Two novel out-of-plane ordered quaternary borides M'_(4)VSiB_(2) (M'=Nb and Mo) have been synthesized. The out-of-plane ordered characteristic has been confirmed by the X-ray diffraction, the neutron powder di...Two novel out-of-plane ordered quaternary borides M'_(4)VSiB_(2) (M'=Nb and Mo) have been synthesized. The out-of-plane ordered characteristic has been confirmed by the X-ray diffraction, the neutron powder diffraction and the scanning transmission electron microscopy with high-angle angular dark field images. By adjusting the stoichiometric ratio of Mo and V, the 16l site preferentially occupied by relatively larger atom and 4c site by relatively smaller atom have been confirmed. The further first-principle calculation demonstrates the dynamical and thermodynamical stability of Mo_(4)VSiB_(2) o-T2 phase. This work confirms the transition metal occupation strategy of o-T2 phase and enriches the out-of-plane ordered laminated borides family.展开更多
Guided by the fundamental principles of the whole petroleum system,the control of tectonism,sedimentation,and diagenesis on hydrocarbon accumulation in a rifted basin is studied using the data of petroleum geology and...Guided by the fundamental principles of the whole petroleum system,the control of tectonism,sedimentation,and diagenesis on hydrocarbon accumulation in a rifted basin is studied using the data of petroleum geology and exploration of the second member of the Paleogene Kongdian Formation(Kong-2 Member)in the Cangdong Sag,Bohai Bay Basin,China.It is clarified that the circle structure and circle effects are the marked features of a continental fault petroliferous basin,and they govern the orderly distribution of conventional and unconventional hydrocarbons in the whole petroleum systems of the rifted basin.Tectonic circle zones control sedimentary circle zones,while sedimentary circle zones and diagenetic circle zones control the spatial distribution of favorable reservoirs,thereby determining the orderly distribution of hydrocarbon accumulations in various circles.A model for the integrated,systematic accumulation of conventional and unconventional hydrocarbons under a multi-circle structure of the whole petroleum system of continental rifted basin has been developed.It reveals that each sag of the rifted basin is an independent whole petroleum system and circle system,which encompasses multiple orderly circles of conventional and unconventional hydrocarbons controlled by the same source kitchen.From the outer circle to the middle circle and then to the inner circle,there is an orderly transition from structural and stratigraphic reservoirs,to lithological and structural-lithological reservoirs,and finally to tight oil/gas and shale oil/gas enrichment zones.The significant feature of the whole petroleum system is the orderly control of hydrocarbons by multi-circle stratigraphic coupling,with the integrated,orderly distribution of conventional and unconventional reserves being the inevitable result of the multi-layered interaction within the whole petroleum system.This concept of multi-circle stratigraphic coupling for the orderly,integrated accumulation of conventional and unconventional hydrocarbons has guided significant breakthroughs in the overall,three-dimensional exploration and shale oil exploration in the Cangdong Sag.展开更多
Higher-order band topology not only enriches our understanding of topological phases but also unveils pioneering lower-dimensional boundary states,which harbors substantial potential for next-generation device applica...Higher-order band topology not only enriches our understanding of topological phases but also unveils pioneering lower-dimensional boundary states,which harbors substantial potential for next-generation device applications.The distinct electronic configurations and tunable attributes of two-dimensional materials position them as a quintessential platform for the realization of second-order topological insulators(SOTIs).This article provides an overview of the research progress in SOTIs within the field of two-dimensional electronic materials,focusing on the characterization of higher-order topological properties and the numerous candidate materials proposed in theoretical studies.These endeavors not only enhance our understanding of higher-order topological states but also highlight potential material systems that could be experimentally realized.展开更多
Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelec...Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelectric effects.However,the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra.Herein,a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPb Br_(4)(NMPB,NMA is N-methylbenzene ammonium,MA is methylammonium)with alternating cation in the interlayer space.Driven by the incorporation of a second MA cation,the perovskite layer transformed from a 2D Pb_(7)Br_(24)anionic network with corner-and face-sharing octahedra to a flat 2D PbBr_(4)perovskite networks only with corner-sharing octahedra.In the crystal structure of NMPB,the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3μC/cm^(2).More intriguingly,the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance,showing a considerable polarization-related dichroism ratio up to 1.87.The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties,overcoming limitations of conventional cation choice.展开更多
In order to calculate the multipoles in real materials with considerable intersite Coulomb interaction V,we develop a self-consistent program which starts from the frst-principles calculations to solve the tight-bindi...In order to calculate the multipoles in real materials with considerable intersite Coulomb interaction V,we develop a self-consistent program which starts from the frst-principles calculations to solve the tight-binding Hamiltonian including onsite Coulomb repulsion U,V,and spin-orbital couplingλ.The program is applied to Ba_(2)MgReO_(6)to fgure out the mechanism of structural instability and magnetic ordering.A comprehensive quadrupole phase diagram versus U and V withλ=0.28 eV is calculated.Our results demonstrate that the easy-plane anisotropy and the intersite Coulomb repulsion V must be considered to remove the orbital frustration.The increase of V to>20 meV would arrange quadrupole Q_(x^(2)-y^(2))antiparallelly,accompanied by small parallel Q_(3z)^(2)-r^(2),and stabilize Ba_(2)MgReO_(6)into the body-centered tetragonal structure.Such antiparallel Q_(x^(2)-y^(2))provides a new mechanism for the Dzyaloshinskii-Moriya interaction and gives rise to the canted antiferromagnetic(CAF)state along the[110]axis.Moreover,sizable octupoles such as O_(21)^(31),O_(21)^(33),O_(21)^(34)and O_(21)^(36)are discovered for the frst time in the CAF state.Our study not only provides a comprehensive understanding of the experimental results in Ba_(2)MgReO_(6),but also serves as a general and useful tool for the study of multipole physics in 5d compounds.展开更多
The microstructure and mechanical properties of Mg94Zn2Y4 extruded alloy containing long-period stacking ordered structures were systematically investigated by SEM and TEM analyses. The results show that the 18R-LPSO ...The microstructure and mechanical properties of Mg94Zn2Y4 extruded alloy containing long-period stacking ordered structures were systematically investigated by SEM and TEM analyses. The results show that the 18R-LPSO structure and α-Mg phase are observed in cast Mg94Zn2Y4 alloy. After extrusion, the LPSO structures are delaminated and Mg-slices with width of 50-200 nm are generated. By ageing at 498 K for 36 h, the ageing peak is attained andβ′phase is precipitated. Due to this novel precipitation, the microhardness ofα-Mg matrix increases apparently from HV108.9 to HV129.7. While the microhardness for LPSO structure is stabilized at about HV145. TEM observations and SAED patterns indicate that the β′ phase has unique orientation relationships betweenα-Mg and LPSO structures, the direction in the close-packed planes ofβ′precipitates perpendicular to that ofα-Mg and LPSO structures. The ultimate tensile strength for the peak-aged alloy achieves 410.7 MPa and the significant strength originates from the coexistence ofβ′precipitates and 18R-LPSO structures.展开更多
Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton cata...Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation. X-ray diffraction and transmission electron microscopy results showed that the TiO2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity. The ordered pore structure of the TiO2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting. Furthermore, iron ions can be controlled by embedding them into the TiO2 framework to prevent iron ion loss and inactivation. After five cycles, the reaction rate of the ordered mesoporous Fe/TiO2 remained unchanged, indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.展开更多
A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and ca...A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.展开更多
Nanocatalysts consisting of three‐dimensionally ordered macroporous(3DOM)TiO2‐supported ultrafine Pd nanoparticles(Pd/3DOM‐TiO2‐GBMR)were readily fabricated by gas bubbling‐assisted membrane reduction(GBMR)method...Nanocatalysts consisting of three‐dimensionally ordered macroporous(3DOM)TiO2‐supported ultrafine Pd nanoparticles(Pd/3DOM‐TiO2‐GBMR)were readily fabricated by gas bubbling‐assisted membrane reduction(GBMR)method.These catalysts had a well‐defined and highly ordered macroporous nanostructure with an average pore size of 280 nm.In addition,ultrafine hemispherical Pd nanoparticles(NPs)with a mean particle size of 1.1 nm were found to be well dispersed over the surface of the 3DOM‐TiO2 support and deposited on the inner walls of the material.The nanostructure of the 3DOM‐TiO2 support ensured efficient contact between soot particles and the catalyst.The large interface area between the ultrafine Pd NPs and the TiO2 also increased the density of sites for O2 activation as a result of the strong metal(Pd)‐support(TiO2)interaction(SMSI).A Pd/3DOM‐TiO2‐GBMR catalyst with ultrafine Pd NPs(1.1 nm)exhibited higher catalytic activity during diesel soot combustion compared with that obtained from a specimen having relatively large Pd NPs(5.0 nm).The T10,T50 and T90 values obtained from the former were 295,370 and 415°C.Both the activity and nanostructure of the Pd/3DOM‐TiO2‐GBMR catalyst were stable over five replicate soot oxidation trials.These results suggest that nanocatalysts having a 3DOM structure together with ultrafine Pd NPs can decrease the amount of Pd required,and that this approach has potential practical applications in the catalytic combustion of diesel soot particles.展开更多
Three-dimensionally ordered（3DOM） macroporous phosphotungstic acid/SiO_2（HPW/SiO_2） materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization（ODS） of the model fue...Three-dimensionally ordered（3DOM） macroporous phosphotungstic acid/SiO_2（HPW/SiO_2） materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization（ODS） of the model fuel oil. The obtained HPW/SiO_2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N_2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO_2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene（DBT） could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.展开更多
Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is f...Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is fabricated by coupling TiO_(2)with three dimensionally ordered macroporous sulfur-doped graphitic carbon nitride(3DOM SCN/T)by electrostatic self-assembly.The optimized photocatalyst achieved a high photocatalytic H_(2)O_(2)production activity with a yield of 2128μmol h^(−1)g^(−1)without the addition of hole scavengers.The remarkable performance was attributed to the synergy between the 3DOM framework and the S-scheme heterojunction.The former enhances light harvesting and provides abundant active sites for surface reactions,while the latter promotes the spatial separation of photogenerated carriers and enhances the redox power.Finally,the mechanism of photocatalytic H_(2)O_(2)production over the 3DOM SCN/T S-scheme composite is proposed.This work provides novel insights into the development of effi-cient photocatalysts for H_(2)O_(2)production from water and O_(2).展开更多
Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance betw...Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance between slow Na^(+)reaction kinetics of battery-type anodes and rapid ion adsorption/desorption of capacitive cathodes is a significant challenge.Here,we propose the high-rate-performance NiS_(2)@OMGC anode material composed of monodispersed NiS_(2) nanocrystals(8.8±1.7 nm in size)and N,S-co-doped graphenic carbon(GC).The NiS_(2)@OMGC material has a three-dimensionally ordered macroporous(3DOM)morphology,and numerous NiS_(2) nanocrystals are uniformly embedded in GC,forming a core-shell structure in the local area.Ultrafine NiS_(2) nanocrystals and their nano-microstructure demonstrate high pseudocapacitive Na-storage capability and thus excellent rate performance(355.7 mAh/g at 20.0 A/g).A SIHC device fabricated using NiS_(2)@OMGC and commercial activated carbon(AC)cathode exhibits ultrahigh energy densities(197.4 Wh/kg at 398.8 W/kg)and power densities(43.9 kW/kg at 41.3 Wh/kg),together with a long life span.This outcome exemplifies the rational architecture and composition design of this type of anode material.This strategy can be extended to the design and synthesis of a wide range of high-performance electrode materials for energy storage applications.展开更多
A series of catalysts consisting of three‐dimensionally ordered macroporous(3DOM)x‐CeO2/Al2O3‐supported Au nanoparticles(x=2,10,20,and40wt%)were successfully synthesized using a reduction‐deposition method.These c...A series of catalysts consisting of three‐dimensionally ordered macroporous(3DOM)x‐CeO2/Al2O3‐supported Au nanoparticles(x=2,10,20,and40wt%)were successfully synthesized using a reduction‐deposition method.These catalysts were characterized using scanning electron microscopy,the Brunauer‐Emmett‐Teller method,X‐ray diffraction,transmission electron microscopy,ultraviolet‐visible spectroscopy,and temperature‐programmed reduction by H2.Au nanoparticles of mean particle size5nm were well dispersed and supported on the inner walls of uniform macropores.The3DOM structure improved the contact efficiency between soot and the catalyst.An Al‐Ce‐O solid solution was formed in the multilayer support,i.e.,x‐CeO2/Al2O3,by the incorporation of Al3+ions into the CeO2lattice,which resulted in the creation of extrinsic oxygen vacancies.Strong interactions between the metal(Au)and the support(Ce)increased the amount of active oxygen species,and this promoted soot oxidation.The catalytic performance in soot combustion was evaluated using a temperature‐programmed oxidation technique.The presence of CeO2nanolayers in the3DOM Au/x‐CeO2/Al2O3catalysts clearly improved the catalytic activities in soot oxidation.Among the prepared catalysts,3DOM Au/20%CeO2/Al2O3showed high catalytic activity and stability in diesel soot oxidation.展开更多
Three dimensionally ordered macroporous （3DOM） Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template （CCT） route. The as-synthesized catalysts showed well- ordered stru...Three dimensionally ordered macroporous （3DOM） Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template （CCT） route. The as-synthesized catalysts showed well- ordered structures with macropores and small interconnected pore windows. The Raman results indi- cate that the catalyst persists pure fluorite cubic phases until the molar ratio of Mn exceeds O.3, therefore MnOx particles form and impede the contact of the active site and the reagent and restraining soot combustion. The doping of Nd into MnOx-CeO2 enhances the catalytic activity because of increased oxygen vacancy, Mn4- content and stronger redox ability. Nd-doping also improves thermal stability of the catalyst due to less sintering and none phase separation after thermal aging. The flesh and aged Mno.3Ceo.6Ndo.lO2 catalysts show the maximum oxidation rate for soot at 331 and 355 ℃in the O2/N2 atmosphere, achieving a nearly 100% CO2 selectivity.展开更多
PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene(PS) colloidal particles.The reaction parameters,such as initial tetraethyl orthosilicate(TEOS) concentration,wat...PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene(PS) colloidal particles.The reaction parameters,such as initial tetraethyl orthosilicate(TEOS) concentration,water concentration and reaction temperature,have been investigated to control the thickness of silica shells.The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration,reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration.It was also found that the shell thickness decreased firstly with the reaction temperature added,then tended to a constant.The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film,then sintered at 570℃ into the ordered macroporous thin film.Compared with the conditional method,the present approach avoids repeatedly filling the precursor in the templetes and save time more.展开更多
基金supported by the National Youth Talent Support Program(No.QNBJ-2022-03)the National Natu-ral Science Foundation of China(No.52371180)the Fundamental Research Funds for the Central Universities(Nos.N2209005 and N2309001).
文摘Two novel out-of-plane ordered quaternary borides M'_(4)VSiB_(2) (M'=Nb and Mo) have been synthesized. The out-of-plane ordered characteristic has been confirmed by the X-ray diffraction, the neutron powder diffraction and the scanning transmission electron microscopy with high-angle angular dark field images. By adjusting the stoichiometric ratio of Mo and V, the 16l site preferentially occupied by relatively larger atom and 4c site by relatively smaller atom have been confirmed. The further first-principle calculation demonstrates the dynamical and thermodynamical stability of Mo_(4)VSiB_(2) o-T2 phase. This work confirms the transition metal occupation strategy of o-T2 phase and enriches the out-of-plane ordered laminated borides family.
基金Supported by the National Science and Technology Major Project of China(2024ZD1400101)China National Key Research and Development Project(2022YFF0801204)Major Science and Technology Project of CNPC(2023ZZ15YJ01,2021DJ0702)。
文摘Guided by the fundamental principles of the whole petroleum system,the control of tectonism,sedimentation,and diagenesis on hydrocarbon accumulation in a rifted basin is studied using the data of petroleum geology and exploration of the second member of the Paleogene Kongdian Formation(Kong-2 Member)in the Cangdong Sag,Bohai Bay Basin,China.It is clarified that the circle structure and circle effects are the marked features of a continental fault petroliferous basin,and they govern the orderly distribution of conventional and unconventional hydrocarbons in the whole petroleum systems of the rifted basin.Tectonic circle zones control sedimentary circle zones,while sedimentary circle zones and diagenetic circle zones control the spatial distribution of favorable reservoirs,thereby determining the orderly distribution of hydrocarbon accumulations in various circles.A model for the integrated,systematic accumulation of conventional and unconventional hydrocarbons under a multi-circle structure of the whole petroleum system of continental rifted basin has been developed.It reveals that each sag of the rifted basin is an independent whole petroleum system and circle system,which encompasses multiple orderly circles of conventional and unconventional hydrocarbons controlled by the same source kitchen.From the outer circle to the middle circle and then to the inner circle,there is an orderly transition from structural and stratigraphic reservoirs,to lithological and structural-lithological reservoirs,and finally to tight oil/gas and shale oil/gas enrichment zones.The significant feature of the whole petroleum system is the orderly control of hydrocarbons by multi-circle stratigraphic coupling,with the integrated,orderly distribution of conventional and unconventional reserves being the inevitable result of the multi-layered interaction within the whole petroleum system.This concept of multi-circle stratigraphic coupling for the orderly,integrated accumulation of conventional and unconventional hydrocarbons has guided significant breakthroughs in the overall,three-dimensional exploration and shale oil exploration in the Cangdong Sag.
基金supported by the National Natu-ral Science Foundation of China(Grants No.12174220 and No.12074217)the Shandong Provincial Science Foundation for Excellent Young Scholars(Grant No.ZR2023YQ001)+1 种基金the Taishan Young Scholar Program of Shandong Provincethe Qilu Young Scholar Pro-gram of Shandong University.
文摘Higher-order band topology not only enriches our understanding of topological phases but also unveils pioneering lower-dimensional boundary states,which harbors substantial potential for next-generation device applications.The distinct electronic configurations and tunable attributes of two-dimensional materials position them as a quintessential platform for the realization of second-order topological insulators(SOTIs).This article provides an overview of the research progress in SOTIs within the field of two-dimensional electronic materials,focusing on the characterization of higher-order topological properties and the numerous candidate materials proposed in theoretical studies.These endeavors not only enhance our understanding of higher-order topological states but also highlight potential material systems that could be experimentally realized.
基金supported by the National Natural Science Foundation of China(Nos.22193042,22125110,22075285,52473283,21921001,U21A2069)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBS-LY-SLH024)the Youth Innovation Promotion of Chinese Academy of Sciences(No.2020307)。
文摘Polar semiconductors,particularly the emerging polar two-dimensional(2D)halide perovskites,have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarizationgenerated photoelectric effects.However,the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra.Herein,a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPb Br_(4)(NMPB,NMA is N-methylbenzene ammonium,MA is methylammonium)with alternating cation in the interlayer space.Driven by the incorporation of a second MA cation,the perovskite layer transformed from a 2D Pb_(7)Br_(24)anionic network with corner-and face-sharing octahedra to a flat 2D PbBr_(4)perovskite networks only with corner-sharing octahedra.In the crystal structure of NMPB,the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3μC/cm^(2).More intriguingly,the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance,showing a considerable polarization-related dichroism ratio up to 1.87.The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties,overcoming limitations of conventional cation choice.
基金was supported by the National Key Research and Development Program of China(Grant Nos.2024YFA1611200 and 2018YFA0307000)the National Natural Science Foundation of China(Grant Nos.12274154 and 12404182)。
文摘In order to calculate the multipoles in real materials with considerable intersite Coulomb interaction V,we develop a self-consistent program which starts from the frst-principles calculations to solve the tight-binding Hamiltonian including onsite Coulomb repulsion U,V,and spin-orbital couplingλ.The program is applied to Ba_(2)MgReO_(6)to fgure out the mechanism of structural instability and magnetic ordering.A comprehensive quadrupole phase diagram versus U and V withλ=0.28 eV is calculated.Our results demonstrate that the easy-plane anisotropy and the intersite Coulomb repulsion V must be considered to remove the orbital frustration.The increase of V to>20 meV would arrange quadrupole Q_(x^(2)-y^(2))antiparallelly,accompanied by small parallel Q_(3z)^(2)-r^(2),and stabilize Ba_(2)MgReO_(6)into the body-centered tetragonal structure.Such antiparallel Q_(x^(2)-y^(2))provides a new mechanism for the Dzyaloshinskii-Moriya interaction and gives rise to the canted antiferromagnetic(CAF)state along the[110]axis.Moreover,sizable octupoles such as O_(21)^(31),O_(21)^(33),O_(21)^(34)and O_(21)^(36)are discovered for the frst time in the CAF state.Our study not only provides a comprehensive understanding of the experimental results in Ba_(2)MgReO_(6),but also serves as a general and useful tool for the study of multipole physics in 5d compounds.
基金Project (BK2010392) supported by the Natural Science Foundation of Jiangsu Province of ChinaProject (3212000502) supported by the Innovation Foundation of Southeast University,China
文摘The microstructure and mechanical properties of Mg94Zn2Y4 extruded alloy containing long-period stacking ordered structures were systematically investigated by SEM and TEM analyses. The results show that the 18R-LPSO structure and α-Mg phase are observed in cast Mg94Zn2Y4 alloy. After extrusion, the LPSO structures are delaminated and Mg-slices with width of 50-200 nm are generated. By ageing at 498 K for 36 h, the ageing peak is attained andβ′phase is precipitated. Due to this novel precipitation, the microhardness ofα-Mg matrix increases apparently from HV108.9 to HV129.7. While the microhardness for LPSO structure is stabilized at about HV145. TEM observations and SAED patterns indicate that the β′ phase has unique orientation relationships betweenα-Mg and LPSO structures, the direction in the close-packed planes ofβ′precipitates perpendicular to that ofα-Mg and LPSO structures. The ultimate tensile strength for the peak-aged alloy achieves 410.7 MPa and the significant strength originates from the coexistence ofβ′precipitates and 18R-LPSO structures.
基金supported by the National Natural Science Foundation of China(21876114,21761142011,51572174)Shanghai Government(17SG44)+2 种基金International Joint Laboratory on Resource Chemistry(IJLRC)Ministry of Education of China(PCSIRT_IRT_16R49)supported by The Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning and Shuguang Research Program of Shanghai Education Committee~~
文摘Ordered mesoporous Fe/TiO2 was prepared by an evaporation-induced self-assembly method. The iron ions were in situ embedded in the pore wall of the TiO2 framework. The catalyst has excellent light-assisted Fenton catalytic performance under UV and visible light irradiation. X-ray diffraction and transmission electron microscopy results showed that the TiO2 samples have an ordered two-dimensional hexagonal pore structure and an anatase phase structure with high crystallinity. The ordered pore structure of the TiO2 photocatalyst with a large specific surface area is beneficial to mass transfer and light harvesting. Furthermore, iron ions can be controlled by embedding them into the TiO2 framework to prevent iron ion loss and inactivation. After five cycles, the reaction rate of the ordered mesoporous Fe/TiO2 remained unchanged, indicating that the material has stable performance and broad application prospects for the purification of environmental pollutants.
基金Supported by the National Nature Science Foundation of China(No.21476177)
文摘A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.
基金supported by the National Natural Science Foundation of China(21673142,21477164)the National High Technology Research and Development Program of China(863 Program,2015AA030903)~~
文摘Nanocatalysts consisting of three‐dimensionally ordered macroporous(3DOM)TiO2‐supported ultrafine Pd nanoparticles(Pd/3DOM‐TiO2‐GBMR)were readily fabricated by gas bubbling‐assisted membrane reduction(GBMR)method.These catalysts had a well‐defined and highly ordered macroporous nanostructure with an average pore size of 280 nm.In addition,ultrafine hemispherical Pd nanoparticles(NPs)with a mean particle size of 1.1 nm were found to be well dispersed over the surface of the 3DOM‐TiO2 support and deposited on the inner walls of the material.The nanostructure of the 3DOM‐TiO2 support ensured efficient contact between soot particles and the catalyst.The large interface area between the ultrafine Pd NPs and the TiO2 also increased the density of sites for O2 activation as a result of the strong metal(Pd)‐support(TiO2)interaction(SMSI).A Pd/3DOM‐TiO2‐GBMR catalyst with ultrafine Pd NPs(1.1 nm)exhibited higher catalytic activity during diesel soot combustion compared with that obtained from a specimen having relatively large Pd NPs(5.0 nm).The T10,T50 and T90 values obtained from the former were 295,370 and 415°C.Both the activity and nanostructure of the Pd/3DOM‐TiO2‐GBMR catalyst were stable over five replicate soot oxidation trials.These results suggest that nanocatalysts having a 3DOM structure together with ultrafine Pd NPs can decrease the amount of Pd required,and that this approach has potential practical applications in the catalytic combustion of diesel soot particles.
基金the National Nature Science Foundation of China(No.21476177)
文摘Three-dimensionally ordered（3DOM） macroporous phosphotungstic acid/SiO_2（HPW/SiO_2） materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization（ODS） of the model fuel oil. The obtained HPW/SiO_2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N_2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO_2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene（DBT） could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.
基金supported by the National Natural Science Foundation of China(Nos.22278324,51932007,22238009,U1905215,52073223,52073034,and 22208332)the Natural Science Foundation of Hubei Province of China(No.2022CFA001)the Innovative Research Funds of SKLWUT(No.2022-CL-A1-01).
文摘Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is fabricated by coupling TiO_(2)with three dimensionally ordered macroporous sulfur-doped graphitic carbon nitride(3DOM SCN/T)by electrostatic self-assembly.The optimized photocatalyst achieved a high photocatalytic H_(2)O_(2)production activity with a yield of 2128μmol h^(−1)g^(−1)without the addition of hole scavengers.The remarkable performance was attributed to the synergy between the 3DOM framework and the S-scheme heterojunction.The former enhances light harvesting and provides abundant active sites for surface reactions,while the latter promotes the spatial separation of photogenerated carriers and enhances the redox power.Finally,the mechanism of photocatalytic H_(2)O_(2)production over the 3DOM SCN/T S-scheme composite is proposed.This work provides novel insights into the development of effi-cient photocatalysts for H_(2)O_(2)production from water and O_(2).
基金supported by the National Natural Science Foundation of Tianjin(No.20JCQNJC01280)the National Natural Science Foundation of China(No.21905201)+1 种基金the support of the scientifi c research project from China Three Gorges Corporation(No.202103406)supported by Tohoku University and JSPS KAKENHI(No.JP16J06828).
文摘Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance between slow Na^(+)reaction kinetics of battery-type anodes and rapid ion adsorption/desorption of capacitive cathodes is a significant challenge.Here,we propose the high-rate-performance NiS_(2)@OMGC anode material composed of monodispersed NiS_(2) nanocrystals(8.8±1.7 nm in size)and N,S-co-doped graphenic carbon(GC).The NiS_(2)@OMGC material has a three-dimensionally ordered macroporous(3DOM)morphology,and numerous NiS_(2) nanocrystals are uniformly embedded in GC,forming a core-shell structure in the local area.Ultrafine NiS_(2) nanocrystals and their nano-microstructure demonstrate high pseudocapacitive Na-storage capability and thus excellent rate performance(355.7 mAh/g at 20.0 A/g).A SIHC device fabricated using NiS_(2)@OMGC and commercial activated carbon(AC)cathode exhibits ultrahigh energy densities(197.4 Wh/kg at 398.8 W/kg)and power densities(43.9 kW/kg at 41.3 Wh/kg),together with a long life span.This outcome exemplifies the rational architecture and composition design of this type of anode material.This strategy can be extended to the design and synthesis of a wide range of high-performance electrode materials for energy storage applications.
基金supported by the National High Technology Research and Development Program of China(863 Program,2015AA034603)the National Natural Science Foundation of China(21477146,21673142 and 21303263)+2 种基金the Beijing Nova Program(Z141109001814072)the Specialized Research Fund for the Doctoral Program of Higher Education(20130007120011)the Science Foundation of China University of Petroleum-Beijing(YJRC-2013-13,2462013BJRC003)~~
文摘A series of catalysts consisting of three‐dimensionally ordered macroporous(3DOM)x‐CeO2/Al2O3‐supported Au nanoparticles(x=2,10,20,and40wt%)were successfully synthesized using a reduction‐deposition method.These catalysts were characterized using scanning electron microscopy,the Brunauer‐Emmett‐Teller method,X‐ray diffraction,transmission electron microscopy,ultraviolet‐visible spectroscopy,and temperature‐programmed reduction by H2.Au nanoparticles of mean particle size5nm were well dispersed and supported on the inner walls of uniform macropores.The3DOM structure improved the contact efficiency between soot and the catalyst.An Al‐Ce‐O solid solution was formed in the multilayer support,i.e.,x‐CeO2/Al2O3,by the incorporation of Al3+ions into the CeO2lattice,which resulted in the creation of extrinsic oxygen vacancies.Strong interactions between the metal(Au)and the support(Ce)increased the amount of active oxygen species,and this promoted soot oxidation.The catalytic performance in soot combustion was evaluated using a temperature‐programmed oxidation technique.The presence of CeO2nanolayers in the3DOM Au/x‐CeO2/Al2O3catalysts clearly improved the catalytic activities in soot oxidation.Among the prepared catalysts,3DOM Au/20%CeO2/Al2O3showed high catalytic activity and stability in diesel soot oxidation.
基金Project supported by the National Natural Science Foundation of China(21006130,51274261)
文摘Three dimensionally ordered macroporous （3DOM） Ce-based catalysts were successfully prepared via a surfactant-assisted colloidal crystal template （CCT） route. The as-synthesized catalysts showed well- ordered structures with macropores and small interconnected pore windows. The Raman results indi- cate that the catalyst persists pure fluorite cubic phases until the molar ratio of Mn exceeds O.3, therefore MnOx particles form and impede the contact of the active site and the reagent and restraining soot combustion. The doping of Nd into MnOx-CeO2 enhances the catalytic activity because of increased oxygen vacancy, Mn4- content and stronger redox ability. Nd-doping also improves thermal stability of the catalyst due to less sintering and none phase separation after thermal aging. The flesh and aged Mno.3Ceo.6Ndo.lO2 catalysts show the maximum oxidation rate for soot at 331 and 355 ℃in the O2/N2 atmosphere, achieving a nearly 100% CO2 selectivity.
基金Supported by the National Natural Science Foundation of China(No.:20221603)
文摘PS/SiO2 particles with core-shell structure were synthesized by coating silica on surface of polystyrene(PS) colloidal particles.The reaction parameters,such as initial tetraethyl orthosilicate(TEOS) concentration,water concentration and reaction temperature,have been investigated to control the thickness of silica shells.The shell thickness was prepositional to the square root of the initial concentration of TEOS and first increased with increasing water concentration,reached a maximum at about 2.0 mol/L and then started decreasing beyond that concentration.It was also found that the shell thickness decreased firstly with the reaction temperature added,then tended to a constant.The so-synthesized PS/SiO2 core-shell particles were directly crystallized into 3-D ordered thin film,then sintered at 570℃ into the ordered macroporous thin film.Compared with the conditional method,the present approach avoids repeatedly filling the precursor in the templetes and save time more.
