A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(w...A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142~150 S·cm 2·mol -1 , indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75~120 ℃ and 120~210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.展开更多
Eight new complexes with the general formula of RE(Gly)(NO_3)_3(phen)_2·3H_2O (RE=La, Ce, Pr, Nd, Gd, Sm, Er, Y) were synthesized and characterized by elemental analysis, molar conductivity, IR spectra, UV spectr...Eight new complexes with the general formula of RE(Gly)(NO_3)_3(phen)_2·3H_2O (RE=La, Ce, Pr, Nd, Gd, Sm, Er, Y) were synthesized and characterized by elemental analysis, molar conductivity, IR spectra, UV spectra and thermal analysis. All the complexes are stable in air and their conductance values in acetonitrile lie in the range of 204.1~239.4 S·cm2·mol -1, indicating 1∶2 type electrolytes. The IR shows that all the COO of glycine and oxygen atom of NO_3- take part in the coordination to the RE ions. The thermal behavior of La complex shows that the weight losses at 75~120 ℃ and 145~170 ℃ correspond to the loss of two lattice water molecules and one coordinated water molecules, respectively.展开更多
Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6...Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.展开更多
Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,B...Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.展开更多
In this paper,complexes of rare earth nitrate with Schiff base derived from vanillin(3-methoxy-4-hydroxy-benzaldehyde)and p-toluidine[LnL_2(NO_3)_2]NO_3(Ln=La-Eu except Pm,L=Schiff base ligand) have been prepared and ...In this paper,complexes of rare earth nitrate with Schiff base derived from vanillin(3-methoxy-4-hydroxy-benzaldehyde)and p-toluidine[LnL_2(NO_3)_2]NO_3(Ln=La-Eu except Pm,L=Schiff base ligand) have been prepared and characterized.展开更多
Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental ana...Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.展开更多
Mixed rare earth nitrates (REi(NO3)3) in the aqueous solution was mixed with tri-n-butyl phosphate (TBP, (n-C4H9O)3PO) dissolved in kerosene for the formation of their corresponding complexes (REi(NO3)3...Mixed rare earth nitrates (REi(NO3)3) in the aqueous solution was mixed with tri-n-butyl phosphate (TBP, (n-C4H9O)3PO) dissolved in kerosene for the formation of their corresponding complexes (REi(NO3)3·ni(n-C4H9O)3PO) at 303 K. The effects of initial concentrations of both TBP and mixed rare earth nitrates on the equilibrium constants of their complex formations were investigated. The complexes were formed almost immediately after mixing. The simultaneous formations reached their chemical equilibria within a few minutes by shaking the mixture at 200 r/min. The chemical equilibrium constants of the complex formations were independent of the initial TBP concentrations. However, they were decreased by reducing the concentration of REi(NO3)3. All equilibrium constants of the simultaneous complex formations were less than 0.7, while the average molar ratio of TBP to REi(NO3)3 of the complexes varied between 1.0 and 1.6. The chemical equilibrium constant for the formation of La(NO3)3·(n-C4H9O)3PO was 0.09, while that of Dy(NO3)3·(n-C4H9O)3PO was 0.68. The ascending sequence of chemical equilibrium constants for the simultaneous formations was La, Ce, Pr, Nd, Eu, Y, Sm, Gd, and Dy.展开更多
A one-dimensional (1D) supramolecular rare earth complex [Nd(NO3)2L2-(C3H6O)][NdL(NO3)4]} (L=N-(6-(4-methylpyridinyl))ketoacetamide) has been prepared and characterized by elemental analysis, IR and elec...A one-dimensional (1D) supramolecular rare earth complex [Nd(NO3)2L2-(C3H6O)][NdL(NO3)4]} (L=N-(6-(4-methylpyridinyl))ketoacetamide) has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146(6), b=1.2581(8), c=2.2316(14) nm, α=99.352(10),β=97.209(9), γ=103.935(9)°, V=2.422(3) nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F(000)=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections (I 〉 2σ(I)). In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.展开更多
Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared (FTIR), and Scanning Electron Microscopy (SEM), after dipping it in phosphating ...Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared (FTIR), and Scanning Electron Microscopy (SEM), after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate (REN). REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO4^3- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.展开更多
A mild,efficient and eco-friendly process for the electrophilic nitration is described using N_2O_5 as a green nitrating agent in the presence of rare earth metal triflates[RE(OTf)_3]under mild conditions.
In order to intensify the leaching process of rare earth(RE) and reduce the impurities in the leachate, ammonium chloride(NH4Cl) and ammonium nitrate(NH4NO3) were mixed as a compound leaching agent to treat the ...In order to intensify the leaching process of rare earth(RE) and reduce the impurities in the leachate, ammonium chloride(NH4Cl) and ammonium nitrate(NH4NO3) were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~+_4Cl and NH_4NO_3, ammonium(NH_4) concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium(Al) was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate(HETP) could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1:1(molar ratio) of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value(around 20 mL) of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent(NH_4Cl/NH_4NO_3). It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.展开更多
Viscosities were measured for the ternary systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, and La(NO3)3+Nd(NO3)3+ H2O and their binary subsystems Y(NO3)3+H2O, La(NO3)3+H2O, Ce(NO3)3+H2O,...Viscosities were measured for the ternary systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, and La(NO3)3+Nd(NO3)3+ H2O and their binary subsystems Y(NO3)3+H2O, La(NO3)3+H2O, Ce(NO3)3+H2O, and Nd(NO3)3+H2O at 293.15, 298.15 and 308.15 K. The results were used to test the applicability of simple equations for the viscosity of the mixed solutions. The predictions agreed well with measured values, implying that the viscosities of the examined electrolyte solutions could be related to those of their constituent binary solutions using these simple equations.展开更多
文摘A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142~150 S·cm 2·mol -1 , indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75~120 ℃ and 120~210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.
文摘Eight new complexes with the general formula of RE(Gly)(NO_3)_3(phen)_2·3H_2O (RE=La, Ce, Pr, Nd, Gd, Sm, Er, Y) were synthesized and characterized by elemental analysis, molar conductivity, IR spectra, UV spectra and thermal analysis. All the complexes are stable in air and their conductance values in acetonitrile lie in the range of 204.1~239.4 S·cm2·mol -1, indicating 1∶2 type electrolytes. The IR shows that all the COO of glycine and oxygen atom of NO_3- take part in the coordination to the RE ions. The thermal behavior of La complex shows that the weight losses at 75~120 ℃ and 145~170 ℃ correspond to the loss of two lattice water molecules and one coordinated water molecules, respectively.
文摘Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.
文摘Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.
基金National Natural Science Foundation of China for financial support of this work
文摘In this paper,complexes of rare earth nitrate with Schiff base derived from vanillin(3-methoxy-4-hydroxy-benzaldehyde)and p-toluidine[LnL_2(NO_3)_2]NO_3(Ln=La-Eu except Pm,L=Schiff base ligand) have been prepared and characterized.
文摘Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.
文摘Mixed rare earth nitrates (REi(NO3)3) in the aqueous solution was mixed with tri-n-butyl phosphate (TBP, (n-C4H9O)3PO) dissolved in kerosene for the formation of their corresponding complexes (REi(NO3)3·ni(n-C4H9O)3PO) at 303 K. The effects of initial concentrations of both TBP and mixed rare earth nitrates on the equilibrium constants of their complex formations were investigated. The complexes were formed almost immediately after mixing. The simultaneous formations reached their chemical equilibria within a few minutes by shaking the mixture at 200 r/min. The chemical equilibrium constants of the complex formations were independent of the initial TBP concentrations. However, they were decreased by reducing the concentration of REi(NO3)3. All equilibrium constants of the simultaneous complex formations were less than 0.7, while the average molar ratio of TBP to REi(NO3)3 of the complexes varied between 1.0 and 1.6. The chemical equilibrium constant for the formation of La(NO3)3·(n-C4H9O)3PO was 0.09, while that of Dy(NO3)3·(n-C4H9O)3PO was 0.68. The ascending sequence of chemical equilibrium constants for the simultaneous formations was La, Ce, Pr, Nd, Eu, Y, Sm, Gd, and Dy.
基金This work was supported by the National Natural Science Foundation of China (No. 20401008)
文摘A one-dimensional (1D) supramolecular rare earth complex [Nd(NO3)2L2-(C3H6O)][NdL(NO3)4]} (L=N-(6-(4-methylpyridinyl))ketoacetamide) has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146(6), b=1.2581(8), c=2.2316(14) nm, α=99.352(10),β=97.209(9), γ=103.935(9)°, V=2.422(3) nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F(000)=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections (I 〉 2σ(I)). In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.
基金Project supported by the Henan Natural Science Foundation Program (200460178)
文摘Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared (FTIR), and Scanning Electron Microscopy (SEM), after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate (REN). REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO4^3- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.
基金the financial support from the National Nature Science Foundation of China Academy of Engineering Physics(No.10976014)Nature Science Foundation of Jiangsu Province(No.BK2011697)
文摘A mild,efficient and eco-friendly process for the electrophilic nitration is described using N_2O_5 as a green nitrating agent in the presence of rare earth metal triflates[RE(OTf)_3]under mild conditions.
基金Project supported by the National Natural Science Foundation of China(51274152 and 41472071)the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China(T201506)
文摘In order to intensify the leaching process of rare earth(RE) and reduce the impurities in the leachate, ammonium chloride(NH4Cl) and ammonium nitrate(NH4NO3) were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~+_4Cl and NH_4NO_3, ammonium(NH_4) concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium(Al) was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate(HETP) could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1:1(molar ratio) of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value(around 20 mL) of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent(NH_4Cl/NH_4NO_3). It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.
基金Project supported by the National Natural Science Foundation of China (20976189, 21076224 and 21036008)the Science Foundation of China University of Petroleum (qzdx-2011-01) for financial sup-port
文摘Viscosities were measured for the ternary systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, and La(NO3)3+Nd(NO3)3+ H2O and their binary subsystems Y(NO3)3+H2O, La(NO3)3+H2O, Ce(NO3)3+H2O, and Nd(NO3)3+H2O at 293.15, 298.15 and 308.15 K. The results were used to test the applicability of simple equations for the viscosity of the mixed solutions. The predictions agreed well with measured values, implying that the viscosities of the examined electrolyte solutions could be related to those of their constituent binary solutions using these simple equations.