Cobalt-free perovskite-type oxides BaFel_yTayO3-6 （0 _〈 y -〈 0.2） were synthesized via a simple solid state reac- tion. The cubic perovskite structure can be obtained when y is over 0.1. BaFeo.Ta0.lO3-6 （BFT0.1）...Cobalt-free perovskite-type oxides BaFel_yTayO3-6 （0 _〈 y -〈 0.2） were synthesized via a simple solid state reac- tion. The cubic perovskite structure can be obtained when y is over 0.1. BaFeo.Ta0.lO3-6 （BFT0.1） membrane shows the highest oxygen permeation flux, which can reach 1.6 ml. min- 1. cm-2 at 950 ℃ under the gradient of air/He. The O2-TPD results reveal that BaFe0.9Ta0.lO3-a material shows an excellent reversibility and phase structure stability in air. The oxygen permeation flux is limited by the bulk diffusion when the membrane thick- ness is over 0.8 mm, and it is limited by both the bulk diffusion and the surface exchange when the membrane thickness is below 0.5 mm. Stable oxygen permeation fluxes are obtained during 180 h operation.展开更多
Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the r...Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.展开更多
The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate ...The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate water-storage capability(hydration)and limited proton mobility within conventional PCEC oxygen electrodes hinder the efficiency of water splitting to oxygen,thereby restricting the broader application of PCECs.Here,we report a Ni-doped perovskite oxygen electrode Sr_(2)Fe_(1.4)Ni_(0.1)Mo_(1.5)O_(6-δ)(SFNM),where the incorporation of nickel can effectively amplify the concentration of oxygen vacancies while synergistically enhancing the hydration interaction between water molecules and the perovskite lattice.The enhanced hydration capacity facilitates proton-defect formation and lowers the energy barrier for proton migration.Benefiting from these synergistic enhancements,SFNM demonstrates a substantially reduced polarization resistance of approximately 0.078Ωcm^(2)at700℃under humidified conditions(pH_(2)O=0.1 atm).A PCEC utilizing the SFNM electrode achieves a remarkable current density of 2.60 A cm^(2)with an applied voltage of 1.3 V at 700℃.Furthermore,the PCEC exhibits favorable stability over a duration of 200 h.These outstanding results emphasize the potential of Ni doping to substantially improve both the hydration efficiency and proton mobility within perovskite electrode materials,positioning them as excellent candidates for high-performance PCECs.展开更多
The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ （SCFM） were investigated and compared with those of SrCo0.8Fe0.2O3-δ（...The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ （SCFM） were investigated and compared with those of SrCo0.8Fe0.2O3-δ（SCF）. Single phase SCFM was successfully prepared by a combined EDTA-citric method. SCFM shows a lower thermal expansion coefficient （24× 10^-6-29× 10^-6/K） than SCF between 500 and 1050 ℃, indicating a more stable structure. SCFM shows a high oxygen permeation flux, although the oxygen flux of SCFM decreases slightly because of Mo dopant. Furthermore, it was demonstrated that the doping of Mo in SCF can prevent the order-disorder transition and improves the chemical stability to CO2.展开更多
In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x ...In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.展开更多
Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so ...Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.展开更多
Bi26MO10O69 nanopowder was prepared by hydrothermal method and used as a surface modification material for oxygen separation membrane to enhance oxygen permeability. Thermal decomposition behavior and phase variation ...Bi26MO10O69 nanopowder was prepared by hydrothermal method and used as a surface modification material for oxygen separation membrane to enhance oxygen permeability. Thermal decomposition behavior and phase variation of the precursor were investigated by thermal analyzer （TG-DSC） and high-temperature X-ray diffraction （HT-XRD）. Bi26MO10O69 porous layer was coated on the air side of BaCo0.7Fe0.2Nb0.1O3-δ （BCFN） oxygen permeable membrane by dipping method. In the partial oxidation experiment of coke oven gas （COG）, the Bi26Mo10O69-coated BCFN membrane exhibits higher oxygen permeability and CH4 conversion than the uncoated BCFN membrane. When the thickness of BCFN membrane was 1 mm and the COG and air fluxes were 120 and 100 mL/min, the oxygen permeation flux reached 16.48 mL/（min.cm^2） at 875℃, which was 16.96% higher than the uncoated BCFN membrane. Therefore, Bi26MoloO69 porous layer on the air side will be promising modification coating on the oxygen permeability of BCFN membrane.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
Based on a comparison between the oxygen isotope records of benthic and plank tonic foraminifers from core 8KL of the South China Sea and sea-level change records derived from the Huon Peninsula, New Guinea, it is fou...Based on a comparison between the oxygen isotope records of benthic and plank tonic foraminifers from core 8KL of the South China Sea and sea-level change records derived from the Huon Peninsula, New Guinea, it is found that both records are very similar from 72 K a B.P. to the present, especially for the benthic oxygen isotope record. The linear regression shows that δ18O changes (0.9995‰ for benthic foraminifers and 1.022‰ for planktonic foraminifers) are equal to 100 m in sea-level fluctuation. After making temperature correction in the δ18O record of benthic foraminifers from 72 to 120 Ka B.P., the curve of sea-level oscillation of the South China Sea since 186 Ka B.P. has been reconstructed. The lowermost sea - level that occurred in the last glacial maximum and oxygen isotope stage 6 is approximately - 130 m.展开更多
To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used t...To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used to prepare the Pd-LSCF composite oxygen electrode.The cell with Pd-LSCF|GDC|YSZ|Ni-YSZ configuration shows perfect electrochemical performance in both solid oxide fuel cell(SOFC)mode and solid oxide electrolysis cell(SOEC)mode.In the SOFC mode,the cell achieves a power density of 1.73 W/cm^(2)at800℃higher than that of the LSCF oxygen electrode with 1.38 W/cm^(2).In the SOEC mode,the current density at 1.5 V is 1.67 A/cm^(2)at 800℃under 50 vol%steam concentration.Moreover,the reversibility and stability of the RSOCs were tested during 192 h long-term reversible operation.The degradation rate of the cell is only 2.2%/100 h and 2.5%/100 h in the SOEC and the SOFC modes,respectively.These results confirm that compositing Pd with the LSCF oxygen electrode can considerably boost the electrochemical performance of LSCF electrode in RSOCs field.展开更多
The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SC...The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SCFNO with a thickness of 1 mm had a high level of oxygen permeation flux of 1.4 ml.min^(-1).cm^(-2) at 850 ℃ under air/He gradient.The bulk diffusion is the rate-limiting step in overall oxygen permeation mechanism for SCFNO when the thickness is higher than 1.0 mm.The partial substitution of Nb for Co suppresses the transition of oxygen vacancies order/disorder proven by DSC measurement and enhances the phase stability under low oxygen partial pressure.During long-term tests under low oxygen pressure,the SCFNO exhibites structural stability and stable oxygen permeation.It is proved that substitution of Nb for Co is an effective way to improve the properties of SCFO.展开更多
It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(...Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.展开更多
Among the perovskite-type oxides with symmetrical structure applied in oxygen permeable membranes, cubic phase structure is the most favorable for oxygen permeation. In order to stabilize the cubic perovskite structur...Among the perovskite-type oxides with symmetrical structure applied in oxygen permeable membranes, cubic phase structure is the most favorable for oxygen permeation. In order to stabilize the cubic perovskite structure of BaFeO3-δ material at room temperature, iron was partially substituted by praseodymium. BaFe1-yPryO3-δ powders were synthesized by a solid state reaction method, and sintered samples were prepared from the synthesized BaFe1-yPryO3-δ powders. X-ray diffraction results reveal that the BaFe1-yPryO3-δ samples remain cubic structure at praseodymium substitution amount of y 0.05, 0.075, 0.1. Scanning electron microscope observation indicates that the sintered samples contain only a small amount of enclosed pores and the grain size of BaFe1-yPryO3-δ increase monotonically with the increase of the praseodymium doping amount, praseodymium doping promotes the grain size growth. Tests of electrical conductivity and oxygen permeation flux show that praseodymium doping improves the conduction properties of BaFe1-yPryO3-δ and BaFe0.9Pr0.1O3-δ composition has an electrical conductivity of 6.5 S/era and an oxygen permeation of 1.112 mL/（cm^2.min） at 900 ℃, respectively. High temperature XRD in- vestigation shows that the crystal structure of BaFe0.975Pr0.025O3-δ membrane completely transform to cubic phase at 700℃. The present test results have shown that partially substitution of Fe by praseodymium in BaFeO3 can stabilize the cubic structure and improve the properties.展开更多
The elemental tellurium nanoparticles （TeNPs） - sucrose sol was prepared by the reaction of sodium tellurite with ascorbic acid in sucrose aqueous solution. The results indicated that TeNPs were dispersion excellent...The elemental tellurium nanoparticles （TeNPs） - sucrose sol was prepared by the reaction of sodium tellurite with ascorbic acid in sucrose aqueous solution. The results indicated that TeNPs were dispersion excellent in the TeNPs - sucrose sol and the morphology of TeNPs was needle-like with about 70 nm in width and 500 nm in length. The antioxidant activity of the TeNPs - sucrose sol in vitro was estimated by pyrogallol autoxidation method, Fenton method and oxygen radical absorbance capacity （ORAC） assay. The results showed that a certain amount of TeNPs - sucrose sol could effectively scavenge superoxide anion free radical and hydroxyl free radical with scavenging rates of 73 % and 57 %, respectively. ORAC assay was used to measure the total antioxidant capacity of TeNPs - sucrose sol. The order of ORAC values was 2.25 μmol.L-1 TeNPs - 0.025 % sucrose sol 〉 0.025 % sucrose 〉 2.25 μmol.L-1 Na2TeO3 〉 1.63 μmol.L-1 ascorbic acid. The results suggested that the TeNPs - sucrose sol had the excellent antioxidant activity and TeNPs were the dominating contributors to antioxidant capacity of the TeNPs - sucrose sol.展开更多
The oxidative polycondensation reaction conditions of 4-[（4-hydroxybenzylidene） amino] phenol （4-HBAP） were studied with H2O2, air oxygen and NaOCl in an aqueous alkaline medium between 50 and 90℃. The structures...The oxidative polycondensation reaction conditions of 4-[（4-hydroxybenzylidene） amino] phenol （4-HBAP） were studied with H2O2, air oxygen and NaOCl in an aqueous alkaline medium between 50 and 90℃. The structures of the obtained monomer and polymer were confirmed by FT-IR, UV-Vis, 1H- and 13C-NMR and elemental analysis. The characterization was made by TG-DTA, size exclusion chromatography （SEC） and solubility tests. At the optimum reaction conditions, the yield of poly[4-（4-hydroxybenzylidene amino） phenol] （P-4-HBAP） was found to be 48.3% （for H2O2 oxidant）, 80.5% （for air O2 oxidant） and 86.4% （for NaOCl oxidant）. According to the SEC analysis, the number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of P-4-HBAP was found to be 8950, 10970 g tool^-1 and 1.225, respectively, using H202; and l l610, 15190 g tool^-1 and 1.308 respectively, using air 02 and 7900, 9610 g mol^-1 and 1.216, respectively, using NaOC1. According to TG-DTA analyses, P-4-HBAP was more stable than 4-HBAP against thermal decomposition. The weight loss of P-4-HBAP was found to be 49.27% at 1000℃. The highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） values calculated from electrochemical measurement. Electrochemical energy gaps （Eg＇） of 4-HBAP and P-4-HBAP were found to be -5.46, -5.28; -2.26, -2.67; 3.20 and 2.61 eV, respectively. According to UV-Vis measurements, optical band gap （Eg） of 4-HBAP and P-4-HBAP were found to be 3.34 and 3.01 eV, respectively. Also, antimicrobial activities of 4-HBAP and P-4-HBAP were examined against selected some bacteria. The electrical conductivity of the polymer was measured after doping with iodine.展开更多
This paper aims at testing oxygen and benzene contents in gasoline by mid-infrared spectroscopy.The experimental results prove that infrared spectroscopy(IR)is reliable.Compared with gas chromatography(GC)technology,t...This paper aims at testing oxygen and benzene contents in gasoline by mid-infrared spectroscopy.The experimental results prove that infrared spectroscopy(IR)is reliable.Compared with gas chromatography(GC)technology,this paper draws a conclusion that IR has several advantages,including rapid analysis,excellent repeatability and low analysis cost.展开更多
A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are pr...A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.展开更多
基金the National Science Fund for Distinguished Young Scholars of China(No.21225625)the National Natural Science Foundation of China(No.21176087)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20110172110013)
文摘Cobalt-free perovskite-type oxides BaFel_yTayO3-6 （0 _〈 y -〈 0.2） were synthesized via a simple solid state reac- tion. The cubic perovskite structure can be obtained when y is over 0.1. BaFeo.Ta0.lO3-6 （BFT0.1） membrane shows the highest oxygen permeation flux, which can reach 1.6 ml. min- 1. cm-2 at 950 ℃ under the gradient of air/He. The O2-TPD results reveal that BaFe0.9Ta0.lO3-a material shows an excellent reversibility and phase structure stability in air. The oxygen permeation flux is limited by the bulk diffusion when the membrane thick- ness is over 0.8 mm, and it is limited by both the bulk diffusion and the surface exchange when the membrane thickness is below 0.5 mm. Stable oxygen permeation fluxes are obtained during 180 h operation.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2023MB061)。
文摘Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.
基金financially supported by the National Key R&D Program of China(No.2022YFB4002501)the National Natural Science Foundation of China(No.52202208)
文摘The proton ceramic electrochemical cell(PCEC),distinguished by its robust all-solid-state construction,emerges as a particularly promising contender in the realm of hydrogen production technologies.However,inadequate water-storage capability(hydration)and limited proton mobility within conventional PCEC oxygen electrodes hinder the efficiency of water splitting to oxygen,thereby restricting the broader application of PCECs.Here,we report a Ni-doped perovskite oxygen electrode Sr_(2)Fe_(1.4)Ni_(0.1)Mo_(1.5)O_(6-δ)(SFNM),where the incorporation of nickel can effectively amplify the concentration of oxygen vacancies while synergistically enhancing the hydration interaction between water molecules and the perovskite lattice.The enhanced hydration capacity facilitates proton-defect formation and lowers the energy barrier for proton migration.Benefiting from these synergistic enhancements,SFNM demonstrates a substantially reduced polarization resistance of approximately 0.078Ωcm^(2)at700℃under humidified conditions(pH_(2)O=0.1 atm).A PCEC utilizing the SFNM electrode achieves a remarkable current density of 2.60 A cm^(2)with an applied voltage of 1.3 V at 700℃.Furthermore,the PCEC exhibits favorable stability over a duration of 200 h.These outstanding results emphasize the potential of Ni doping to substantially improve both the hydration efficiency and proton mobility within perovskite electrode materials,positioning them as excellent candidates for high-performance PCECs.
文摘The phase composition, microstructure, thermal expansion coefficients, oxygen permeation properties and chemical stability of SrCo0.8Fe0.2O3-δ （SCFM） were investigated and compared with those of SrCo0.8Fe0.2O3-δ（SCF）. Single phase SCFM was successfully prepared by a combined EDTA-citric method. SCFM shows a lower thermal expansion coefficient （24× 10^-6-29× 10^-6/K） than SCF between 500 and 1050 ℃, indicating a more stable structure. SCFM shows a high oxygen permeation flux, although the oxygen flux of SCFM decreases slightly because of Mo dopant. Furthermore, it was demonstrated that the doping of Mo in SCF can prevent the order-disorder transition and improves the chemical stability to CO2.
文摘In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.
基金The National Basic Research Program of China (973 Program) (No.2007CB936300)the Natural Science Foundation of Jiangsu Province (No.BK2009293)
文摘Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.
基金Projects(51272154,51472156)supported by the National Natural Science Foundation of ChinaProjects(sdcx2012033,sdcx2012062)supported by the Innovation Fund of Shanghai University,China+1 种基金Project(14ZR1416400)supported by Special Research Foundation for Training and Selecting Outstanding Young Teachers of Universities in Shanghai,Chinasupported by Shanghai Science and Technology Committee,China
文摘Bi26MO10O69 nanopowder was prepared by hydrothermal method and used as a surface modification material for oxygen separation membrane to enhance oxygen permeability. Thermal decomposition behavior and phase variation of the precursor were investigated by thermal analyzer （TG-DSC） and high-temperature X-ray diffraction （HT-XRD）. Bi26MO10O69 porous layer was coated on the air side of BaCo0.7Fe0.2Nb0.1O3-δ （BCFN） oxygen permeable membrane by dipping method. In the partial oxidation experiment of coke oven gas （COG）, the Bi26Mo10O69-coated BCFN membrane exhibits higher oxygen permeability and CH4 conversion than the uncoated BCFN membrane. When the thickness of BCFN membrane was 1 mm and the COG and air fluxes were 120 and 100 mL/min, the oxygen permeation flux reached 16.48 mL/（min.cm^2） at 875℃, which was 16.96% higher than the uncoated BCFN membrane. Therefore, Bi26MoloO69 porous layer on the air side will be promising modification coating on the oxygen permeability of BCFN membrane.
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 49206062 funded by the National Natural Science Foundation of China
文摘Based on a comparison between the oxygen isotope records of benthic and plank tonic foraminifers from core 8KL of the South China Sea and sea-level change records derived from the Huon Peninsula, New Guinea, it is found that both records are very similar from 72 K a B.P. to the present, especially for the benthic oxygen isotope record. The linear regression shows that δ18O changes (0.9995‰ for benthic foraminifers and 1.022‰ for planktonic foraminifers) are equal to 100 m in sea-level fluctuation. After making temperature correction in the δ18O record of benthic foraminifers from 72 to 120 Ka B.P., the curve of sea-level oscillation of the South China Sea since 186 Ka B.P. has been reconstructed. The lowermost sea - level that occurred in the last glacial maximum and oxygen isotope stage 6 is approximately - 130 m.
基金Project supported by the National Key Research&Development Project(2020YFB1506304)the National Natural Science Foundation of China(52172199,52072135,52002121)。
文摘To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used to prepare the Pd-LSCF composite oxygen electrode.The cell with Pd-LSCF|GDC|YSZ|Ni-YSZ configuration shows perfect electrochemical performance in both solid oxide fuel cell(SOFC)mode and solid oxide electrolysis cell(SOEC)mode.In the SOFC mode,the cell achieves a power density of 1.73 W/cm^(2)at800℃higher than that of the LSCF oxygen electrode with 1.38 W/cm^(2).In the SOEC mode,the current density at 1.5 V is 1.67 A/cm^(2)at 800℃under 50 vol%steam concentration.Moreover,the reversibility and stability of the RSOCs were tested during 192 h long-term reversible operation.The degradation rate of the cell is only 2.2%/100 h and 2.5%/100 h in the SOEC and the SOFC modes,respectively.These results confirm that compositing Pd with the LSCF oxygen electrode can considerably boost the electrochemical performance of LSCF electrode in RSOCs field.
基金supported by the National Natural Science Foundation of China (No. 51174133)the National High Technology Research and Development Program of China(No. 2006AA11A189)the Science and Technology Commission of Shanghai Municipality (No. 11ZR1412900)
文摘The effect of Nb doping on the oxygen permeation and stability of SrCo_(0.8)Fe_(0.2)O_(3-δ)(SCFO) was investigated comprehensively.Cubic perovskite phase was formed in SrCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ)(SCFNO).The SCFNO with a thickness of 1 mm had a high level of oxygen permeation flux of 1.4 ml.min^(-1).cm^(-2) at 850 ℃ under air/He gradient.The bulk diffusion is the rate-limiting step in overall oxygen permeation mechanism for SCFNO when the thickness is higher than 1.0 mm.The partial substitution of Nb for Co suppresses the transition of oxygen vacancies order/disorder proven by DSC measurement and enhances the phase stability under low oxygen partial pressure.During long-term tests under low oxygen pressure,the SCFNO exhibites structural stability and stable oxygen permeation.It is proved that substitution of Nb for Co is an effective way to improve the properties of SCFO.
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
基金support from the National Natural Science Foundation of China(51402100,21905088,21573066 and U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5044,2022JJ10006)。
文摘Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.
基金supported by the National Natural Science Foundation of China(No.216060647)the Industry-University-Research Project of Aviation Industry Corporation of China (No.cxy2012HFGD025)
文摘Among the perovskite-type oxides with symmetrical structure applied in oxygen permeable membranes, cubic phase structure is the most favorable for oxygen permeation. In order to stabilize the cubic perovskite structure of BaFeO3-δ material at room temperature, iron was partially substituted by praseodymium. BaFe1-yPryO3-δ powders were synthesized by a solid state reaction method, and sintered samples were prepared from the synthesized BaFe1-yPryO3-δ powders. X-ray diffraction results reveal that the BaFe1-yPryO3-δ samples remain cubic structure at praseodymium substitution amount of y 0.05, 0.075, 0.1. Scanning electron microscope observation indicates that the sintered samples contain only a small amount of enclosed pores and the grain size of BaFe1-yPryO3-δ increase monotonically with the increase of the praseodymium doping amount, praseodymium doping promotes the grain size growth. Tests of electrical conductivity and oxygen permeation flux show that praseodymium doping improves the conduction properties of BaFe1-yPryO3-δ and BaFe0.9Pr0.1O3-δ composition has an electrical conductivity of 6.5 S/era and an oxygen permeation of 1.112 mL/（cm^2.min） at 900 ℃, respectively. High temperature XRD in- vestigation shows that the crystal structure of BaFe0.975Pr0.025O3-δ membrane completely transform to cubic phase at 700℃. The present test results have shown that partially substitution of Fe by praseodymium in BaFeO3 can stabilize the cubic structure and improve the properties.
基金Funded by the National Natural Science Foundation of China(No.21075053)
文摘The elemental tellurium nanoparticles （TeNPs） - sucrose sol was prepared by the reaction of sodium tellurite with ascorbic acid in sucrose aqueous solution. The results indicated that TeNPs were dispersion excellent in the TeNPs - sucrose sol and the morphology of TeNPs was needle-like with about 70 nm in width and 500 nm in length. The antioxidant activity of the TeNPs - sucrose sol in vitro was estimated by pyrogallol autoxidation method, Fenton method and oxygen radical absorbance capacity （ORAC） assay. The results showed that a certain amount of TeNPs - sucrose sol could effectively scavenge superoxide anion free radical and hydroxyl free radical with scavenging rates of 73 % and 57 %, respectively. ORAC assay was used to measure the total antioxidant capacity of TeNPs - sucrose sol. The order of ORAC values was 2.25 μmol.L-1 TeNPs - 0.025 % sucrose sol 〉 0.025 % sucrose 〉 2.25 μmol.L-1 Na2TeO3 〉 1.63 μmol.L-1 ascorbic acid. The results suggested that the TeNPs - sucrose sol had the excellent antioxidant activity and TeNPs were the dominating contributors to antioxidant capacity of the TeNPs - sucrose sol.
基金This work was financially supported by the TUBITAK Grants Commission for a research grant(No.TBAG-2451(104T062)).
文摘The oxidative polycondensation reaction conditions of 4-[（4-hydroxybenzylidene） amino] phenol （4-HBAP） were studied with H2O2, air oxygen and NaOCl in an aqueous alkaline medium between 50 and 90℃. The structures of the obtained monomer and polymer were confirmed by FT-IR, UV-Vis, 1H- and 13C-NMR and elemental analysis. The characterization was made by TG-DTA, size exclusion chromatography （SEC） and solubility tests. At the optimum reaction conditions, the yield of poly[4-（4-hydroxybenzylidene amino） phenol] （P-4-HBAP） was found to be 48.3% （for H2O2 oxidant）, 80.5% （for air O2 oxidant） and 86.4% （for NaOCl oxidant）. According to the SEC analysis, the number-average molecular weight （Mn）, weight-average molecular weight （Mw） and polydispersity index （PDI） values of P-4-HBAP was found to be 8950, 10970 g tool^-1 and 1.225, respectively, using H202; and l l610, 15190 g tool^-1 and 1.308 respectively, using air 02 and 7900, 9610 g mol^-1 and 1.216, respectively, using NaOC1. According to TG-DTA analyses, P-4-HBAP was more stable than 4-HBAP against thermal decomposition. The weight loss of P-4-HBAP was found to be 49.27% at 1000℃. The highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） values calculated from electrochemical measurement. Electrochemical energy gaps （Eg＇） of 4-HBAP and P-4-HBAP were found to be -5.46, -5.28; -2.26, -2.67; 3.20 and 2.61 eV, respectively. According to UV-Vis measurements, optical band gap （Eg） of 4-HBAP and P-4-HBAP were found to be 3.34 and 3.01 eV, respectively. Also, antimicrobial activities of 4-HBAP and P-4-HBAP were examined against selected some bacteria. The electrical conductivity of the polymer was measured after doping with iodine.
文摘This paper aims at testing oxygen and benzene contents in gasoline by mid-infrared spectroscopy.The experimental results prove that infrared spectroscopy(IR)is reliable.Compared with gas chromatography(GC)technology,this paper draws a conclusion that IR has several advantages,including rapid analysis,excellent repeatability and low analysis cost.
文摘A composite paste electrode based on Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)—initially synthesized by solgel method—and multiwall carbon nanotube (MWCNT) as a cathode in fuel cells is developed. The composite pastes are prepared by the direct mixing of BSCF:MWCNT at 90:10, 80:20 and 70:30 (% w/W). These electrodes are then characterized by the x-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherm, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The XRD and SEM confirm the inclusion and the uniform dispersal of the MWCNT within BSCF, respectively. The nitrogen adsorption isotherm study shows that the porosity of the composite paste electrode has been improved by two-fold from the BSCF electrode. The EIS and CV demonstrate that the higher ratios of MWCNT in the composites are critical in improving the electronic conductivity as well as the kinetics. It is also noticeable that the electrode has increased the catalysis of oxygen in 0.1 M KOH (pH 12.0). Cyclic voltammetric studies on the oxygen reduction reaction (ORR) suggest that the incorporation of MWCNT is vital in improving the electrode (cathode) properties of a fuel cell.
