-temperature ferromagnetism, with a larger saturation magnetization at 400℃ due to the presence of large density of defects such as oxygen vacancies. Zn-Cu-codoped SnO2 nanoparticles exhibit large optical band gap energies and room temperature ferromagnetism, which make them potential candidates for applications in optoelectronics and spintronics.展开更多
Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What ...Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What is more,as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster,how Zn surface distribution affects catalytic activity is still not clear.In this work,we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface,where the surface oxidation was shown to play the critical role.Before surface oxidation,the Zn single atom/Cu is more active than the Zn small cluster/Cu,but its surface oxidation is difficult to take place.Instead,after the easy surface oxidation by CO_(2)decomposition,the oxidized Zn small cluster/Cu becomes much more active,which even exceeds the hardlyoxidized Zn single atom/Cu to become the active phase.Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors:i)The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster.That makes the O intermediates bind at the Zn/Cu interface,preventing their too tight binding for further hydrogenation;ii)The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates.This work provided one more example that under certain condition,the metal cluster can be more active than the single atom in heterogeneous catalysis.展开更多
文摘In a previous greenhouse experiment, we showed that there was an interaction between Cu and Zn, which affected growth and metal uptake by young barley plants grown on soil to which Cd, Cu, Pb, and Zn had been added. We suggested that the underlying mechanism was the control of the amount of plant-available Zn by competitive adsorption between Cu and Zn. In order to test this hypothesis, the adsorption of Zn alone, and in the presence of added Cd, Cu and Pb, has been measured using the same soil. Following adsorption, the extractability of the Zn in CaCl2 solution was measured. The adsorption isotherms showed that of the added metals only Cu had a large effect on Zn adsorption. The effect of Cu was to reduce Zn adsorption and to increase the amount of CaCl2-extractable (i.e. plant-available) Zn, in agreement with the conclusions from the greenhouse experiment. The magnitude of the effect of Cu on plant-available Zn was similar in both experiments.
基金This work was supported by the National Natural Science Foundation of China (Nos. 21373097 and 51072067) and the National Basic Research Program of China (No. 2011CB935800).
文摘The global demand for resource sustainability is growing. Thus, the development of single-source, environment-friendly colloidal semiconductor nanocrystal (NC) phosphors with broadband emission spectra is highly desirable for use as color converters in white light-emitting diodes (WLEDs). We report herein the gram-scale synthesis of single-source, cadmium-free, dual-emissive Mn-doped Zn-Cu-In-S NCs (d-dots) by a simple, non-injection, low-cost, one-pot approach. This synthesis method led to the formation of NCs with continuously varying compositions in a radial direction because each precursor had a different reactivity. Consequently, the d-dots exhibited two emission bands, one that could be attributed to Mn emission and a second that could be ascribed to the band edge of the Zn-Cu-In-S NCs. The emission peaks assigned to band edge were tunable by modifying the particle size and composition. The prepared d-dots also exhibited the characteristic zero self-absorption, a quantum yield of 46%, and good thermal stability. Combining a commercial blue light-emitting diode (LED) chip with optimized d-dots as color converters gave a high color rendering index of up to 90, Commission Internationale de l'eclairage color coordinates of (0.332, 0.321), and a correlated color temperature of 5,680 K. These results suggest that cadmium-free, thermally stable, single-phase d-dot phosphors have potential applications in WLEDs.
基金supported financially by the Research Funds of the Wenzhou Science and Technology Bureau (Nos.ZG2019022 and 2018ZG008)support for this research by the Australian Research Council (ARC) through the Discovery Project (No.DP170102557)+1 种基金the Future Fellowship(No.FT160100252)support of the ARC Research Hub for Advanced Manufacturing of Medical Devices (No.IH150100024)。
文摘Zinc(Zn) and its alloys have been proposed as biodegradable implant materials due to their unique combination of biodegradability, biocompatibility, and biofunctionality. However, the insufficient mechanical properties of pure Zn greatly limit its clinical application. Here, we report on the microstructure, mechanical properties, friction and wear behavior, corrosion and degradation properties, hemocompatibility, and cytocompatibility of Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys under three different conditions of as-cast(AC),hot-rolling(HR), and hot-rolling plus cold-rolling(HR + CR). The HR + CR Zn–3 Cu–0.2 Ti exhibited the best set of comprehensive properties among all the alloy samples, with yield strength of 211.0 MPa, ultimate strength of 271.1 MPa, and elongation of 72.1 %. Immersion tests of the Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys in Hanks’ solution for 3 months indicated that the AC samples showed the lowest degradation rate,followed by the HR samples, and then the HR + CR samples, while the HR + CR Zn–3 Cu exhibited the highest degradation rate of 23.9 m/a. Friction and wear testing of the Zn–3 Cu and Zn–3 Cu–0.2 Ti alloys in Hanks’ solution indicated that the AC samples showed the highest wear resistance, followed by the HR samples, and then the HR + CR samples, while the AC Zn–3 Cu–0.2 Ti showed the highest wear resistance.The diluted extracts of HR + CR Zn–3 Cu and Zn–3 Cu–0.2 Ti at a concentration of ≤25 % exhibited noncytotoxicity. Furthermore, both the HR + CR Zn–3 Cu and Zn–3 Cu–0.2 Ti exhibited effective antibacterial properties against S. aureus.
基金supported by the National Natural Science Foundation of China(Grant Nos.51971035 and U1964204).
文摘In this work,trace Li was introduced to strengthen Zn–4Cu alloys.The results indicated that trace amounts of Li contributed to a significant increase in strength,resulting in an acceptable loss of elongation at fracture.Additionally,Li in the form of LiZn_(4) led to more intensive galvanic corrosion,which accelerated the early corrosion rate.The release of a large amount of Zn^(2+),caused by the addition of Li,affected the phase composition of the main Zn-containing corrosion products.Moreover,the inhibition effect of the alloy on Staphylococcus aureus(S.aureus)was enhanced by the addition of 0.02 wt.%Li.
基金financially supported by the Postdoctoral Research Foundation of Central South University,China(No.140050037)。
文摘An anion-exchange-based chromatographic separation approach was developed to selectively recover zinc and copper from the high-chlorine raffinate generated in the process of germanium chlorination distillation using 717 resins based on the coordination difference between Zn^(2+)/Cu^(2+)and Cl^(-).The theoretical calculation and spectroscopic analyses suggested that the coordination between Zn^(2+)and Cl^(-)is much stronger than that between Cu^(2+)and Cl^(-),and the Cl-concentration significantly affects Zn(Ⅱ)and Cu(Ⅱ)species.The factors involving Cl-concentration,resin dosage,shaking speed,and temperature were investigated to determine the optimal condition,and the maximum separation factor of Zn/Cu reached as high as 479.2.The results of the adsorption isotherms,adsorption kinetics,SEM,FTIR,and XPS analyses indicated that the process followed the monolayer uniform chemisorption.Through the continuous adsorption experiments,Zn(Ⅱ)and Cu(Ⅱ)in the high-chlorine raffinate were separately recovered,allowing the reuse of residual waste acid and germanium.
基金Project supported by the National Natural Science Foundation of China (Grant Nos 50201012 and 50471065).
文摘This paper reports on laser surface remelting experiments performed on a Zn-2wt.%Cu hypoperitectic alloy by employing a 5kW CW CO2 laser at scanning velocities between 6 and 1207mm/s. The growth velocities of the mi- crostructures in the laser molten pool were accurately measured. The planar interface structure caused by the high velocity absolute stability was achieved at a growth velocity of 210 mm/s. An implicit expression of the critical solidification velocity for the cellular-planar transition was carried out by nonlinear stability analyses of the planar interface. The results showed a better agreement with the measured critical velocity than that predicted by M-S theory. Cell-free structures were observed throughout the whole molten pool at a scanning velocity of 652 mm/s and the calculated minimum temperature gradient in this molten pool was very close to the critical temperature gradient for high gradient absolute stability (HGAS) of the η phase. This indicates that HGAS was successfully achieved in the present experiments.
基金Project supported by the Natural Science Foundation of Zhejiang Province,China(Grant No.LR16F040001)
文摘Zn-Cu-codoped SnO2 nanoparticles have been synthesized by chemical precipitation method. All nanoparticles are crystalline, with the average size increases from 2.55 nm to 4.13 nm as the calcination temperature increases from 400℃ to 600℃. The high calcination temperature can enhance the crystalline quality and grain growth. The oxygen content decreases with decreasing calcination temperature; at a low temperature of 400℃, Zn-Cu-codoped SnO2 nanoparticles are in a rather oxygen-poor state having many oxygen vacancies. The optical band gap energies of Zn-Cu-codoped SnO2 nanoparticles calcined at 400℃ and 600℃ are decreased from 3.93 eV to 3.62 eV due to quantum confinement effects. Both samples exhibit room-temperature ferromagnetism, with a larger saturation magnetization at 400℃ due to the presence of large density of defects such as oxygen vacancies. Zn-Cu-codoped SnO2 nanoparticles exhibit large optical band gap energies and room temperature ferromagnetism, which make them potential candidates for applications in optoelectronics and spintronics.
基金financially supported by the NSFC,China(No.22022504)the Guangdong“Pearl River”Talent Plan,China(No.2019QN01L353)+3 种基金the Higher Education Innovation Strong School Project of Guangdong Province of China,China(2020KTSCX122)the Guangdong Provincial Key Laboratory of Catalysis,China(No.2020B121201002)support from the Center for Computational Science and Engineering at SUSTechfinancial support by the National Key Research and Development Program of China,China(No.2017YFC0210905)。
文摘Methanol synthesis from CO_(2)hydrogenation catalyzed by Zn/Cu alloy has been widely studied,but there is still debate on its catalytic active phase and whether the Zn can be oxidized during the reaction process.What is more,as Zn atoms could locate on Zn/Cu alloy surface in forms of both single atom and cluster,how Zn surface distribution affects catalytic activity is still not clear.In this work,we performed a systematic theoretical study to compare the mechanistic natures and catalytic pathways between Zn single atom and small cluster on catalyst surface,where the surface oxidation was shown to play the critical role.Before surface oxidation,the Zn single atom/Cu is more active than the Zn small cluster/Cu,but its surface oxidation is difficult to take place.Instead,after the easy surface oxidation by CO_(2)decomposition,the oxidized Zn small cluster/Cu becomes much more active,which even exceeds the hardlyoxidized Zn single atom/Cu to become the active phase.Further analyses show this dramatic promotion of surface oxidation can be ascribed to the following factors:i)The O from surface oxidation could preferably occupy the strongest binding sites on the center of Zn cluster.That makes the O intermediates bind at the Zn/Cu interface,preventing their too tight binding for further hydrogenation;ii)The higher positive charge and work function on the oxidized surface could also promote the hydrogenation of O intermediates.This work provided one more example that under certain condition,the metal cluster can be more active than the single atom in heterogeneous catalysis.