CexZr1-xO2 complex oxides doped by transition metal(Fe, Mn, Cu) were prepared by precipitation method. Thermal stability of samples was characterized by XRD, surface areas were measured by BET method and reductive pro...CexZr1-xO2 complex oxides doped by transition metal(Fe, Mn, Cu) were prepared by precipitation method. Thermal stability of samples was characterized by XRD, surface areas were measured by BET method and reductive property was characterized by TPR. The results show that MnO2 can be dispersed in solid solution after calcined at 1273 K, when the loading is 12%, while Fe and Cu is easy to separate from samples at this temperature. Samples doped simultaneously by Fe, Mn or Fe, Cu demonstrated high reactive property at low temperature. The starting reduction temperature are 413 and 373 K, respectively. TPR results also show a broad range of reductive temperature exists in these bi-metal doped samples.展开更多
In order to reduce the oxidizing and volatilizing caused by Mg element in the traditional methods for synthesizing Mg2Sil-xSnx （x=0.2, 0.4, 0.6, 0.8） solid solutions, microwave irradiation techniques were used in pr...In order to reduce the oxidizing and volatilizing caused by Mg element in the traditional methods for synthesizing Mg2Sil-xSnx （x=0.2, 0.4, 0.6, 0.8） solid solutions, microwave irradiation techniques were used in preparing them as thermoelectric materials. Structure and phase composition of the obtained materials were investigated by X-ray diffraction （XRD）. The electrical conductivity, Seebeck coefficient and thermal conductivity were measured as a function of temperature from 300 to 750 K. It is found that Mg2Si1-xSnx solid solutions are well formed with excessive content of 5% （molar fraction） Mg from the stoichiometric MgESil.xSnx under microwave irradiation. A maximum dimensionless figure of merit, ZT, of about 0.26 is obtained for Mg2Si1-xSnx solid solutions at about 500 K for x=0.6.展开更多
The Ce_xTh_(1-x)O_2 solid solutions were prepared by citrate sol-gel method,and their structure and reduction properties were studied. XRD shows that solid solution with cubicphase formed in all the solid solutions (x...The Ce_xTh_(1-x)O_2 solid solutions were prepared by citrate sol-gel method,and their structure and reduction properties were studied. XRD shows that solid solution with cubicphase formed in all the solid solutions (x = 0.2, 0.5, 0.8) Ce_xTh_(1-x)O_2. Raman spectrum showsthat Ce-Th complex oxides can promote the formation of oxygen vacancies. Two reduction peaks appearin the TPR profiles of Ce_xTh_(1-x)O_2 solid solution. The a peak is attributed to the reduction ofCe^(4+) on the surface, and the β peak is attributed to the reduction of bulk CeO_2. Theincorporation of Th atom into CeO_2 improves the reduction of CeO_2. Ce_xTh_(1-x)O_2 mixed oxidesare promising materials for oxygen vacancies produced, as well as catalysts for many reactionsinvolved oxygen, such as the catalysts for three-way reactions for reducing the releasing pollutantsor combustion of VOCs.展开更多
Nanosized Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions（x = 0.00-0.20） were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the...Nanosized Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions（x = 0.00-0.20） were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the Mg2Ni–Ni–5 mol% Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） composites.The structures and spectrum characteristics of the Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F^2g mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu^3＋ and Nd^3＋ ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg2Ni–Ni–5 mol% Ce1-x（Nd0.5Eu0.5xO2-δ composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S20 increased from 25.0%（x = 0.00） to 42.2%（x = 0.20）.The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce1-x（Nd0.5Eu0.5）xO2-δ solid solutions.展开更多
The transition metals （Cu, Co, and Fe） were applied to modify Ni/Ce0.2Zr0.1Al0.7Oδ catalyst. The effects of transition metals on the catalytic properties of Ni/Ce0.2Zr0.1Al0.7Oδ autothermal reforming of methane we...The transition metals （Cu, Co, and Fe） were applied to modify Ni/Ce0.2Zr0.1Al0.7Oδ catalyst. The effects of transition metals on the catalytic properties of Ni/Ce0.2Zr0.1Al0.7Oδ autothermal reforming of methane were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS. Tests in autothermal reforming of methane to hydrogen showed that the addition of transition metals （Cu and Co） significantly increased the activity of catalyst under the conditions of lower reaction temperature, and Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ was found to have the highest conversion of CH4 among all catalysts in the operation temperatures ranging from 923 K to 1023 K. TPR, XRD and XPS measurements indicated that the cubic phases of CexZr1-xO2 solid solution were formed in the preparation process of catalysts. Strong interaction was found to exist between NiO and CexZr1-xO2 solid solution. The addition of Cu improved the dispersion of NiO, inhibited the formation of NiAl2O4, and thus significantly promoted the activity of the catalyst Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ展开更多
Fe^3+and Zn^2+ions were doped into the lattice of CeO2 via the hydrothermal method.The micro structure and spectra features were analyzed systemically.XRD results show that the solid solubility of Fe^3+and Zn^2+ions i...Fe^3+and Zn^2+ions were doped into the lattice of CeO2 via the hydrothermal method.The micro structure and spectra features were analyzed systemically.XRD results show that the solid solubility of Fe^3+and Zn^2+ions in Ce1-x(Fe0.5Zn0.5)xO2 can be identified as x=0.16.The cell volumes are decreased by increasing the doped content.The TEM graphs prove that the grain size of the sample is about 10 nm,and the EDS result indicates that the doped contents are in accordance with that of the theory concentrations.Meanwhile,the doping also causes the increasing concentrations of the defects and oxygen vacancies which are supported by the XPS,Raman,UV and PL characterizations.The samples exhibit better catalytic activities for improving the hydrogen storage properties and the electrochemical kinetics of the ball milled Mg2Ni based composites.Further,the catalysis effects are improved by increasing the doped contents,which can be ascribed to the increasing contents of the oxygen vacancies,defects,the special electron transition states and the nature of the doped ions in CeO2-based solid solutions.展开更多
In this paper,effect of two strategies on afterglow behavior of Lu_(2)O_(3):Eu single crystal scintillato r,Pr^(3+)codoping and solid solution with Sc_(2)O_(3),were studied systematically.Two groups of Lu_(2)O_(3):5 a...In this paper,effect of two strategies on afterglow behavior of Lu_(2)O_(3):Eu single crystal scintillato r,Pr^(3+)codoping and solid solution with Sc_(2)O_(3),were studied systematically.Two groups of Lu_(2)O_(3):5 at%Eu,x at%Pr(x=0,0.2,0.5,1,2 and 5)and(Lu1-yScy)_(2)O_(3):5 at%Eu(y=0,20 at%,50 at%and 70 at%)single crystals were grown by floating zone(FZ)method in air atmosphere.The structures of as-grown crystals were determined by X-ray diffraction(XRD).The scintillation,photoluminescence properties and carrier trap states were investigated through afterglow,X-ray excitation luminescence(XEL),transmittance,photoluminescence excitation(PLE)and photoluminescence(PL),PL decay and thermal stimulated luminescence(TSL)curves.It is found that with the increase of Pr^(3+)concentration,the afterglow level of the system decreases at the expense of scintillation luminescence efficiency.Meanwhile,although Sc_(2)O_(3):Eu presents much lower afterglow intensity than Lu_(2)O_(3):Eu,the addition of Sc_(2)O_(3)will just increase the afterglow level of the(Lu1-yScy)_(2)O_(3):5 at%Eu single crystal system.Possible mechanisms for above phenomena are discussed based on experimental results.展开更多
Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneousl...Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneously. Nevertheless, it is still challenging to exploit low-cost and stable Zscheme photocatalysts with highly-efficient H2 evolution from solar water-splitting so far. Herein, we report a novel all-solidstate Z-scheme photocatalyst Cd1-xZnxS@WO3-x consisting of Cd1-xZnxS nanorods coated with oxygen-deficient WO3-x amorphous layers. The Cd1-xZnxS@WO3-x exhibits an outstanding H2 evolution reaction(HER) activity as compared with Pt-loaded Cd1-xZnxS and most WO3- and Cd S-based photocatalysts, due to the generation of stronger reducing electrons through the appropriate Zn-doping in Cd1-xZnxS and the enhanced charge transfer by introducing oxygen vacancies(W^5+/OVs) into the ultrathin WO3-x amorphous coatings. The optimal HER rate of Cd1-xZnxS@WO3- xis determined to be 21.68 mmol h^-1 g^-1, which is further raised up to 28.25 mmol h^-1 g^-1(about 12 times more than that of Pt/Cd1-xZnxS) when Cd1-xZnxS@WO3-x is hybridized by Co Ox and Ni Oxdual cocatalysts(Cd1-xZnxS@WO3-x/CoOx/NiOx)through in-situ photo-deposition. Moreover, the corresponding apparent quantum yield(AQY) at 420 nm is significantly increased from 34.6% for Cd1-xZnxS@WO3-x to 60.8% for Cd1-xZnxS@WO3-x/CoOx/NiOx. In addition, both Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx demonstrate good stability towards HER. The results displayed in this work will inspire the rational design and synthesis of high-performance nanostructures for photocatalytic applications.展开更多
文摘CexZr1-xO2 complex oxides doped by transition metal(Fe, Mn, Cu) were prepared by precipitation method. Thermal stability of samples was characterized by XRD, surface areas were measured by BET method and reductive property was characterized by TPR. The results show that MnO2 can be dispersed in solid solution after calcined at 1273 K, when the loading is 12%, while Fe and Cu is easy to separate from samples at this temperature. Samples doped simultaneously by Fe, Mn or Fe, Cu demonstrated high reactive property at low temperature. The starting reduction temperature are 413 and 373 K, respectively. TPR results also show a broad range of reductive temperature exists in these bi-metal doped samples.
基金Project(2009BB4228) supported by the Natural Science Foundation of Chongqing City,ChinaProject(CK2010Z09) supported by the Research Foundation of Chongqing University of Science and Technology,China
文摘In order to reduce the oxidizing and volatilizing caused by Mg element in the traditional methods for synthesizing Mg2Sil-xSnx （x=0.2, 0.4, 0.6, 0.8） solid solutions, microwave irradiation techniques were used in preparing them as thermoelectric materials. Structure and phase composition of the obtained materials were investigated by X-ray diffraction （XRD）. The electrical conductivity, Seebeck coefficient and thermal conductivity were measured as a function of temperature from 300 to 750 K. It is found that Mg2Si1-xSnx solid solutions are well formed with excessive content of 5% （molar fraction） Mg from the stoichiometric MgESil.xSnx under microwave irradiation. A maximum dimensionless figure of merit, ZT, of about 0.26 is obtained for Mg2Si1-xSnx solid solutions at about 500 K for x=0.6.
文摘The Ce_xTh_(1-x)O_2 solid solutions were prepared by citrate sol-gel method,and their structure and reduction properties were studied. XRD shows that solid solution with cubicphase formed in all the solid solutions (x = 0.2, 0.5, 0.8) Ce_xTh_(1-x)O_2. Raman spectrum showsthat Ce-Th complex oxides can promote the formation of oxygen vacancies. Two reduction peaks appearin the TPR profiles of Ce_xTh_(1-x)O_2 solid solution. The a peak is attributed to the reduction ofCe^(4+) on the surface, and the β peak is attributed to the reduction of bulk CeO_2. Theincorporation of Th atom into CeO_2 improves the reduction of CeO_2. Ce_xTh_(1-x)O_2 mixed oxidesare promising materials for oxygen vacancies produced, as well as catalysts for many reactionsinvolved oxygen, such as the catalysts for three-way reactions for reducing the releasing pollutantsor combustion of VOCs.
基金supported by the National Natural Science Foundations of China(51501095,51371094)the Natural Science Foundation of Inner Mongolia(2017MS(LH)0516)
文摘Nanosized Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions（x = 0.00-0.20） were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg2Ni and Ni powders for 20 h to get the Mg2Ni–Ni–5 mol% Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） composites.The structures and spectrum characteristics of the Ce^1-x）（Nd^0.5）Eu^0.5））xO^2-δ） solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F^2g mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu^3＋ and Nd^3＋ ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg2Ni–Ni–5 mol% Ce1-x（Nd0.5Eu0.5xO2-δ composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S20 increased from 25.0%（x = 0.00） to 42.2%（x = 0.20）.The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce1-x（Nd0.5Eu0.5）xO2-δ solid solutions.
基金This work was supported by Guangdong Natural Science Foundation of China (030514)Science and Technology Programs of Guangdong Province of China (2004B33401006)
文摘The transition metals （Cu, Co, and Fe） were applied to modify Ni/Ce0.2Zr0.1Al0.7Oδ catalyst. The effects of transition metals on the catalytic properties of Ni/Ce0.2Zr0.1Al0.7Oδ autothermal reforming of methane were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS. Tests in autothermal reforming of methane to hydrogen showed that the addition of transition metals （Cu and Co） significantly increased the activity of catalyst under the conditions of lower reaction temperature, and Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ was found to have the highest conversion of CH4 among all catalysts in the operation temperatures ranging from 923 K to 1023 K. TPR, XRD and XPS measurements indicated that the cubic phases of CexZr1-xO2 solid solution were formed in the preparation process of catalysts. Strong interaction was found to exist between NiO and CexZr1-xO2 solid solution. The addition of Cu improved the dispersion of NiO, inhibited the formation of NiAl2O4, and thus significantly promoted the activity of the catalyst Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ
基金supported by the National Natural Science Foundation of China(51962028,51501095)the Natural Science Foundation of Inner Mongolia(2017MS(LH)0516,2018MS05040,2018BS05010,2017MS(LH)0519)the Innovation Fund of Inner Mongolia University of Science and Technology(2018YQL02).
文摘Fe^3+and Zn^2+ions were doped into the lattice of CeO2 via the hydrothermal method.The micro structure and spectra features were analyzed systemically.XRD results show that the solid solubility of Fe^3+and Zn^2+ions in Ce1-x(Fe0.5Zn0.5)xO2 can be identified as x=0.16.The cell volumes are decreased by increasing the doped content.The TEM graphs prove that the grain size of the sample is about 10 nm,and the EDS result indicates that the doped contents are in accordance with that of the theory concentrations.Meanwhile,the doping also causes the increasing concentrations of the defects and oxygen vacancies which are supported by the XPS,Raman,UV and PL characterizations.The samples exhibit better catalytic activities for improving the hydrogen storage properties and the electrochemical kinetics of the ball milled Mg2Ni based composites.Further,the catalysis effects are improved by increasing the doped contents,which can be ascribed to the increasing contents of the oxygen vacancies,defects,the special electron transition states and the nature of the doped ions in CeO2-based solid solutions.
基金supported by National Natural Science Foundation of China(12175130,11875187)the Opening Project of State Key Laboratory of Key Laboratory of Transparent Opto-functional Inorganic Materials,Chinese Academy of Sciences(KLTOIM202002)。
文摘In this paper,effect of two strategies on afterglow behavior of Lu_(2)O_(3):Eu single crystal scintillato r,Pr^(3+)codoping and solid solution with Sc_(2)O_(3),were studied systematically.Two groups of Lu_(2)O_(3):5 at%Eu,x at%Pr(x=0,0.2,0.5,1,2 and 5)and(Lu1-yScy)_(2)O_(3):5 at%Eu(y=0,20 at%,50 at%and 70 at%)single crystals were grown by floating zone(FZ)method in air atmosphere.The structures of as-grown crystals were determined by X-ray diffraction(XRD).The scintillation,photoluminescence properties and carrier trap states were investigated through afterglow,X-ray excitation luminescence(XEL),transmittance,photoluminescence excitation(PLE)and photoluminescence(PL),PL decay and thermal stimulated luminescence(TSL)curves.It is found that with the increase of Pr^(3+)concentration,the afterglow level of the system decreases at the expense of scintillation luminescence efficiency.Meanwhile,although Sc_(2)O_(3):Eu presents much lower afterglow intensity than Lu_(2)O_(3):Eu,the addition of Sc_(2)O_(3)will just increase the afterglow level of the(Lu1-yScy)_(2)O_(3):5 at%Eu single crystal system.Possible mechanisms for above phenomena are discussed based on experimental results.
基金financially supported by the National Natural Science Foundation of China (51572136, 51772162, 21571112, 51802170 and 21801150)the Natural Science Foundation of Shandong Province (ZR2018BEM014, ZR2018LB008 andZR2019MB001)+2 种基金Taishan Scholar Foundation of Shandong Province (H. W., ts201712047)the Special Fund Project to Guide Development of Local Science and Technology by Central Government (H.W.)Taishan Scholar Program of Advantage and Characteristic Discipline Team of Eco Chemical Process and Technology
文摘Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneously. Nevertheless, it is still challenging to exploit low-cost and stable Zscheme photocatalysts with highly-efficient H2 evolution from solar water-splitting so far. Herein, we report a novel all-solidstate Z-scheme photocatalyst Cd1-xZnxS@WO3-x consisting of Cd1-xZnxS nanorods coated with oxygen-deficient WO3-x amorphous layers. The Cd1-xZnxS@WO3-x exhibits an outstanding H2 evolution reaction(HER) activity as compared with Pt-loaded Cd1-xZnxS and most WO3- and Cd S-based photocatalysts, due to the generation of stronger reducing electrons through the appropriate Zn-doping in Cd1-xZnxS and the enhanced charge transfer by introducing oxygen vacancies(W^5+/OVs) into the ultrathin WO3-x amorphous coatings. The optimal HER rate of Cd1-xZnxS@WO3- xis determined to be 21.68 mmol h^-1 g^-1, which is further raised up to 28.25 mmol h^-1 g^-1(about 12 times more than that of Pt/Cd1-xZnxS) when Cd1-xZnxS@WO3-x is hybridized by Co Ox and Ni Oxdual cocatalysts(Cd1-xZnxS@WO3-x/CoOx/NiOx)through in-situ photo-deposition. Moreover, the corresponding apparent quantum yield(AQY) at 420 nm is significantly increased from 34.6% for Cd1-xZnxS@WO3-x to 60.8% for Cd1-xZnxS@WO3-x/CoOx/NiOx. In addition, both Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx demonstrate good stability towards HER. The results displayed in this work will inspire the rational design and synthesis of high-performance nanostructures for photocatalytic applications.
