Ce0.8Sm0.2O2–δ―Sm0.1Sr0.9Cu0.2Fe0.8O3–δ dual-phase membranes were prepared with one-pot method and citric acid sol-gel process. After calcination of the powder at 850 ℃, the dual-phase membranes were prepared by uniaxially pressing the powder. The dual-phase membranes were sintered at 1150 ℃ for 5h with heating/cooling rates of 2 ℃/min. The phase structure and microstructure of the sintered membrane were studied by XRD and SEM. Elemental analysis of the membrane surface and cross section was performed. The oxygen permeation fluxes of Cu-containing dual-phase membranes were evaluated in the temperature range of 800―950 ℃ with He and CO2 as the sweep gas.
Novel N2O2 tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the para position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, 1H NMR, 13C NMR, UV-visible, and mass spectra. The proton dissociation constants (logKn H) of the phenol hydroxyl group and secondary amine of the synthesized N2O2 ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants (logβp) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of para Hammett substituent constants(δp). The stability constants(logKML) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of logβp of the ligands. The order of the logKML value of the each transition metal (II) ion was Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ), which agreed well with that of Iriving-Williams series.
new N3-O2 pentadentate ligand, H-BHPT, was synthesized. Hydrochloric acid salts of Br-BHPT, Cl-BHPT, CH3O-BHPT and CH3-BHPT, having Br-, Cl-, CH3- and CH3O- substituents at the para position of the phenol hydroxyl group of H-BHPT were synthesized. Hydrochloric acid salts of 3OH-BHPT and 4OH-BHPT, having different position of the phenol hydroxyl group of H-BHPT were also synthesized. The synthesis of each ligand was confirmed by C. H. N. atomic analysis and 1H NMR, 13C NMR, UV-visible, and mass spectra. The calculated proton dissociation constants (logKn H) of the phenol hydroxyl group and secondary amine group of the synthesized N3-O2 ligands showed five steps of the proton dissociations. The order of the overall proton dissociation constants (logβp) of the ligands was Br-BHPT < Cl-BHPT < H-BHPT < CH3O-BHPT < CH3-BHPT. The order agreed with that of Hammett substituent constants (δp). However, dissociation steps of 3OH-BHPT were four and that of 4OH-BHPT was three. The calculated stability constants (logKML) between the ligands and transition metal ions agreed with the order of logβp values of the ligands. The order of the stability constants between the transition metal ions with the synthesized ligands was Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ). The order agreed well with that of the Iriving-Williams.
A new N3O2 pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET․3HCl) was synthesized. The hydrochloric acid salts of Br-BHET․3HCl, Cl-BHET․3HCl, CH3O-BHET․3HCl and CH3-BHET․3HCl containing Br-, Cl-, H-, CH3O- and CH3- groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and 1H NMR, 13C NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(logKnH) of the synthesized N3O2 ligands showed six steps of the proton dissociation. The orders of the overall protonation constants(logβp) of the ligands were Br-BHET < Cl-BHET < H-BHET < CH3O-BHET < CH3-BHET. The orders agreed well with that of para Hammett substituent constants(δp). The calculated stability constants(logKML) between the ligands and heavy metal ions (Co(Ⅱ) , Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(δp). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) > Zn(Ⅱ) > Cd(Ⅱ) > Pb(Ⅱ).