The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries(NIBs) due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective...The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries(NIBs) due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective because it needs to be sintered under oxygen atmosphere at high temperature and followed by a quenching procedure. Here we first report that the pure β phase can be stabilized by Cu-doping and easily synthesized by replacing a proportion of Mn with Cu via a simplified process including sintering in air and cooling to room temperature naturally. Based on the first-principle calculations, the band gap decreases from 0.7 eV to 0.3 eV, which indicates that the electronic conductivity can be improved by Cu-doping. The designed -NaCu(0.1)Mn(0.9)O2 is applied as cathode in NIBs, exhibiting an energy density of 419 Wh/kg and better performance in terms of rate capability and cycling stability than those in the undoped case.展开更多
ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO:Cu film can be enhanced by a moderate level ...ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO:Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO:Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaC...Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaCl flux method.The solubility of Cd in Cu2Se at room temperature was less than 6%,and a second phase of CdSe was found in the samples with large initial Cd content(x=0.01 and 0.02).Field-emission scanning electron microscopic image showed that the arranged lamellae formed a large-scale layered structure with an average thickness of approximately 100 nm.Transmission electron microscopy demonstrated that doping of Cd atoms did not destroy the crystal integrity of Cu2Se.A small amount of Cd in Cu2Se could reduce the electrical and thermal conductivities of the material,thus significantly enhancing its thermoelectric performance.With the increase in Cd content in the sample,the carrier concentration decreased and the mobility increased gradually.Thermogravimetric differential thermal analysis showed that no weight loss occurred below the melting point.Excessive Cd doping led to the emergence of the second phase of CdSe in the sample,thus significantly increasing the thermal conductivity of the material.A maximum ZT value of 1.67 at 700 K was obtained in the Cu1.9925SeCd0.0075 sample.展开更多
Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are char...Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are characterized by scanning electron microscopy and Doppler broadening positron annihilation spectroscopy. The results show that plenty of point defects can be produced by introducing He during the growth of the multilayer nanofilms. With the increasing natural storage time, He located in the near surface of the Cu//W multilayer nanofilm at room temperature could be released gradually and induce the segregation of He-related defects due to the diffusion of He and defects. However, more He in the deep region spread along the interface of the Cu/W multilayer nanofilm. Meanwhile, the layer interfaces can still maintain their stability.展开更多
A sintered Ti13Cus7 target was sputtered by reactive direct current (DC) magnetron sputtering with a gas mixture of argon/nitrogen for different sputtering powers. Titanium-coppernitrogen thin films were deposited o...A sintered Ti13Cus7 target was sputtered by reactive direct current (DC) magnetron sputtering with a gas mixture of argon/nitrogen for different sputtering powers. Titanium-coppernitrogen thin films were deposited on Si (111), glass slide and potassium bromide (KBr) substrates. Phase analysis and structural properties of titanium-copper-nitrogen thin films were studied by X-ray diffraction (XRD). The chemical bonding was characterized by Fourier transform infrared (FTIR) spectroscopy. The results from XRD show that the observed phases are nano-crystallite cubic anti rhenium oxide (anti ReO3) structures of titanium doped Cu3N (Ti:Cu3N) and nanocrystallite face centered cubic (fcc) structures of copper. Scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM/EDX) were used to determine the film morphology and atomic titanium/copper ratio, respectively. The films possess continuous and agglomerated structure with an atomic titanium/copper ratio (-0.07) below that of the original target (- 0.15). The transmittance spectra of the composite films were measured in the range of 360 nm to 1100 nm. Film thickness, refractive index and extinction coefficient were extracted from the measured transmittance using a reverse engineering method. In the visible range, the higher absorption coefficient of the films prepared at lower sputtering power indicates more nitrification in comparison to those prepared at higher sputtering power. This is consistent with the formation of larger Ti:Cu3N crystallites at lower sputtering power. The deposition rate vs. sputtering power shows an abrupt transition from metallic mode to poisoned mode. A complicated behavior of the films' resistivity upon sputtering power is shown.展开更多
基金Supported by the National Key Technologies R&D Program of China under Grant No 2016YFB0901500the National Nature Science Foundation of China under Grant Nos 51725206 and 51421002
文摘The high-temperature β-phase NaMnO2 is a promising material for Na-ion batteries(NIBs) due to its high capacity and abundant resources. However, the synthesis of phase-pure -NaMnO2 is burdensome and costineffective because it needs to be sintered under oxygen atmosphere at high temperature and followed by a quenching procedure. Here we first report that the pure β phase can be stabilized by Cu-doping and easily synthesized by replacing a proportion of Mn with Cu via a simplified process including sintering in air and cooling to room temperature naturally. Based on the first-principle calculations, the band gap decreases from 0.7 eV to 0.3 eV, which indicates that the electronic conductivity can be improved by Cu-doping. The designed -NaCu(0.1)Mn(0.9)O2 is applied as cathode in NIBs, exhibiting an energy density of 419 Wh/kg and better performance in terms of rate capability and cycling stability than those in the undoped case.
基金Project supported by the Natural Science Foundation of Gansu Province, China (Grant No. 0803RJZA008)the Fundamental Research Funds for the Central Universities, China (Grant No. zyz2012057)+1 种基金the National Natural Science Foundation of China (Grant No. 11004141)the Program for New Century Excellent Talents in University, China (Grant No. 11-0351)
文摘ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO:Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO:Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61864012 and 21701140)the Program for Innovative Research Team(in Science and Technology)in University of Yunnan Province,China.
文摘Cu2Se is a promising"phonon liquid-electron crystal"thermoelectric material with excellent thermoelectric performance.In this work,Cd-doped Cu2-xSeCdx(x=0,0.0075,0.01,and 0.02)samples were prepared using NaCl flux method.The solubility of Cd in Cu2Se at room temperature was less than 6%,and a second phase of CdSe was found in the samples with large initial Cd content(x=0.01 and 0.02).Field-emission scanning electron microscopic image showed that the arranged lamellae formed a large-scale layered structure with an average thickness of approximately 100 nm.Transmission electron microscopy demonstrated that doping of Cd atoms did not destroy the crystal integrity of Cu2Se.A small amount of Cd in Cu2Se could reduce the electrical and thermal conductivities of the material,thus significantly enhancing its thermoelectric performance.With the increase in Cd content in the sample,the carrier concentration decreased and the mobility increased gradually.Thermogravimetric differential thermal analysis showed that no weight loss occurred below the melting point.Excessive Cd doping led to the emergence of the second phase of CdSe in the sample,thus significantly increasing the thermal conductivity of the material.A maximum ZT value of 1.67 at 700 K was obtained in the Cu1.9925SeCd0.0075 sample.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11275132,51171124 and 11505121the International Science and Technology Cooperation Program of China under Grant No 2014DFR50710the Scientific and Technical Supporting Programs Funded by the Science and Technology Department of Sichuan Province under Grant No 2014GZ0004
文摘Cu/W multilayer nanofilms are prepared in pure Ar and He/At mixing atmosphere by the rf magnetron sputtering method. The cross-sectional morphology and the defect distribution of the Cu/W multilayer nanofilms are characterized by scanning electron microscopy and Doppler broadening positron annihilation spectroscopy. The results show that plenty of point defects can be produced by introducing He during the growth of the multilayer nanofilms. With the increasing natural storage time, He located in the near surface of the Cu//W multilayer nanofilm at room temperature could be released gradually and induce the segregation of He-related defects due to the diffusion of He and defects. However, more He in the deep region spread along the interface of the Cu/W multilayer nanofilm. Meanwhile, the layer interfaces can still maintain their stability.
基金the financial support of the Iranian nanotechnology initiative
文摘A sintered Ti13Cus7 target was sputtered by reactive direct current (DC) magnetron sputtering with a gas mixture of argon/nitrogen for different sputtering powers. Titanium-coppernitrogen thin films were deposited on Si (111), glass slide and potassium bromide (KBr) substrates. Phase analysis and structural properties of titanium-copper-nitrogen thin films were studied by X-ray diffraction (XRD). The chemical bonding was characterized by Fourier transform infrared (FTIR) spectroscopy. The results from XRD show that the observed phases are nano-crystallite cubic anti rhenium oxide (anti ReO3) structures of titanium doped Cu3N (Ti:Cu3N) and nanocrystallite face centered cubic (fcc) structures of copper. Scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM/EDX) were used to determine the film morphology and atomic titanium/copper ratio, respectively. The films possess continuous and agglomerated structure with an atomic titanium/copper ratio (-0.07) below that of the original target (- 0.15). The transmittance spectra of the composite films were measured in the range of 360 nm to 1100 nm. Film thickness, refractive index and extinction coefficient were extracted from the measured transmittance using a reverse engineering method. In the visible range, the higher absorption coefficient of the films prepared at lower sputtering power indicates more nitrification in comparison to those prepared at higher sputtering power. This is consistent with the formation of larger Ti:Cu3N crystallites at lower sputtering power. The deposition rate vs. sputtering power shows an abrupt transition from metallic mode to poisoned mode. A complicated behavior of the films' resistivity upon sputtering power is shown.