Water electrolysis for energy-efficient H_(2)production coupled with hydrazine oxidation reaction(HzOR)is prevailing,while the sluggish electrocatalysts are strongly hindering its scalable application.Herein,we scheme...Water electrolysis for energy-efficient H_(2)production coupled with hydrazine oxidation reaction(HzOR)is prevailing,while the sluggish electrocatalysts are strongly hindering its scalable application.Herein,we schemed a novel porous Ce-doped Ni3N nanosheet arrays grown on nickel foam(Ce-Ni3N/NF)as a remarkable bifunctional catalyst for both hydrogen evolution reaction and HzOR.Significantly,the overall hydrazine splitting system can achieve low cell voltages of 0.156 and 0.671 V at 10 and 400 mA·cm^(−2),and the system is remarkably stable to operate over 100 h continuous test at the high-current-density of 400 mA·cm^(−2).Various characterizations prove that the porous nanosheet arrays expose more active sites,and more excellent diffusion kinetics and lower charge-transfer resistance,therefore boosting catalytic performance.Furthermore,density functional theory calculation reveals that the incorporation of Ce can effectively optimize the free energy of hydrogen adsorption and promote intrinsic catalytic activity of Ni_(3)N.展开更多
Pristine LiNi_（0.5）Mn_（1.5）O_4 and cerium doped LiCe_xNi_（0.5–x）Mn_（1.5）O_4（x=0.005, 0.01, 0.02） cathode materials were synthesized by solid-state method. The effect of Ce doping content on structure and el...Pristine LiNi_（0.5）Mn_（1.5）O_4 and cerium doped LiCe_xNi_（0.5–x）Mn_（1.5）O_4（x=0.005, 0.01, 0.02） cathode materials were synthesized by solid-state method. The effect of Ce doping content on structure and electrochemical properties of LiNi_（0.5）Mn_（1.5）O_4 cathode material was systematically investigated. The samples were characterized by X-ray diffraction（XRD）, Fourier transformation infrared spectrometer（FT-IR）, scanning electron microscopy（SEM）, electrochemical impedance spectroscopy（EIS）, cyclic voltammetry（CV） and constant-current charge/discharge tests. The results showed that Ce doping did not change the cubic spinel structure with Fd3m space group, but effectively restrained the formation of Li_xNi_（1–x）O impurity phase. Appropriate Ce doping（x=0.005） could decrease the extent of confusion between lithium ions and transition metal ions, increase the lattice parameter and Ni/Mn disordering degree（Mn^（3＋） content）. The synergic effects of the above factors led to the optimal electrochemical performance of LiCe_（0.005）Ni_（0.495）Mn_（1.5）O_4 sample. The discharge capacity at 10 C rate could reach 115.4 mAh/g, 94.82% of that at 0.2C rate, and the capacity retention rate after 100 cycles at 1C rate could reach 94.51%. However, heavier Ce doping had an adverse effect on the electrochemical properties, which might be due to the lower disordering degree and existence of more CeO_2 secondary phase.展开更多
A solid state reaction method was used to synthesize barium titanate （BT） and barium cerium titanate （BCT） ceramics at sintering temperature of 1473 K for 4 h. The effect of cerium （Ce） on the structure, microst...A solid state reaction method was used to synthesize barium titanate （BT） and barium cerium titanate （BCT） ceramics at sintering temperature of 1473 K for 4 h. The effect of cerium （Ce） on the structure, microstructure and dielectric properties of BCT was investigated. The scanning electron microscopy （SEM） investigations revealed that the grain size increases with increasing Ce content. The X-ray diffraction （XI^D） patterns showed mostly the BT phase, where the lattice parameter decreased with the addition of Ce. The temperature dependence of dielectric constant showed decrease in the phase transition temperature with higher Ce content. The dielectric constant decreased slightly with increasing frequency. The direct current （dc） density-voltage characteristics of the ceramics showed ohmic behavior for both the BT and BCT. As the temperature increased, the dc resistivity of the ceramics decreased. The activation energy increased with increasing Ce content.展开更多
The acid-proof anode Ti/SnO2+Mn2O3/PbO2 doped with Ce was prepared by thermal decomposition and electrodeposition combination technology, the effect of Ce on the morphology and structure of anode was also studied in t...The acid-proof anode Ti/SnO2+Mn2O3/PbO2 doped with Ce was prepared by thermal decomposition and electrodeposition combination technology, the effect of Ce on the morphology and structure of anode was also studied in this paper. The results obtained by cyclic voltammetry (CV), electrochemical impedance spectroscopic (EIS), X-ray Diffraction (XRD) and scanning electron microscopy (SEM) indicated that PbO2 crystal grains presented honeycomb structure were formed on the electrode surface by doping with Ce. The specific surface areas and catalytic active sites of the Ce-PbO2 doped electrode were increased and the catalytic activity was evidently greater than the undoped one. However, when Ce was doped into the intermediate layer (SnO2+Mn2O3), a more cracked surface structure formed, thus leading electrode deactivation by passivation of the Ti-substrate. So the anodic stability was decreased according to the accelerated life tests.展开更多
Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and UV/Vis diffus...Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and UV/Vis diffuse reflectance spectra （DRS）. The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.展开更多
Metal-organic framework（MOF） material MIL-53（A1） with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst（Ce-Cu）/MIL-53（A1） material for C...Metal-organic framework（MOF） material MIL-53（A1） with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst（Ce-Cu）/MIL-53（A1） material for CO oxidation with high catalytic activity.The catalytic performance between the（CuCe）/MIL-53（A1） and the Cu/MIL-53（A1） catalytic material was compared to understand the catalytic behavior of the catalysts.The catalysts were characterized by thermogravimetric-differential scanning calorimetry（TGDSC）,N2 adsorption- desorption,X-ray diffraction（XRD）,and transmission electron microscopy（TEM）.The characterization results showed that MIL-53（A1） had good stability and high surface areas,the（Ce-Cu）nanoparticles on the MIL-53（A1） support was uniform.Therefore,the heterogeneous catalytic composite materials（Ce-Cu）/MIL-53（A1） catalyst exhibited much higher activity than that of the Cu/MIL- 53（A1） catalyst in CO oxidation test,with 100%conversion at 80 ℃.The results reveal that（Cu-Ce）/MIL-53（A1） is the suitable candidate for achieving low temperature and higher activity CO oxidation catalyst of MOFs.展开更多
Al2O3 powders with different morphologies,namely fibrous,sheet-like,and spherical,were prepared by the hydrothermal-thermolysis method.Subsequently,polycrystalline,transparent cerium doped lutetium aluminum garnet（Lu...Al2O3 powders with different morphologies,namely fibrous,sheet-like,and spherical,were prepared by the hydrothermal-thermolysis method.Subsequently,polycrystalline,transparent cerium doped lutetium aluminum garnet（Lu3Al5O（12）：Ce^3＋）green phosphors were synthesized by high temperature solidstate method using commercial lutetium（III）oxide,cerium（III）oxide,and as-prepared Al2O3 powders with different morphologies.The phases,morphologies,and photoluminescent properties of the prepared phosphors were investigated by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and photoluminescence spectroscopy（PL）.Moreover,the influences of the morphologies ofα-Al2O3 on the types of crystal structure,morphologies,and photoluminescent properties of LuAG：Ce^3＋green phosphors were investigated.The results indicated that the morphologies and particle sizes of theα-Al2O3 powders could be controlled by the additives and parameters.Notably,the sphericalα-Al2O3 powders with good dispersibility were found to be the excellent base materials of LuAG：Ce^3＋green phosphors for white light emitting diodes.展开更多
In this paper,factors influencing themineralization of dimethyl phthalate(DMP)during catalytic ozonation with a cerium-doped Ru/Al_(2)O_(3) catalyst were studied.The catalytic contribution was calculated through the r...In this paper,factors influencing themineralization of dimethyl phthalate(DMP)during catalytic ozonation with a cerium-doped Ru/Al_(2)O_(3) catalyst were studied.The catalytic contribution was calculated through the results of a comparison experiment.It showed that doping cerium significantly enhanced catalytic activity.The total organic carbon(TOC)removal over the doped catalyst at 100 min reached 75.1%,61.3% using Ru/Al_(2)O_(3) catalyst and only 14.0% using ozone alone.Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al_(2)O_(3) support.Results of experiments on oxidation by ozone alone,adsorption of the catalyst,Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%,which showed the obvious effect of Ru-Ce/Al_(2)O_(3) on catalytic activity.展开更多
Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-sit...Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.展开更多
锂金属由于其高理论比容量(3860 mA g^-1)而被认为是最具潜力的高能量密度锂电池用负极材料.然而,锂枝晶的不可控生长和金属锂对电解液的高反应活性严重阻碍了其实际应用.区别于以往广泛使用的电解液优化或界面修饰工艺,本文采用一种原...锂金属由于其高理论比容量(3860 mA g^-1)而被认为是最具潜力的高能量密度锂电池用负极材料.然而,锂枝晶的不可控生长和金属锂对电解液的高反应活性严重阻碍了其实际应用.区别于以往广泛使用的电解液优化或界面修饰工艺,本文采用一种原位铈掺杂的策略,从根本上改变了锂金属的电沉积行为.通过锂电极表面的原位铈掺杂促进锂在电化学过程中沿[200]方向优先沉积,显著降低金属锂的表面能.光谱、形貌和电化学测试等结果证明,原位铈掺杂大大降低了锂电极对电解液的反应活性,使得电极在沉积/脱出过程中具有无枝晶形貌.采用这种策略装配的对称电池中,锂电极具有低腐蚀电流密度,甚至在贫液条件下循环寿命也得到显著提升.采用铈掺杂锂负极的锂-钴酸锂全电池可稳定循环300周,库伦效率和循环寿命得到明显提高.本工作为金属锂负极在高能量密度电池中的实用化研究提供了一种具有启发性的策略.展开更多
基金supported by Nantong University Analysis&Testing Center。
文摘Water electrolysis for energy-efficient H_(2)production coupled with hydrazine oxidation reaction(HzOR)is prevailing,while the sluggish electrocatalysts are strongly hindering its scalable application.Herein,we schemed a novel porous Ce-doped Ni3N nanosheet arrays grown on nickel foam(Ce-Ni3N/NF)as a remarkable bifunctional catalyst for both hydrogen evolution reaction and HzOR.Significantly,the overall hydrazine splitting system can achieve low cell voltages of 0.156 and 0.671 V at 10 and 400 mA·cm^(−2),and the system is remarkably stable to operate over 100 h continuous test at the high-current-density of 400 mA·cm^(−2).Various characterizations prove that the porous nanosheet arrays expose more active sites,and more excellent diffusion kinetics and lower charge-transfer resistance,therefore boosting catalytic performance.Furthermore,density functional theory calculation reveals that the incorporation of Ce can effectively optimize the free energy of hydrogen adsorption and promote intrinsic catalytic activity of Ni_(3)N.
基金supported by the Natural Science Foundation of Hebei Province(E2015202356)Key R&D Plan Self-raised Project of Hebei Province(16214406)Technology Innovation Foundation Project for Outstanding Youth of Hebei University of Technology(2013009)
文摘Pristine LiNi_（0.5）Mn_（1.5）O_4 and cerium doped LiCe_xNi_（0.5–x）Mn_（1.5）O_4（x=0.005, 0.01, 0.02） cathode materials were synthesized by solid-state method. The effect of Ce doping content on structure and electrochemical properties of LiNi_（0.5）Mn_（1.5）O_4 cathode material was systematically investigated. The samples were characterized by X-ray diffraction（XRD）, Fourier transformation infrared spectrometer（FT-IR）, scanning electron microscopy（SEM）, electrochemical impedance spectroscopy（EIS）, cyclic voltammetry（CV） and constant-current charge/discharge tests. The results showed that Ce doping did not change the cubic spinel structure with Fd3m space group, but effectively restrained the formation of Li_xNi_（1–x）O impurity phase. Appropriate Ce doping（x=0.005） could decrease the extent of confusion between lithium ions and transition metal ions, increase the lattice parameter and Ni/Mn disordering degree（Mn^（3＋） content）. The synergic effects of the above factors led to the optimal electrochemical performance of LiCe_（0.005）Ni_（0.495）Mn_（1.5）O_4 sample. The discharge capacity at 10 C rate could reach 115.4 mAh/g, 94.82% of that at 0.2C rate, and the capacity retention rate after 100 cycles at 1C rate could reach 94.51%. However, heavier Ce doping had an adverse effect on the electrochemical properties, which might be due to the lower disordering degree and existence of more CeO_2 secondary phase.
文摘A solid state reaction method was used to synthesize barium titanate （BT） and barium cerium titanate （BCT） ceramics at sintering temperature of 1473 K for 4 h. The effect of cerium （Ce） on the structure, microstructure and dielectric properties of BCT was investigated. The scanning electron microscopy （SEM） investigations revealed that the grain size increases with increasing Ce content. The X-ray diffraction （XI^D） patterns showed mostly the BT phase, where the lattice parameter decreased with the addition of Ce. The temperature dependence of dielectric constant showed decrease in the phase transition temperature with higher Ce content. The dielectric constant decreased slightly with increasing frequency. The direct current （dc） density-voltage characteristics of the ceramics showed ohmic behavior for both the BT and BCT. As the temperature increased, the dc resistivity of the ceramics decreased. The activation energy increased with increasing Ce content.
基金the National Natural Science Foundation of China (20476070,20771080)Natural Science Foundation of Shanxi Province (20031024 ,20041020)
文摘The acid-proof anode Ti/SnO2+Mn2O3/PbO2 doped with Ce was prepared by thermal decomposition and electrodeposition combination technology, the effect of Ce on the morphology and structure of anode was also studied in this paper. The results obtained by cyclic voltammetry (CV), electrochemical impedance spectroscopic (EIS), X-ray Diffraction (XRD) and scanning electron microscopy (SEM) indicated that PbO2 crystal grains presented honeycomb structure were formed on the electrode surface by doping with Ce. The specific surface areas and catalytic active sites of the Ce-PbO2 doped electrode were increased and the catalytic activity was evidently greater than the undoped one. However, when Ce was doped into the intermediate layer (SnO2+Mn2O3), a more cracked surface structure formed, thus leading electrode deactivation by passivation of the Ti-substrate. So the anodic stability was decreased according to the accelerated life tests.
文摘Cerium-doped titanium dioxide nano-powders were prepared through the sol-gel method and the compound sampies were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and UV/Vis diffuse reflectance spectra （DRS）. The photocatalytic activity was evaluated by photocatalytic degradation of phenol in water. The results of XRD, TEM, and DRS show that pure TiO2 and Ce-doped TiO2 powder crystallines are a mixture of anatase and rutile ; the doping can retard the development of the grain size of TiO2 and decrease the diameter of TiO2 from more than 20 nm of pure TiO2 to about 10 nm; the doped TiO2 can improve the light absorption of TiO2 and suitable doping content tends to move the DRS spectrum of TiO2 towards visible light, but too much doping is not good for the light absorption ability. The results of the photocatalytic experiments show that doping with Ce content of 0.08% -0.4% can increase the photocatalytic activity of TiO2; however, doping with Ce content of 0.5% -2.5% can significantly decrease the photocatalytic activity of TiO2. The favorite doping content is 0.4% in the range of our experiments.
基金Funded by the Guiding Research Project of Hubei Province Department of Education(No.B2016098)
文摘Metal-organic framework（MOF） material MIL-53（A1） with high thermal stability was prepared by a solvothermal method,serving as a support material of cerium doped copper catalyst（Ce-Cu）/MIL-53（A1） material for CO oxidation with high catalytic activity.The catalytic performance between the（CuCe）/MIL-53（A1） and the Cu/MIL-53（A1） catalytic material was compared to understand the catalytic behavior of the catalysts.The catalysts were characterized by thermogravimetric-differential scanning calorimetry（TGDSC）,N2 adsorption- desorption,X-ray diffraction（XRD）,and transmission electron microscopy（TEM）.The characterization results showed that MIL-53（A1） had good stability and high surface areas,the（Ce-Cu）nanoparticles on the MIL-53（A1） support was uniform.Therefore,the heterogeneous catalytic composite materials（Ce-Cu）/MIL-53（A1） catalyst exhibited much higher activity than that of the Cu/MIL- 53（A1） catalyst in CO oxidation test,with 100%conversion at 80 ℃.The results reveal that（Cu-Ce）/MIL-53（A1） is the suitable candidate for achieving low temperature and higher activity CO oxidation catalyst of MOFs.
基金Funded by Shan’xi Educational Committee(No.17JK0395)
文摘Al2O3 powders with different morphologies,namely fibrous,sheet-like,and spherical,were prepared by the hydrothermal-thermolysis method.Subsequently,polycrystalline,transparent cerium doped lutetium aluminum garnet（Lu3Al5O（12）：Ce^3＋）green phosphors were synthesized by high temperature solidstate method using commercial lutetium（III）oxide,cerium（III）oxide,and as-prepared Al2O3 powders with different morphologies.The phases,morphologies,and photoluminescent properties of the prepared phosphors were investigated by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and photoluminescence spectroscopy（PL）.Moreover,the influences of the morphologies ofα-Al2O3 on the types of crystal structure,morphologies,and photoluminescent properties of LuAG：Ce^3＋green phosphors were investigated.The results indicated that the morphologies and particle sizes of theα-Al2O3 powders could be controlled by the additives and parameters.Notably,the sphericalα-Al2O3 powders with good dispersibility were found to be the excellent base materials of LuAG：Ce^3＋green phosphors for white light emitting diodes.
基金This work was supported by the National Natural Science Foundation of China(Grant No.50238020).
文摘In this paper,factors influencing themineralization of dimethyl phthalate(DMP)during catalytic ozonation with a cerium-doped Ru/Al_(2)O_(3) catalyst were studied.The catalytic contribution was calculated through the results of a comparison experiment.It showed that doping cerium significantly enhanced catalytic activity.The total organic carbon(TOC)removal over the doped catalyst at 100 min reached 75.1%,61.3% using Ru/Al_(2)O_(3) catalyst and only 14.0% using ozone alone.Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al_(2)O_(3) support.Results of experiments on oxidation by ozone alone,adsorption of the catalyst,Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%,which showed the obvious effect of Ru-Ce/Al_(2)O_(3) on catalytic activity.
基金The APXPS experiments were performed at BL02B01 of SSRF with the approval of the Proposal Assessing Committee of SiP.ME2 platform project(Proposal No.2019-SSRF-PT-011613)the Natural Science Foundation of China(No.11227902)the Shanghai Key Research Program(No.20ZR1436700).
文摘Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.
基金This work was supported by the National Natural Science Foundation of China(51602250,51802256 and 21875181)the Innovation Capability Support Program of Shaanxi(2018PT-28 and 2019PT-05).
文摘锂金属由于其高理论比容量(3860 mA g^-1)而被认为是最具潜力的高能量密度锂电池用负极材料.然而,锂枝晶的不可控生长和金属锂对电解液的高反应活性严重阻碍了其实际应用.区别于以往广泛使用的电解液优化或界面修饰工艺,本文采用一种原位铈掺杂的策略,从根本上改变了锂金属的电沉积行为.通过锂电极表面的原位铈掺杂促进锂在电化学过程中沿[200]方向优先沉积,显著降低金属锂的表面能.光谱、形貌和电化学测试等结果证明,原位铈掺杂大大降低了锂电极对电解液的反应活性,使得电极在沉积/脱出过程中具有无枝晶形貌.采用这种策略装配的对称电池中,锂电极具有低腐蚀电流密度,甚至在贫液条件下循环寿命也得到显著提升.采用铈掺杂锂负极的锂-钴酸锂全电池可稳定循环300周,库伦效率和循环寿命得到明显提高.本工作为金属锂负极在高能量密度电池中的实用化研究提供了一种具有启发性的策略.
