Ceria-zirconia mixed oxides(CZMO)are widely used in many important catalysis fields.However,pure CZMO is known to have poor thermal stability.In this paper,a strategy was proposed to design Ce_(0.475)Zr_(0.475)M_(0.05...Ceria-zirconia mixed oxides(CZMO)are widely used in many important catalysis fields.However,pure CZMO is known to have poor thermal stability.In this paper,a strategy was proposed to design Ce_(0.475)Zr_(0.475)M_(0.05)O_(2)(M=La,Y,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Er,Lu,and,Yb)oxide surface with high thermal stability by using first-principles molecular dynamics(FPMD)simulation and experiment method.Through the structure stability analysis at different temperatures,the surface energyγas a function of R_(ion)/D_(ave)is identified as a quantitative structure descriptor for analyzing the doping effect of rare earth(RE)elements on the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).By doping the suitable RE,γcan be adjusted to the optimal range to enhance the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).With this strategy,it can be predicted that the sequence of thermal stability improvement is Y>La>Gd>Nd>Pr>Pm>Sm>Eu>Tb>Er>Yb>Lu,which was further verified by our experiment results.After thermal treatment at 1100℃for 10 h,the specific surface area(SSA)of aged Y-CZ and La-CZ samples can reach 21.34 and 19.51 m~2/g,which is 63.02%and 49.04%higher than the CZMO sample without doping because the surface doping of Y and La is in favor of inhibiting the surface atoms thermal displacement.In a word,the strategy proposed in this work can be expected to provide a viable way for designing the highly efficient CZMO materials in extensive applications and promoting the usages of the high-abundance rare-earth elements Y and La.展开更多
As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a ...As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.展开更多
In order to clarify the solvent extraction and separation behaviors of rare earths and impurity of Al during the extraction and enrichment of low-concentration leach solution of ion-adsorption rare earth ore,the extra...In order to clarify the solvent extraction and separation behaviors of rare earths and impurity of Al during the extraction and enrichment of low-concentration leach solution of ion-adsorption rare earth ore,the extraction mechanism and separation behaviors of Nd^(3+)and Al^(3+)in the Nd_(2)(SO_(4))_(3)-AI_(2)(SO_(4))_(3) mixed solution using P507 were studied in this work.The extraction of Nd^(3+)and Al^(3+)follows the cation exchange mechanism.With the increase of the equilibrium pH,β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution using P507 is always higher than that in the extraction of single Nd_(2)(SO_(4))_(3) and Al_(2)(SO_(4))_(3) solutions.It can be attributed to the fact that the extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),and Al^(3+)is more prone to be hydrolyzed at lower pH.β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution decreases gradually with the increase of mixing time within the equilibrium pH range of 1.5-1.9.The extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),but the stability of Al^(3+)-Ioaded organic phase is better than that of Nd^(3+)-loaded organic phase,thus Nd^(3+)in the Nd^(3+)-loaded organic phase is gradually replaced by Al^(3+)in the aqueous phase with the increase of mixing time.展开更多
基金Project supported by China Postdoctoral Science Foundation(2020M680616)Major State Research Development Program of Hebei province(20374202D)。
文摘Ceria-zirconia mixed oxides(CZMO)are widely used in many important catalysis fields.However,pure CZMO is known to have poor thermal stability.In this paper,a strategy was proposed to design Ce_(0.475)Zr_(0.475)M_(0.05)O_(2)(M=La,Y,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Er,Lu,and,Yb)oxide surface with high thermal stability by using first-principles molecular dynamics(FPMD)simulation and experiment method.Through the structure stability analysis at different temperatures,the surface energyγas a function of R_(ion)/D_(ave)is identified as a quantitative structure descriptor for analyzing the doping effect of rare earth(RE)elements on the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).By doping the suitable RE,γcan be adjusted to the optimal range to enhance the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).With this strategy,it can be predicted that the sequence of thermal stability improvement is Y>La>Gd>Nd>Pr>Pm>Sm>Eu>Tb>Er>Yb>Lu,which was further verified by our experiment results.After thermal treatment at 1100℃for 10 h,the specific surface area(SSA)of aged Y-CZ and La-CZ samples can reach 21.34 and 19.51 m~2/g,which is 63.02%and 49.04%higher than the CZMO sample without doping because the surface doping of Y and La is in favor of inhibiting the surface atoms thermal displacement.In a word,the strategy proposed in this work can be expected to provide a viable way for designing the highly efficient CZMO materials in extensive applications and promoting the usages of the high-abundance rare-earth elements Y and La.
基金Project supported by the Beijing Nova Program(Z181100006218030)Major State Research Development Program of Hebei province(20374202D)。
文摘As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.
基金Project supported by the Major Research Plan of the National Natural Science Foundation of China(91962211)National Key Research and Development Program of China(2018YFC1801803)+1 种基金National Natural Science Foundation of China(51804273)Major Project of Guangxi Science and Technology(Guike-AA18242022)。
文摘In order to clarify the solvent extraction and separation behaviors of rare earths and impurity of Al during the extraction and enrichment of low-concentration leach solution of ion-adsorption rare earth ore,the extraction mechanism and separation behaviors of Nd^(3+)and Al^(3+)in the Nd_(2)(SO_(4))_(3)-AI_(2)(SO_(4))_(3) mixed solution using P507 were studied in this work.The extraction of Nd^(3+)and Al^(3+)follows the cation exchange mechanism.With the increase of the equilibrium pH,β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution using P507 is always higher than that in the extraction of single Nd_(2)(SO_(4))_(3) and Al_(2)(SO_(4))_(3) solutions.It can be attributed to the fact that the extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),and Al^(3+)is more prone to be hydrolyzed at lower pH.β_(Nd/Al) in the extraction of the Nd_(2)(SO_(4))_(3)-Al_(2)(SO_(4))_(3) mixed solution decreases gradually with the increase of mixing time within the equilibrium pH range of 1.5-1.9.The extraction of Nd^(3+)using P507 is much faster than that of Al^(3+),but the stability of Al^(3+)-Ioaded organic phase is better than that of Nd^(3+)-loaded organic phase,thus Nd^(3+)in the Nd^(3+)-loaded organic phase is gradually replaced by Al^(3+)in the aqueous phase with the increase of mixing time.
