Several crosslinked proton exchange membranes with high proton conductivities and low methanol permeability coefficients were prepared, based on the sulfonated poly[(4-fluorophenoxy)(phenoxy)] phosphazene(SPFPP) and n...Several crosslinked proton exchange membranes with high proton conductivities and low methanol permeability coefficients were prepared, based on the sulfonated poly[(4-fluorophenoxy)(phenoxy)] phosphazene(SPFPP) and newly synthesized water soluble sulfonated poly(cyclophosphazene)(SPCP) containing clustered flexible pendant sulfonic acids. The structure of SPCP was characterized by fourier transform infrared spectroscopy(FTIR) and ~1H NMR spectra. The membranes showed moderate proton conductivities and much lower methanol permeability coefficients when compared to Nafion 117. Transmission electron microscopy(TEM) results indicated the well-defined phase separation between the locally and densely sulfonated units and hydrophobic units, which induced efficient proton conduction. In comparison with SPFPP membrane, the proton conductivities, oxidative stabilities and mechanical properties of crosslinked membranes remarkably were improved. The selectivity values of all the crosslinked membranes were also much higher than that of Nafion 117(0.74×10~5S· s/cm~3). These results suggested that the c SPFPP/SPCP membranes were promising candidate materials for proton exchange membrane in direct methanol fuel cells.展开更多
Here,we report a series of Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)(0≤x≤1.0 mol)phosphors by using the traditional high temperature solid-state reaction.To achieve the structural and photoluminescent(PL)information,...Here,we report a series of Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)(0≤x≤1.0 mol)phosphors by using the traditional high temperature solid-state reaction.To achieve the structural and photoluminescent(PL)information,several experimental characterizations and theoretical calculations were carried out,including X-ray diffraction(XRD),Rietveld refinement,UV-visible diffuse reflectance and PL spectra,temperature dependent PL spectra,and density functional theo retical(DFT)calculations.The XRD results show that the Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)samples belong to the double-perovskite phase with a cubic space group of Fm3 m,and the diffraction positions shift toward high diffraction angle when the larger Y^(3+)ions are gradually replaced by the smaller Sc^(3+)ions.In addition,the refined XRD findings show that the Bi^(3+)ions tend to substitute the Y^(3+)and Sc^(3+)sites in the Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)0<x<1.0 mol)solid solutions.The PL spectra show that the emission positions of the solid solution samples tune from446 to 497 nm with the increase of Sc^(3+) content,which can be attributed to the modification of crystal field strength around Bi^(3+)ions.Moreover,there is energy transfer from the Ba_(2)YNbO_(6)host to Bi^(3+)ions,which is dominated by a resonant type via a dipole-quadrupole(d-q)interaction.The Ba_(2)Y_(0.6)Sc_(0.4)NbO_(6):0.02 molBi^(3+)shows the strongest PL intensity under 365 nm excitation,with the best quantum efficiency(QE)of 68%,and it keeps 60%of the room temperature emission intensity when the temperature increases to 150℃,meaning that the Ba_(2)Y_(0.6)Sc_(0.4)NbO_(6):Bi^(3+)features excellent thermal quenching of luminescence.By combining this optimal sample with a commercial red-emitting Sr_(2)Si_(5)N_(8):Eu^(2+)phosphor,and a commercial 365 nm UV LED chip,a white LED device,with the color temperature(CT)of 3678 K,color rendering index(CRI)of 67.9,and CIE coordinates at(0.371,0.376),is achieved.展开更多
文摘Several crosslinked proton exchange membranes with high proton conductivities and low methanol permeability coefficients were prepared, based on the sulfonated poly[(4-fluorophenoxy)(phenoxy)] phosphazene(SPFPP) and newly synthesized water soluble sulfonated poly(cyclophosphazene)(SPCP) containing clustered flexible pendant sulfonic acids. The structure of SPCP was characterized by fourier transform infrared spectroscopy(FTIR) and ~1H NMR spectra. The membranes showed moderate proton conductivities and much lower methanol permeability coefficients when compared to Nafion 117. Transmission electron microscopy(TEM) results indicated the well-defined phase separation between the locally and densely sulfonated units and hydrophobic units, which induced efficient proton conduction. In comparison with SPFPP membrane, the proton conductivities, oxidative stabilities and mechanical properties of crosslinked membranes remarkably were improved. The selectivity values of all the crosslinked membranes were also much higher than that of Nafion 117(0.74×10~5S· s/cm~3). These results suggested that the c SPFPP/SPCP membranes were promising candidate materials for proton exchange membrane in direct methanol fuel cells.
基金Project supported by the Key R&D Project of Hebei Province(18214321)the Research Foundation of Hengshui University for High-level Talents(2019GC10)+1 种基金National Innovation and Entrepreneurship Training Program for College Students(202010101001)the Science Technology Program of Hengshui city(2018011002Z)。
文摘Here,we report a series of Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)(0≤x≤1.0 mol)phosphors by using the traditional high temperature solid-state reaction.To achieve the structural and photoluminescent(PL)information,several experimental characterizations and theoretical calculations were carried out,including X-ray diffraction(XRD),Rietveld refinement,UV-visible diffuse reflectance and PL spectra,temperature dependent PL spectra,and density functional theo retical(DFT)calculations.The XRD results show that the Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)samples belong to the double-perovskite phase with a cubic space group of Fm3 m,and the diffraction positions shift toward high diffraction angle when the larger Y^(3+)ions are gradually replaced by the smaller Sc^(3+)ions.In addition,the refined XRD findings show that the Bi^(3+)ions tend to substitute the Y^(3+)and Sc^(3+)sites in the Bi^(3+)-doped Ba_(2)Y_(1-x)Sc_(x)NbO_(6)0<x<1.0 mol)solid solutions.The PL spectra show that the emission positions of the solid solution samples tune from446 to 497 nm with the increase of Sc^(3+) content,which can be attributed to the modification of crystal field strength around Bi^(3+)ions.Moreover,there is energy transfer from the Ba_(2)YNbO_(6)host to Bi^(3+)ions,which is dominated by a resonant type via a dipole-quadrupole(d-q)interaction.The Ba_(2)Y_(0.6)Sc_(0.4)NbO_(6):0.02 molBi^(3+)shows the strongest PL intensity under 365 nm excitation,with the best quantum efficiency(QE)of 68%,and it keeps 60%of the room temperature emission intensity when the temperature increases to 150℃,meaning that the Ba_(2)Y_(0.6)Sc_(0.4)NbO_(6):Bi^(3+)features excellent thermal quenching of luminescence.By combining this optimal sample with a commercial red-emitting Sr_(2)Si_(5)N_(8):Eu^(2+)phosphor,and a commercial 365 nm UV LED chip,a white LED device,with the color temperature(CT)of 3678 K,color rendering index(CRI)of 67.9,and CIE coordinates at(0.371,0.376),is achieved.
