A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5+δ (CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y) were synthesized through a sol-gel route and effects of the Ln3+ catio...A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5+δ (CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y) were synthesized through a sol-gel route and effects of the Ln3+ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3+ cations (La3+, Pr3+ and Nd3+) successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones (Sm3+, Gd3+, and Y3+) resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.展开更多
Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ (BRCFT, R = Ca, La or Sr) membranes were synthesized by a solid-state reaction. Metal cation Ca2+, La3+ or Sr2+ doping on A-site partially substituted Ba2+ in BaCoo.TFe0.225Ta0....Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ (BRCFT, R = Ca, La or Sr) membranes were synthesized by a solid-state reaction. Metal cation Ca2+, La3+ or Sr2+ doping on A-site partially substituted Ba2+ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2+, La3+ or Sr2+, whose ionic radii are smaller than that of Ba2+, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2+ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation (Ba2+〉La3+〉SrZ+〉Ca2+).展开更多
Mechanosensory elastomers attract intense interests in the academic and industrial fields.However,molecular insight of macroscopic properties remains a significant challenge.Herein,we build up a correlation between th...Mechanosensory elastomers attract intense interests in the academic and industrial fields.However,molecular insight of macroscopic properties remains a significant challenge.Herein,we build up a correlation between the microscopic and macroscopic level by designing a mechanosensory elastomer with aggregation-induced emission luminogens(AIEgens)that monitors chain deformation in situ.The key constituents are the mechanosensory units,which are dynamic dimers bonded by ureidopyrimidinone(UPy)groups and tetraphenylethylene(TPE)for the fluorescence signal output.The photoluminescence(PL)technique successfully monitors elastomer chain deformation under external forces.The PL intensity increases linearly at low elongation,in excellent agreement with Hooke’s law for ideal chains.Strong deviation from linear PL intensity is measured at high elongation,which can be theoretically described by the Langevin function.A correlation between the microscopic and the macroscopic level is then built.展开更多
Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d(0 x 2) were prepared by a combined citrate and ethylene diamine tetraacetic acid(EDTA) complexing method. X-ray diffraction(XRD)results re...Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d(0 x 2) were prepared by a combined citrate and ethylene diamine tetraacetic acid(EDTA) complexing method. X-ray diffraction(XRD)results revealed the good chemical compatibility between ion-conducting phase CGO and electron-conducting phases PBC2 xFxO after sintering in air. The Fe ionic dopant had a significant effect on the phase structure stability and oxygen permeability under CO2 atmosphere, which was confirmed by XRD, thermogravimetrye differential scanning calorimetry(TGeD SC), scanning electron microscopy(SEM) and oxygen permeation experiments. CGOeP BC0.5F1.5O dual-phase membrane demonstrated a stable oxygen permeation flux of2.71x10-7mol cm 2s 1with 50 mol% He/CO2 as the sweep gas at 925 C, and this value was much higher than that of perovskite-type membranes. The rate-limiting step in the oxygen permeation process changed from the bulk diffusion to the surface oxygen exchange when the CGOeP BC0.5F1.5O membrane thickness decreased to 0.8 mm or less. Due to the high oxygen permeation fluxes and the excellent structural stability under CO2 atmosphere, the CGOeP BC0.5F1.5O membrane is a great potential candidate material for separating oxygen from air in the oxy-fuel combustion techniques.展开更多
基金supported by the National Natural Science Foundation of China(51004069 and 51474145)the National Science Fund for Distinguished Young Scholars(51225401)
文摘A series of oxygen permeable dual-phase composite oxides 60 wt% Ce0.8Gd0.2O2-δ-40 wt% LnBaCo2O5+δ (CGO-LBCO, Ln = La, Pr, Nd, Sin, Gd and Y) were synthesized through a sol-gel route and effects of the Ln3+ cations on their phase structure, oxygen permeability and chemical stability against CO2 were investigated systemically by XRD, SEM, TG-DSC and oxygen permeation experiments. XRD patterns reveal that the larger Ln3+ cations (La3+, Pr3+ and Nd3+) successfully stabilized the double-layered perovskite structure of sintered LBCO, while the smaller ones (Sm3+, Gd3+, and Y3+) resulted in the partial decomposition of LBCO with some impurities formed. CGO-PBCO yields the highest oxygen permeation flux, reaching 2.8× 10^-7 mol.s-1.cm-2 at 925 ℃ with 1 mm thickness under air/He gradient. The TG-DSC profiles in 20 mol% CO2/N2 and oxygen permeability experiments with CO2 as sweep gas show that CGO-YBCO demonstrates the best chemical stability against CO2, possibly due to its minimum basicity. The stable oxygen permeation flux of CGO-YBCO under CO2 atmosphere reveals its potential application in the oxy-fuel combustion route for CO2 capture.
基金supported by the National Natural Science Foundation of China(51004069)the National Science Fund for Distinguished Young Scholars(51225401)+1 种基金China Postdoctoral Science Foundation(201104254)the Innovation Program of Shanghai Municipal Education Commission and Shanghai University(14YZ013 and SDCX2012002)
文摘Ba0.9R0.1Co0.TFe0.225Ta0.07503-δ (BRCFT, R = Ca, La or Sr) membranes were synthesized by a solid-state reaction. Metal cation Ca2+, La3+ or Sr2+ doping on A-site partially substituted Ba2+ in BaCoo.TFe0.225Ta0.07503-δ oxides, and its subsequent effects on phase structure stability, oxygen permeability and oxygen desorption were systematically investigated by XRD, TG-DSC, Hz-TPR, O2-TPD techniques and oxygen permeation experiments. The partial substitution with Ca2+, La3+ or Sr2+, whose ionic radii are smaller than that of Ba2+, succeeded in stabilizing the cubic perovskite structure without formation of impurity phases, as revealed by XRD analysis. Oxygen-involving experi- ments showed that BRCFT with A-site fully occupied by Ba2+ exhibited good oxygen permeation flux under He flow, reaching about 2.3 mL.min-l .cm-2 at 900 with I mm thickness. Of all the membranes, BLCFT membrane showed better chemical stability in CO2, owing to the reduction in alkalinity of the mixed conductor oxide by La doping. In addition, we also found the stability of the perovskite structure under reducing atmospheres was strengthened by increasing the size of A-site cation (Ba2+〉La3+〉SrZ+〉Ca2+).
基金supported by the National Natural Science Foundation of China(nos.21875009 and 51973227)the National Key Research and Development Program of China(nos.2017YFA0206904 and 2017YFA0206900)+1 种基金the Youth Innovation Promotion Association CAS(no.2020028)the Fundamental Research Funds for the Central Universities。
文摘Mechanosensory elastomers attract intense interests in the academic and industrial fields.However,molecular insight of macroscopic properties remains a significant challenge.Herein,we build up a correlation between the microscopic and macroscopic level by designing a mechanosensory elastomer with aggregation-induced emission luminogens(AIEgens)that monitors chain deformation in situ.The key constituents are the mechanosensory units,which are dynamic dimers bonded by ureidopyrimidinone(UPy)groups and tetraphenylethylene(TPE)for the fluorescence signal output.The photoluminescence(PL)technique successfully monitors elastomer chain deformation under external forces.The PL intensity increases linearly at low elongation,in excellent agreement with Hooke’s law for ideal chains.Strong deviation from linear PL intensity is measured at high elongation,which can be theoretically described by the Langevin function.A correlation between the microscopic and the macroscopic level is then built.
基金supported by the National Natural Science Foundation of China (Nos. 51004069 and 51474145)the National Science Fund for Distinguished Young Scholars (No. 51225401)the Innovation Program of Shanghai Municipal Education Commission and Shanghai University (Nos. 14YZ013 and SDCX2012002)
文摘Dual-phase membranes of 60 wt% Ce0.8Gd0.2O2-δ-40 wt% Pr Ba Co2exFexO3 d(0 x 2) were prepared by a combined citrate and ethylene diamine tetraacetic acid(EDTA) complexing method. X-ray diffraction(XRD)results revealed the good chemical compatibility between ion-conducting phase CGO and electron-conducting phases PBC2 xFxO after sintering in air. The Fe ionic dopant had a significant effect on the phase structure stability and oxygen permeability under CO2 atmosphere, which was confirmed by XRD, thermogravimetrye differential scanning calorimetry(TGeD SC), scanning electron microscopy(SEM) and oxygen permeation experiments. CGOeP BC0.5F1.5O dual-phase membrane demonstrated a stable oxygen permeation flux of2.71x10-7mol cm 2s 1with 50 mol% He/CO2 as the sweep gas at 925 C, and this value was much higher than that of perovskite-type membranes. The rate-limiting step in the oxygen permeation process changed from the bulk diffusion to the surface oxygen exchange when the CGOeP BC0.5F1.5O membrane thickness decreased to 0.8 mm or less. Due to the high oxygen permeation fluxes and the excellent structural stability under CO2 atmosphere, the CGOeP BC0.5F1.5O membrane is a great potential candidate material for separating oxygen from air in the oxy-fuel combustion techniques.