It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced ...It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.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
A temperature stable Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics were fabricated using a conventional solid-state route sintered at 1100℃for 4 h.The XRD results indicate that the main phase Li2ZnTi3O8 and secondary...A temperature stable Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics were fabricated using a conventional solid-state route sintered at 1100℃for 4 h.The XRD results indicate that the main phase Li2ZnTi3O8 and secondary phase including SrxCa1-xTiO3(0≤x≤1)solid solution and TiO2 co-exist in composite and form a stable composite system when the(CaxSr1-x)(0≤x≤1)substitutes for Zn of Li2ZnTi3O8 ceramic.As x is increased from 0 to 1,the relative permittivity(εr)increases from 26.65 to 27.12,and the quality factor(Q×f)increases from 63300 to 66600 GHz.With the increased of x,the temperature coefficient of resonant frequency(τf)increases from 0.27 to 8.23 ppm/℃,and then decreases to 3.51 ppm/℃.On the whole,the Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics show excellent comprehensive properties of middleεr=25-27,higher Q×f≥60000 GHz andτf≤±8.5 ppm/℃.展开更多
In an effort to improve the performance of superconductors in the field and high temperatures it is important to study the superconducting mechanism. For this reason, the cation substitution can be conducted. One of t...In an effort to improve the performance of superconductors in the field and high temperatures it is important to study the superconducting mechanism. For this reason, the cation substitution can be conducted. One of the high Tc superconductors Gd1Ba2Cu3O7−δ phase with Sr substitution has been synthesized, i.e. Gd1(Ba2−xSrx)Cu3O7−δ compound. The sample was synthesized by using a solid-state reaction method with a wet mixing, sintered for 12 hours at temperature 900°C. The synthesis results are characterized by using XRD. The results of Match-3 software analysis showed high (higher 85%) Gd1Ba2Cu3O7−δ phase was formed. The Sr substitution causes changes to the structure, i.e. the lattice parameters a, b and c, where the orthorhombicity tends to decrease with increasing Sr content. Refinement results show that based on the oxygen occupancy, the total oxygen content tends to increase.展开更多
The magnetic and dielectric properties of Sr-substituted Zn2-Y hexagonal ferrites (Ba2-x SrxZn2Fe12O22, 1.0 〈 x ≤ 1.5) are studied in this paper. Sr substitution will lead to the variation of cation occupation, wh...The magnetic and dielectric properties of Sr-substituted Zn2-Y hexagonal ferrites (Ba2-x SrxZn2Fe12O22, 1.0 〈 x ≤ 1.5) are studied in this paper. Sr substitution will lead to the variation of cation occupation, which influences both the magnetic and electric properties. As Sr content x rises from 1.0 to 1.5, magnetic hysteresis loop gets wider gradually and the permeability drops rapidly due to the transformation from ferrimagnetic to antiferromagnetic phase. Moreover, permittivity rises with increasing Sr content. Under a certain external magnetic field, the phase transition of helical spin structure of Ba0.5Srl.5Zn2Fe12O22 at about 295 K seems to open a possibility for the room-temperature ferroelectricity induced by magnetic field. But its low resistivity prevents the observation of ferroelectric and magnetoelectric properties at room-temperature.展开更多
Polycrystalline particles of Ca3-xErxCo2O6 (x=0.0, 0.15, 0.3, 0.45 and 0.6) were synthesized using sol-gel method combined with Low Temperature Sintering procedure (LTS) to evaluate the effect of Er substitution o...Polycrystalline particles of Ca3-xErxCo2O6 (x=0.0, 0.15, 0.3, 0.45 and 0.6) were synthesized using sol-gel method combined with Low Temperature Sintering procedure (LTS) to evaluate the effect of Er substitution on the thermoelectric properties of Ca3Co2O6. The crystal structure and microstructure were investigated using X-ray diffraction, infrared spectroscopy and scanning electron microscope. The electrical conductivity and Seebeck coefficient of the complex oxides were measured from 300 to 1073 K. The results showed that all the sampies were p-type semiconductors. The electrical conductivity increased with the increase in temperature. Er substitutions at Ca site affected carrier concentrations and carder mobility, resulting an increase in Seebeck coefficient and decrease in electrical conductivity. The power factor of Ca2.85Er0.15Co2O6 reached 10.66 μw/mK^2 at 1073 K.展开更多
MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still chal...MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still challenges in modifying the surface functional groups of MXene to further improve the electrochemical performance and increase the structure variety for MXene-based sulfur host.Herein,we report an efficient and flexible nucleophilic substitution(S_(N))strategy to modify the Ti_(3)C_(2)T_(x) surface terminations and purposefully designed Magnolol-modified Ti_(3)C_(2)T_(x)(M-Ti_(3)C_(2)T_(x))as powerful cathode host materials.Benefiting from more C-Ti-O bonds forming and diallyl groups terminations reducing after the dehalogenation and nucleophilic addition reactions,the given M-Ti_(3)C_(2)T_(x) electrode could effectively suppress the lithium polysulfides shuttling via chemisorption and C—S covalent bond formation.Besides,the Magnolol-modified Ti_(3)C_(2)T_(x) significantly accelerates polysulfide redox reaction and reduces the activation energy of Li_(2) S decomposition.As a result,the as-prepared M-Ti_(3)C_(2)T_(x) electrode displays an excellent rate capability and a high reversible capacity of 7.68 mAh cm^(-2)even under 7.2 mg cm^(-2)S-loaded with a low decay rate of 0.07%(from 2 nd cycle).This flexible surface-modified strategy for MXene terminations is expected to be extended to other diverse MXene applications.展开更多
The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large ...The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.展开更多
Barium ferrite micro/nano fibers were successfully prepared via the electrostatic spinning by using dimethyl formamide(DMF) as the solvent, and poly vinyl pyrrolidone(PVP) as the spinning auxiliaries. Effects of s...Barium ferrite micro/nano fibers were successfully prepared via the electrostatic spinning by using dimethyl formamide(DMF) as the solvent, and poly vinyl pyrrolidone(PVP) as the spinning auxiliaries. Effects of strontium substitution on the structure, morphology, and magnetic properties were investigated by scanning electron microscope(SEM), X-ray diffraction analysis(XRD), and vibration sample magnetometer(VSM). XRD patterns of the samples confirm that pure barium ferrite fibers form, and the Sr substitution makes the main peaks(110),(107), and(114) move to right slightly. Also, the FE-SEM images show that the Sr substituted fibers can keep complete fibrous morphology. Moreover, the VSM results demonstrate that the saturation magnetization can reach 56.7 emu/g when the fibers are calcined at 800℃.展开更多
基金the National Natural Science Foundation of China (22209091)the Natural Science Foundation of Shandong Province (ZR2020QB057)+1 种基金the Key Program of National Natural Science Foundation of China (22133006)the Yankuang Group 2019 Science and Technology Program (YKKJ2019AJ05JG-R60)。
文摘It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.
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Funded by the Open Project Program of Key Laboratory of Inorganic Functional Materials and Devices,Chinese Academy of Sciences(No.KLIFMD201606)the Open Fund of National Innovation Platform(No.2017YJ163)+1 种基金the National Natural Science Foundation of China(Nos.51502220,51521001,and 51672197)the Open Foundation of Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics(Wuhan University of Technology)(No.TAM201802)。
文摘A temperature stable Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics were fabricated using a conventional solid-state route sintered at 1100℃for 4 h.The XRD results indicate that the main phase Li2ZnTi3O8 and secondary phase including SrxCa1-xTiO3(0≤x≤1)solid solution and TiO2 co-exist in composite and form a stable composite system when the(CaxSr1-x)(0≤x≤1)substitutes for Zn of Li2ZnTi3O8 ceramic.As x is increased from 0 to 1,the relative permittivity(εr)increases from 26.65 to 27.12,and the quality factor(Q×f)increases from 63300 to 66600 GHz.With the increased of x,the temperature coefficient of resonant frequency(τf)increases from 0.27 to 8.23 ppm/℃,and then decreases to 3.51 ppm/℃.On the whole,the Li2Zn0.95(SrxCa1-x)0.05Ti3O8(0≤x≤1)ceramics show excellent comprehensive properties of middleεr=25-27,higher Q×f≥60000 GHz andτf≤±8.5 ppm/℃.
基金This report is part of the fundamental research report with contract No.486 127/UN14.2/PNL.01.03.00/2016.
文摘In an effort to improve the performance of superconductors in the field and high temperatures it is important to study the superconducting mechanism. For this reason, the cation substitution can be conducted. One of the high Tc superconductors Gd1Ba2Cu3O7−δ phase with Sr substitution has been synthesized, i.e. Gd1(Ba2−xSrx)Cu3O7−δ compound. The sample was synthesized by using a solid-state reaction method with a wet mixing, sintered for 12 hours at temperature 900°C. The synthesis results are characterized by using XRD. The results of Match-3 software analysis showed high (higher 85%) Gd1Ba2Cu3O7−δ phase was formed. The Sr substitution causes changes to the structure, i.e. the lattice parameters a, b and c, where the orthorhombicity tends to decrease with increasing Sr content. Refinement results show that based on the oxygen occupancy, the total oxygen content tends to increase.
基金Project supported by the National Natural Science Foundation of China (Grant No 50702005)the Specialized Research Fund for the Doctoral Program of Higher Education (Grant No 20070008027)the Beijing Municipal Commission of Education (Grant No SYS100080419)
文摘The magnetic and dielectric properties of Sr-substituted Zn2-Y hexagonal ferrites (Ba2-x SrxZn2Fe12O22, 1.0 〈 x ≤ 1.5) are studied in this paper. Sr substitution will lead to the variation of cation occupation, which influences both the magnetic and electric properties. As Sr content x rises from 1.0 to 1.5, magnetic hysteresis loop gets wider gradually and the permeability drops rapidly due to the transformation from ferrimagnetic to antiferromagnetic phase. Moreover, permittivity rises with increasing Sr content. Under a certain external magnetic field, the phase transition of helical spin structure of Ba0.5Srl.5Zn2Fe12O22 at about 295 K seems to open a possibility for the room-temperature ferroelectricity induced by magnetic field. But its low resistivity prevents the observation of ferroelectric and magnetoelectric properties at room-temperature.
基金the National Natural Science Foundation of China (20571019)Scientific Research Foundation for the Returned Overseas Chinese Scholars, Heilongjiang (LC06C130)Program of Harbin Subject Chief Scientist
文摘Polycrystalline particles of Ca3-xErxCo2O6 (x=0.0, 0.15, 0.3, 0.45 and 0.6) were synthesized using sol-gel method combined with Low Temperature Sintering procedure (LTS) to evaluate the effect of Er substitution on the thermoelectric properties of Ca3Co2O6. The crystal structure and microstructure were investigated using X-ray diffraction, infrared spectroscopy and scanning electron microscope. The electrical conductivity and Seebeck coefficient of the complex oxides were measured from 300 to 1073 K. The results showed that all the sampies were p-type semiconductors. The electrical conductivity increased with the increase in temperature. Er substitutions at Ca site affected carrier concentrations and carder mobility, resulting an increase in Seebeck coefficient and decrease in electrical conductivity. The power factor of Ca2.85Er0.15Co2O6 reached 10.66 μw/mK^2 at 1073 K.
基金the support from CNPC Innovation Found(2021DQ02-1001)Liao Ning Revitalization Talents Program(XLYC1907144)Xinghai Talent Cultivation Plan(X20200303)。
文摘MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still challenges in modifying the surface functional groups of MXene to further improve the electrochemical performance and increase the structure variety for MXene-based sulfur host.Herein,we report an efficient and flexible nucleophilic substitution(S_(N))strategy to modify the Ti_(3)C_(2)T_(x) surface terminations and purposefully designed Magnolol-modified Ti_(3)C_(2)T_(x)(M-Ti_(3)C_(2)T_(x))as powerful cathode host materials.Benefiting from more C-Ti-O bonds forming and diallyl groups terminations reducing after the dehalogenation and nucleophilic addition reactions,the given M-Ti_(3)C_(2)T_(x) electrode could effectively suppress the lithium polysulfides shuttling via chemisorption and C—S covalent bond formation.Besides,the Magnolol-modified Ti_(3)C_(2)T_(x) significantly accelerates polysulfide redox reaction and reduces the activation energy of Li_(2) S decomposition.As a result,the as-prepared M-Ti_(3)C_(2)T_(x) electrode displays an excellent rate capability and a high reversible capacity of 7.68 mAh cm^(-2)even under 7.2 mg cm^(-2)S-loaded with a low decay rate of 0.07%(from 2 nd cycle).This flexible surface-modified strategy for MXene terminations is expected to be extended to other diverse MXene applications.
基金supported by the National Natural Science Foundation of China(61874159,62074052,61974173,52072327,51702085 and 51802081)the Joint Talent Cultivation Funds of NSFC-HN(U1704151 and U1904192)+1 种基金the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(202101510004)the Science and Technology Innovation Talents in Universities of Henan Province(21HASTIT023)。
文摘The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.
基金Funded by the Qilu Program in Shandong University and the Natural Science Foundation of Shandong Province(ZR2014EMM001)
文摘Barium ferrite micro/nano fibers were successfully prepared via the electrostatic spinning by using dimethyl formamide(DMF) as the solvent, and poly vinyl pyrrolidone(PVP) as the spinning auxiliaries. Effects of strontium substitution on the structure, morphology, and magnetic properties were investigated by scanning electron microscope(SEM), X-ray diffraction analysis(XRD), and vibration sample magnetometer(VSM). XRD patterns of the samples confirm that pure barium ferrite fibers form, and the Sr substitution makes the main peaks(110),(107), and(114) move to right slightly. Also, the FE-SEM images show that the Sr substituted fibers can keep complete fibrous morphology. Moreover, the VSM results demonstrate that the saturation magnetization can reach 56.7 emu/g when the fibers are calcined at 800℃.