The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the relate...The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the related EMW loss mechanisms for current researches.In this study,a novel two-dimensional MXene(Ti_(3)C_(2)T_(x))nanosheet decorated with Ni nanoclusters(Ni-NC)system to construct an effective electron localization model based on electronic orbital structure is explored.Theoretical simulations and experimental results reveal that the metal-support interaction between Ni-NC and MXene disrupts symmetric electronic environments,leading to enhanced electron localization and dipole polarization.Additionally,Ni-NC generate a strong interfacial electric field,strengthening heterointerface interactions and promoting interfacial polarization.As a result,the optimized material achieves an exceptional reflection loss(RLmin)of-54 dB and a broad effective absorption bandwidth of 6.8 GHz.This study offers critical insights into the in-depth relationship between electron localization and EMW dissipation,providing a pathway for electron localization engineering in functional materials such as semiconductors,spintronics,and catalysis.展开更多
Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts f...Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.展开更多
Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structu...Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO_(2)into formate with high activity and selectivity in a wide potential window.By combining experimental and computational investigations,our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO_(2)reduction and in the competing hydrogen evolution.By comparing the experimental observations with the density functional theory,the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled.This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO_(2)conversion.展开更多
We theoretically investigate the electron localization around two nuclei in harmonic emission from asymmetric molecular ion. The results show that the ionization process of electron localized around one nucleus compet...We theoretically investigate the electron localization around two nuclei in harmonic emission from asymmetric molecular ion. The results show that the ionization process of electron localized around one nucleus competes with its transfer process to the other nucleus. By increasing the initial vibrational level, more electrons localized around the nucleus D＋ tend to transfer to the nucleus He2＋ so that the ionizations of electrons localized around the nucleus He2＋ increase. In this case, the difference in harmonic efficiency between Hell2＋ and HeD2＋ decreases while the difference in harmonic spectral structure increases. The evident minimum can be observed the spectral structure of HeD2＋, which is due to the strong in the harmonic spectrum of Hell2＋ compared with that in interference of multiple recombination channels originating from two nuclei. Time-dependent nuclear probability density, electron-nuclear probability density, double-well model, and time-frequency maps are presented to explain the underlying mechanisms.展开更多
The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, e...The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, especially, Cu-Sb-No three center conjugated π bonds and No-St-No conjugated π bonds were accounted for.展开更多
Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was ...Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was pointed out that the interstitial transition metal atom Co in the octahedral Sc skeleton forms strong covalent bond with six Sc atoms and the bonding of Sc- Cl is mainly ionic in character.There are nine valence molecular orbitals in the cluster.展开更多
The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and th...The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and the rim π-bonds with larger localization form reactive regions for formation of buckminsterfullerene.展开更多
The recent discovery of three-dimensional（3D） topological insulators（TIs） has provided a fertile ground for obtaining further insights into electron localization in condensed matter systems.In the past few years,a...The recent discovery of three-dimensional（3D） topological insulators（TIs） has provided a fertile ground for obtaining further insights into electron localization in condensed matter systems.In the past few years,a tremendous amount of research effort has been devoted to investigate electron transport properties of 3D TIs and their low dimensional structures in a wide range of disorder strength,covering transport regimes from weak antilocalization to strong localization.The knowledge gained from these studies not only offers sensitive means to probe the surface states of 3D TIs but also forms a basis for exploring novel topological phases.In this article,we briefly review the main experimental progress in the study of the localization in 3D TIs,with a focus on the latest results on ultrathin TI films.Some new transport data will also be presented in order to complement those reported previously in the literature.展开更多
Changes of calmodulin (CaM) distribution in the embryo sac of rice (Oryza sativa subsp. Japonica) at various stages before and after fertilization have been investigated by using immunogold electron microscopy. Before...Changes of calmodulin (CaM) distribution in the embryo sac of rice (Oryza sativa subsp. Japonica) at various stages before and after fertilization have been investigated by using immunogold electron microscopy. Before pollination, both cytoplasm and vacuoles of the egg cell, synergids and central cell were labeled by gold particles. A small amount of gold particles were localized in the nucleus, endoplasmic reticulum, mitochondria and dictyosomes. From pollination to fertilization, CaM amount increased in these cells, especially rich in the starch of amyloplasts. Increase of gold particles in the central cell began about 2 h earlier than that in the egg cell. There was no distinct difference of CaM amount between the degenerated and the persistent synergids. It is interesting to observe an obvious change of CaM distribution form during pollination and fertilization from scattered single particles to clustered particles, and back again to single particles after the fertilization finished. CaM was also localized extracellularly in the embryo sac wall as well as in the wall and intercellular space of nucellus cells. The extracellular CaM also changes in its amount and form after pollination. These results suggest that CaM, either intra- or extra-cellular, may play important roles in fertilization and zygote formation.展开更多
To improve the microstructure and properties of the electron beam welded joints, the vacuum or furnace whole post weld heat treatment (FWPWHT) usually should be done on it. The electron beam local post weld heat treat...To improve the microstructure and properties of the electron beam welded joints, the vacuum or furnace whole post weld heat treatment (FWPWHT) usually should be done on it. The electron beam local post weld heat treatment (EBLPWHT) is a rather new heat treatment procedure that provides the advantages of high precision, flexibility and efficiency, energy saving and higher productivity. In this paper, the microstructure, mechanical properties, fracture toughness and fatigue properties of electron beam welded joints of 30CrMnSiNi2A steel in as-welded (AW) and EBLPWHT conditions have been investigated respectively. The results show that the microstructures of different zones of joints in as-welded condition are changed by EBLPWHT procedure, in which the welds from coarse needle martensite into lath-shaped martensite; the main structures of heat affected zones (HAZ) from lath-shaped martensite into lower bainite. The properties of welded joints can be improved by the EBLPWHT in some extent, especially the fracture toughness of the welds and the fatigue crack resistance of welded joints can be sufficiently improved. However, more appropriate heat treatment parameters of the EBLPWHT have to be studied in order to increase the mechanical properties of base metal near by the HAZ.展开更多
Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilit...Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilities of various CeO2 （100） termination structures are discussed, and calculated energetics are presented. The most stable Ce〇2 （100） surface was obtained by removing half the outermost full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO2 （100） surface, we determined that the formation of carbonate species competed with CO2 desorption. However, during CO oxidation on the less stable CeO2 （100） surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO2 formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4/ orbitals are directly involved in deter-mining the surface stabilities and reactivities.展开更多
A three-dimensional finite-element model (FEM) used for calculating electron beam (EB) welding temperature and stresses fields of thin plates of BT20 titanium has been developed in which the nonlinear thermophysical a...A three-dimensional finite-element model (FEM) used for calculating electron beam (EB) welding temperature and stresses fields of thin plates of BT20 titanium has been developed in which the nonlinear thermophysical and thermo-mechanical properties of the material has been considered. The welding temperature field, the distributions of residual stresses in as-welded (AW) and electron beam local post-weld heat treatment (EBLPWHT) conditions have been successfully simulated. The results show that: (1) In the weld center, the maximum magnitude of residual tensile stresses of BT20 thin plates of Ti alloy is equal to 60%- 70% of its yield strength σs. (2) The residual tensile stresses in weld center can be even decreased after EBLPWHT and the longitudinal tensile stresses are decreased about 50% compared to joints in AW conditions. (3) The numerical calculating results of residual stresses by using FEM are basically in agreement with the experimental results. Combined with numerical calculating results, the effects of electron beam welding and EBLPWHT on the distribution of welding residual stresses in thin plates of BT20 have been analyzed in detail.展开更多
The Coulomb potential recapture effect in above-barrier ionization with ultrashort long-wavelength laser pulses is investigated theoretically by solving the one-dimensional time-dependent Schrodinger equation. We find...The Coulomb potential recapture effect in above-barrier ionization with ultrashort long-wavelength laser pulses is investigated theoretically by solving the one-dimensional time-dependent Schrodinger equation. We find that electrons can be recaptured with considerable possibility by the Coulomb potential near the end of the pulse though atoms are ionized almost completely within the first few half optical cycles. Therefore there is a high probability of the atom surviving after the pulse. We also check this process in the three-dimensional case and find that this kind of stabilization can still exist in three-dimensional atoms.展开更多
Local electron mean energy （LEME） has a direct effect on the rates of collisional ionization of molecules and atoms by electrons. Electron-impact ionization plays an important role and is the main process for the pr...Local electron mean energy （LEME） has a direct effect on the rates of collisional ionization of molecules and atoms by electrons. Electron-impact ionization plays an important role and is the main process for the production of charged particles in a primary streamer discharge. Detailed research on the LEME profile in a primary streamer discharge is extremely important for a comprehensive understanding of the local physical mechanism of a streamer. In this study, the LEME profile of the primary streamer discharge in oxygen-nitrogen mixtures with a pin-plate gap of 0.5 cm under an impulse voltage is investigated using a fluid model. The fluid model includes the electron mean energy density equation, as well as continuity equations for electrons and ions and Poisson＇s electric field equation. The study finds that, except in the initial stage of the primary streamer, the LEME in the primary streamer tip tends to increase as the oxygen-nitrogen mole ratio increases and the pressure decreases. When the primary streamer bridges the gap, the LEME in the primary streamer channel is smaller than the first ionization energies of oxygen and nitrogen. The LEME in the primary streamer channel then decreases as the oxygen-nitrogen mole ratio increases and the pressure increases. The LEME in the primary streamer tip is primarily dependent on the reduced electric field with mole ratios of oxygen-nitrogen given in the oxygen-nitrogen mixtures.展开更多
The pursuit of high energy density has promoted the development of high-performance lithium metal batteries(LMBs).However,the underestimated but non-negligible dendrites of Li anode have been observed to shorten batte...The pursuit of high energy density has promoted the development of high-performance lithium metal batteries(LMBs).However,the underestimated but non-negligible dendrites of Li anode have been observed to shorten battery lifespan.Herein,a composite separator(TiO_(2-x)@PP),in which TiO_(2)with electron-localized oxygen vacancies(TiO_(2-x))is coated on a commercial PP separator,is fabricated to homogenize lithium ion transport and stabilize the lithium anode interface.With the utilization of TiO_(2-x)@PP separators,the symmetric lithium metal battery displays enhanced cycle stability over 800 h under a high current density of 8 m A cm^(-2).Moreover,the LMBs assembled with high-loading LiFePO_(4)(9.24 mg cm^(-2))deliver a stable cycling performance over 900 cycles at a rate of 0.5 C.Comprehensive theoretical studies based on density functional theory(DFT)further unveil the mechanism.The favorable TiO_(2-x)is beneficial for facilitating fast Li+migration and impeding anions transfer.In addressing the Li dendrite issues,the use of TiO_(2-x)@PP separator potentially provides a facile and attractive strategy for designing well-performing LMBs,which are expected to meet the application requirements of rechargeable batteries.展开更多
The effects of two post-weld heat treatment processes on the microstructure and fatigue properties of the electron beam welded joints of 30CrMnSiNi2A steel were studied. Electron beam local post-weld heat treatment (E...The effects of two post-weld heat treatment processes on the microstructure and fatigue properties of the electron beam welded joints of 30CrMnSiNi2A steel were studied. Electron beam local post-weld heat treatment (EBLPWHT), in a vacuum chamber, immediately after welding and a traditional furnace whole post-weld heat treatment (FWPWHT) were accepted. The experimental results show that, after EBLPWHT, the main microstructure of weld is changed from coarse acicular martensite into lath martensite, and base metal is changed from ferrite and perlite into upper bainite and residual austenite, however the microstructures of different zones of joints in FWPWHT conditions are tempered sorbite. The fatigue crack growth rate da/dN of welds and base metal are not obviously changed among EBLPWHT, FWPWHT test and as-welded (AW) test, as the mechanical properties of materials have a certain but not large effect on the da/dN of welded joints. The resistance to near threshold fatigue crack growth data of welded joints can be largely improved by EBLPWHT and it is related to microstructure and crack closure effect.展开更多
Defect engineering presents great promise in addressing lower specific capacity,sluggish diffusion kinetics and poor cycling life issues in energy storage devices.Herein,multidimensional(0D/2D/3D) structural defects a...Defect engineering presents great promise in addressing lower specific capacity,sluggish diffusion kinetics and poor cycling life issues in energy storage devices.Herein,multidimensional(0D/2D/3D) structural defects are constructed in WO_(3)/MoO_(2) simultaneously via competing for and sharing with O atoms during simple hydrothermal process.OD and 2D defects tailor local electron,activating more sites and generating built-in electric fields to yield ion reservoir,meanwhile,3D defect owning lower anisotropic property tailors Mg^(2+) diffusion channels to fully exploit Mg^(2+) adsorbed sites induced by OD and 2D defects,enhance the kinetics and maintain structural stability.Benefitted from synergistic effect of 0D/2D/3D structural defects,the designed WO_(3)/MoO_(2) shows the higher specific capacity(112.8 mA h g^(-1) at 50 mA g^(-1) with average attenuation rate per cycle of 0.068%),superior rate capability and excellent cycling stability(specific capacity retention of 80% after 1500 cycles at 1000 mA g^(-1)).This strategy provides design ideas of introducing multidimensional structural defects for tailoring local electron and microstructure to improve energy storage property.展开更多
Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex con...Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex concentrated solution,a variety of sub-systems of species exist to induce the metastable ordered compounds as candidates for ultimate CSROs.The issues remain pending on the origin of CSROs as to how to judge if CSRO will form in an H/MEA and particularly,what kind of CSROs would be stably produced if there were multiple possibilities.Here,the first-principles method,along with the proposed local formation energy calculation in allusion to the atomic-scale chemical heterogeneities,is used to predict the CSRO formation based on the mechanical stability,thermodynamic formation energy,and electronic characteristics.The simulations are detailed in an equiatomic ternary VCoNi MEA with three kinds of potential compounds,i.e.,L1_(1),L1_(2),and B2,in the face-centered cubic matrix.It turns out that L1_(1)is stable but hard to grow up so as to become the final CSRO.L1_(1)is further predicted as CSROs in CrCoNi,but unable to form in FeCoNi and CrMnFeCoNi alloys.These predictions are consistent with the experimental observations.Our findings shed light on understanding the formation of CSROs.This method is applicable to other H/MEAs to design and tailor CSROs by tuning chemical species/contents and thermal processing for high performance.展开更多
Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with se...Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with self-activated dual-wavelength emissions toward high-sensitivity optical thermometers.Herein,a novel ratiometric thermometric strategy of Bi^(3+)-activated dual-wavelength emission band was realized in the same lattice position with two local electronic states of La_(3)Sb_(1-x)Ta_xO_(7):Bi^(3+)(0≤x≤1.0)materials based on the different temperature-dependent emission behaviors,benefiting from the highlysensitive and regulable emission to the coordination environment of Bi^(3+).The structural and spectral results demonstrate that the emission tremendously shifted from green to blue with 68 nm and the intensity was enhanced 2.6 times.Especially,the visual dual-wavelength emitting from two emission centers was presented by increasing the Ta^(5+)substitution concentration to 20%or 25%,mainly originating from the two local electronic states around the Bi^(3+)emission center.Significantly,the dual-wavelength with different thermal-quenching performance provided high-temperature sensitivity and good discrimination signals for optical thermometry in the range between 303 and 493 K.The maximum relative sensitivity reached 2.64%/K(La_(3)Sb_(0.8)Ta_(0.2)O_(7):0.04Bi^(3+)@383 K)and 1.91%/K(La_(3)Sb_(0.75)Ta_(0.25)O_(7):0.04Bi^(3+)@388 K).This work reveals a rational design strategy of different local electronic states around the singledoping multiple emission centers towards practical applications,such as luminescence thermometry and white LED lighting.展开更多
Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different...Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2展开更多
基金supported by the National Key Research and Development Program of China (Grant No. 2024YFE0100600)the National Natural Science Foundation of China (No 52373303)+2 种基金the Shanghai Municipal Science and Technology Major Project (2021SHZDZX0100)the Fundamental Research Funds for the Central Universitiesthe Interdisciplinary Joint Research and Development Project of Tongji University (No 2024-4-ZD-03)
文摘The electron localization is considered as a promising approach to optimize electromagnetic waves(EMW)dissipation.However,it is still difficult to realize well-controlled electron localization and elucidate the related EMW loss mechanisms for current researches.In this study,a novel two-dimensional MXene(Ti_(3)C_(2)T_(x))nanosheet decorated with Ni nanoclusters(Ni-NC)system to construct an effective electron localization model based on electronic orbital structure is explored.Theoretical simulations and experimental results reveal that the metal-support interaction between Ni-NC and MXene disrupts symmetric electronic environments,leading to enhanced electron localization and dipole polarization.Additionally,Ni-NC generate a strong interfacial electric field,strengthening heterointerface interactions and promoting interfacial polarization.As a result,the optimized material achieves an exceptional reflection loss(RLmin)of-54 dB and a broad effective absorption bandwidth of 6.8 GHz.This study offers critical insights into the in-depth relationship between electron localization and EMW dissipation,providing a pathway for electron localization engineering in functional materials such as semiconductors,spintronics,and catalysis.
基金support from the National Natural Science Foundation of China(22278006)Open Project Fund from Guangdong Provincial Key Laboratory of Materials and Technology for Energy Conversion,Guangdong Technion-Israel Institute of Technology(MATEC2024KF009)Open Research Fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D13)。
文摘Nickle-based catalysts are commonly used for CO_(2)methanation.However,there is still potential to improve their catalytic performanc under mild conditions.In this study,we synthesized a series of Ru-Ni-Al catalysts from Ru-doped NiAl-hydrotalcite using a hydrotherma method.The Ru-Ni-Al catalyst demonstrated much higher activity for CO_(2)methanation than the Ni-Al catalyst that did not have Ru doping Both experimental results and theoretical calculations indicate that the enhanced performance of the Ru-Ni-Al catalyst is related to electroni interactions between nickel(Ni)and ruthenium(Ru).The Ru sites transfer electrons to the Ni sites,increasing the local electron density of Ni which enhances the adsorption and activation of H_(2).Furthermore,the Ru-Ni metal interface sites improve the adsorption and activation of CO_(2)In situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)analysis indicates that adjusting the electronic structure of N sites can accelerate the production of intermediates HCOO^(*),while Ru-Ni intermetallic interface sites can directly dissociate CO_(2)into CO^(*).In addition,CO_(2)methanation on the Ru-Ni-Al catalyst follows HCOO^(*)-and CO^(*)-mediated pathways.This study underscores the potential fo enhancing CO_(2)methanation performance by modulating the electronic structure of Ni sites.
基金This work was supported by the Shenzhen Science and Technology Program(KQTD20190929173914967)。
文摘Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO_(2)into formate with high activity and selectivity in a wide potential window.By combining experimental and computational investigations,our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO_(2)reduction and in the competing hydrogen evolution.By comparing the experimental observations with the density functional theory,the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled.This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO_(2)conversion.
基金Project supported by the National Natural Science Foundation of China(Grant No.11404204)the Key Project of Chinese Ministry of Education(Grant No.211025)+2 种基金the Research Fund for the Doctoral Program of Higher Education of China(Grant No.20111404120004)the Natural Science Foundation for Young Scientists of Shanxi Province,China(Grant No.2009021005)the Innovation Project for Postgraduates of Shanxi Province,China(Grant No.20133081)
文摘We theoretically investigate the electron localization around two nuclei in harmonic emission from asymmetric molecular ion. The results show that the ionization process of electron localized around one nucleus competes with its transfer process to the other nucleus. By increasing the initial vibrational level, more electrons localized around the nucleus D＋ tend to transfer to the nucleus He2＋ so that the ionizations of electrons localized around the nucleus He2＋ increase. In this case, the difference in harmonic efficiency between Hell2＋ and HeD2＋ decreases while the difference in harmonic spectral structure increases. The evident minimum can be observed the spectral structure of HeD2＋, which is due to the strong in the harmonic spectrum of Hell2＋ compared with that in interference of multiple recombination channels originating from two nuclei. Time-dependent nuclear probability density, electron-nuclear probability density, double-well model, and time-frequency maps are presented to explain the underlying mechanisms.
文摘The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, especially, Cu-Sb-No three center conjugated π bonds and No-St-No conjugated π bonds were accounted for.
文摘Spin-unrestricted localized INDO method was used to calculate the electronic structure of rare earth cluster Sc(Sc_6Cl_(12)Co).Based on the analysis of the composition of the molecular orbitals and bond orders,it was pointed out that the interstitial transition metal atom Co in the octahedral Sc skeleton forms strong covalent bond with six Sc atoms and the bonding of Sc- Cl is mainly ionic in character.There are nine valence molecular orbitals in the cluster.
文摘The localized molecular orbitals for typical bowl-shaped circulenes are obtained by the use of INDO-LMO method. It is found that these bowl-shaped circulenes with strained π-electron systems are still aromatic and the rim π-bonds with larger localization form reactive regions for formation of buckminsterfullerene.
基金Project supported by the National Basic Research Program of China(Grant Nos.2012CB921703 and 2015CB921102)the National Natural Science Foundation of China(Grant Nos.61425015,11374337,and 91121003)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB070202)
文摘The recent discovery of three-dimensional（3D） topological insulators（TIs） has provided a fertile ground for obtaining further insights into electron localization in condensed matter systems.In the past few years,a tremendous amount of research effort has been devoted to investigate electron transport properties of 3D TIs and their low dimensional structures in a wide range of disorder strength,covering transport regimes from weak antilocalization to strong localization.The knowledge gained from these studies not only offers sensitive means to probe the surface states of 3D TIs but also forms a basis for exploring novel topological phases.In this article,we briefly review the main experimental progress in the study of the localization in 3D TIs,with a focus on the latest results on ultrathin TI films.Some new transport data will also be presented in order to complement those reported previously in the literature.
文摘Changes of calmodulin (CaM) distribution in the embryo sac of rice (Oryza sativa subsp. Japonica) at various stages before and after fertilization have been investigated by using immunogold electron microscopy. Before pollination, both cytoplasm and vacuoles of the egg cell, synergids and central cell were labeled by gold particles. A small amount of gold particles were localized in the nucleus, endoplasmic reticulum, mitochondria and dictyosomes. From pollination to fertilization, CaM amount increased in these cells, especially rich in the starch of amyloplasts. Increase of gold particles in the central cell began about 2 h earlier than that in the egg cell. There was no distinct difference of CaM amount between the degenerated and the persistent synergids. It is interesting to observe an obvious change of CaM distribution form during pollination and fertilization from scattered single particles to clustered particles, and back again to single particles after the fertilization finished. CaM was also localized extracellularly in the embryo sac wall as well as in the wall and intercellular space of nucellus cells. The extracellular CaM also changes in its amount and form after pollination. These results suggest that CaM, either intra- or extra-cellular, may play important roles in fertilization and zygote formation.
文摘To improve the microstructure and properties of the electron beam welded joints, the vacuum or furnace whole post weld heat treatment (FWPWHT) usually should be done on it. The electron beam local post weld heat treatment (EBLPWHT) is a rather new heat treatment procedure that provides the advantages of high precision, flexibility and efficiency, energy saving and higher productivity. In this paper, the microstructure, mechanical properties, fracture toughness and fatigue properties of electron beam welded joints of 30CrMnSiNi2A steel in as-welded (AW) and EBLPWHT conditions have been investigated respectively. The results show that the microstructures of different zones of joints in as-welded condition are changed by EBLPWHT procedure, in which the welds from coarse needle martensite into lath-shaped martensite; the main structures of heat affected zones (HAZ) from lath-shaped martensite into lower bainite. The properties of welded joints can be improved by the EBLPWHT in some extent, especially the fracture toughness of the welds and the fatigue crack resistance of welded joints can be sufficiently improved. However, more appropriate heat treatment parameters of the EBLPWHT have to be studied in order to increase the mechanical properties of base metal near by the HAZ.
基金supported the National Natural Science Foundation of China(21421004,21573067)~~
文摘Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilities of various CeO2 （100） termination structures are discussed, and calculated energetics are presented. The most stable Ce〇2 （100） surface was obtained by removing half the outermost full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO2 （100） surface, we determined that the formation of carbonate species competed with CO2 desorption. However, during CO oxidation on the less stable CeO2 （100） surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO2 formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4/ orbitals are directly involved in deter-mining the surface stabilities and reactivities.
文摘A three-dimensional finite-element model (FEM) used for calculating electron beam (EB) welding temperature and stresses fields of thin plates of BT20 titanium has been developed in which the nonlinear thermophysical and thermo-mechanical properties of the material has been considered. The welding temperature field, the distributions of residual stresses in as-welded (AW) and electron beam local post-weld heat treatment (EBLPWHT) conditions have been successfully simulated. The results show that: (1) In the weld center, the maximum magnitude of residual tensile stresses of BT20 thin plates of Ti alloy is equal to 60%- 70% of its yield strength σs. (2) The residual tensile stresses in weld center can be even decreased after EBLPWHT and the longitudinal tensile stresses are decreased about 50% compared to joints in AW conditions. (3) The numerical calculating results of residual stresses by using FEM are basically in agreement with the experimental results. Combined with numerical calculating results, the effects of electron beam welding and EBLPWHT on the distribution of welding residual stresses in thin plates of BT20 have been analyzed in detail.
基金Supported by the National Natural Science Foundation of China under Grant Nos 60478031 and 10474008, the National Key Basic Research and Development Programme of China, and the ICF Research Fund under Grant No 2004AA84ts08.
文摘The Coulomb potential recapture effect in above-barrier ionization with ultrashort long-wavelength laser pulses is investigated theoretically by solving the one-dimensional time-dependent Schrodinger equation. We find that electrons can be recaptured with considerable possibility by the Coulomb potential near the end of the pulse though atoms are ionized almost completely within the first few half optical cycles. Therefore there is a high probability of the atom surviving after the pulse. We also check this process in the three-dimensional case and find that this kind of stabilization can still exist in three-dimensional atoms.
基金Project supported by the Funds for Innovative Research Groups of China (Grant No. 51021005)the National Basic Research Program of China (Grant No. 2009CB724504)the National Natural Science Foundation of China (Grant No. 50707036)
文摘Local electron mean energy （LEME） has a direct effect on the rates of collisional ionization of molecules and atoms by electrons. Electron-impact ionization plays an important role and is the main process for the production of charged particles in a primary streamer discharge. Detailed research on the LEME profile in a primary streamer discharge is extremely important for a comprehensive understanding of the local physical mechanism of a streamer. In this study, the LEME profile of the primary streamer discharge in oxygen-nitrogen mixtures with a pin-plate gap of 0.5 cm under an impulse voltage is investigated using a fluid model. The fluid model includes the electron mean energy density equation, as well as continuity equations for electrons and ions and Poisson＇s electric field equation. The study finds that, except in the initial stage of the primary streamer, the LEME in the primary streamer tip tends to increase as the oxygen-nitrogen mole ratio increases and the pressure decreases. When the primary streamer bridges the gap, the LEME in the primary streamer channel is smaller than the first ionization energies of oxygen and nitrogen. The LEME in the primary streamer channel then decreases as the oxygen-nitrogen mole ratio increases and the pressure increases. The LEME in the primary streamer tip is primarily dependent on the reduced electric field with mole ratios of oxygen-nitrogen given in the oxygen-nitrogen mixtures.
基金financial support provided by the National Natural Science Foundation of China(52064049)the Key National Natural Science Foundation of Yunnan Province(2018FA028 and 2019FY003023)+1 种基金the International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)the Key Laboratory of Solid State Ions for Green Energy of Yunnan University(2019),the Analysis and Measurements Center of Yunnan University for the sample testing service,and the Postgraduate Research and Innovation Foundation of Yunnan University(2021Y348)。
文摘The pursuit of high energy density has promoted the development of high-performance lithium metal batteries(LMBs).However,the underestimated but non-negligible dendrites of Li anode have been observed to shorten battery lifespan.Herein,a composite separator(TiO_(2-x)@PP),in which TiO_(2)with electron-localized oxygen vacancies(TiO_(2-x))is coated on a commercial PP separator,is fabricated to homogenize lithium ion transport and stabilize the lithium anode interface.With the utilization of TiO_(2-x)@PP separators,the symmetric lithium metal battery displays enhanced cycle stability over 800 h under a high current density of 8 m A cm^(-2).Moreover,the LMBs assembled with high-loading LiFePO_(4)(9.24 mg cm^(-2))deliver a stable cycling performance over 900 cycles at a rate of 0.5 C.Comprehensive theoretical studies based on density functional theory(DFT)further unveil the mechanism.The favorable TiO_(2-x)is beneficial for facilitating fast Li+migration and impeding anions transfer.In addressing the Li dendrite issues,the use of TiO_(2-x)@PP separator potentially provides a facile and attractive strategy for designing well-performing LMBs,which are expected to meet the application requirements of rechargeable batteries.
基金thefoundationoftheNationalDefenseTechnologyKeyLaboratory (No .99JS5 0 .3 .2JW14 0 2 )
文摘The effects of two post-weld heat treatment processes on the microstructure and fatigue properties of the electron beam welded joints of 30CrMnSiNi2A steel were studied. Electron beam local post-weld heat treatment (EBLPWHT), in a vacuum chamber, immediately after welding and a traditional furnace whole post-weld heat treatment (FWPWHT) were accepted. The experimental results show that, after EBLPWHT, the main microstructure of weld is changed from coarse acicular martensite into lath martensite, and base metal is changed from ferrite and perlite into upper bainite and residual austenite, however the microstructures of different zones of joints in FWPWHT conditions are tempered sorbite. The fatigue crack growth rate da/dN of welds and base metal are not obviously changed among EBLPWHT, FWPWHT test and as-welded (AW) test, as the mechanical properties of materials have a certain but not large effect on the da/dN of welded joints. The resistance to near threshold fatigue crack growth data of welded joints can be largely improved by EBLPWHT and it is related to microstructure and crack closure effect.
基金supported by the National Natural Science Foundation of China under Grant No. 52072196, 52002199, 52002200, 52102106Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No. ZR2020ZD09+5 种基金the Natural Science Foundation of Shandong Province under Grant No. ZR2019BEM042, ZR2020QE063the Innovation and Technology Program of Shandong Province under Grant No. 2020KJA004the Taishan Scholars Program of Shandong Province under No. ts201511034Postdoctoral Program in Qingdao under No. QDBSH20220202019the innovation Capability Improvement Project of Small and Medium-sized Technological Enterprises in Shandong Province under No. 2021TSGC1156the Financial Support From the Qingdao West Coast New Area Science and Technology Project under No. 2020-104。
文摘Defect engineering presents great promise in addressing lower specific capacity,sluggish diffusion kinetics and poor cycling life issues in energy storage devices.Herein,multidimensional(0D/2D/3D) structural defects are constructed in WO_(3)/MoO_(2) simultaneously via competing for and sharing with O atoms during simple hydrothermal process.OD and 2D defects tailor local electron,activating more sites and generating built-in electric fields to yield ion reservoir,meanwhile,3D defect owning lower anisotropic property tailors Mg^(2+) diffusion channels to fully exploit Mg^(2+) adsorbed sites induced by OD and 2D defects,enhance the kinetics and maintain structural stability.Benefitted from synergistic effect of 0D/2D/3D structural defects,the designed WO_(3)/MoO_(2) shows the higher specific capacity(112.8 mA h g^(-1) at 50 mA g^(-1) with average attenuation rate per cycle of 0.068%),superior rate capability and excellent cycling stability(specific capacity retention of 80% after 1500 cycles at 1000 mA g^(-1)).This strategy provides design ideas of introducing multidimensional structural defects for tailoring local electron and microstructure to improve energy storage property.
基金supported by the National Key Re-search and Development Program of the Ministry of Science and Technology of China(No.2019YFA0209902)the Natural Sci-ence Foundation of China(Nos.11988102 and 11972350).
文摘Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex concentrated solution,a variety of sub-systems of species exist to induce the metastable ordered compounds as candidates for ultimate CSROs.The issues remain pending on the origin of CSROs as to how to judge if CSRO will form in an H/MEA and particularly,what kind of CSROs would be stably produced if there were multiple possibilities.Here,the first-principles method,along with the proposed local formation energy calculation in allusion to the atomic-scale chemical heterogeneities,is used to predict the CSRO formation based on the mechanical stability,thermodynamic formation energy,and electronic characteristics.The simulations are detailed in an equiatomic ternary VCoNi MEA with three kinds of potential compounds,i.e.,L1_(1),L1_(2),and B2,in the face-centered cubic matrix.It turns out that L1_(1)is stable but hard to grow up so as to become the final CSRO.L1_(1)is further predicted as CSROs in CrCoNi,but unable to form in FeCoNi and CrMnFeCoNi alloys.These predictions are consistent with the experimental observations.Our findings shed light on understanding the formation of CSROs.This method is applicable to other H/MEAs to design and tailor CSROs by tuning chemical species/contents and thermal processing for high performance.
基金supported by the National Natural Science Foundation of China(Nos.52072101,51972088,52172205)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.GK229909299001-003)the Postgraduate Research Innovation Fund of Hangzhou Dianzi University(No.CXJJ2022032)。
文摘Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with self-activated dual-wavelength emissions toward high-sensitivity optical thermometers.Herein,a novel ratiometric thermometric strategy of Bi^(3+)-activated dual-wavelength emission band was realized in the same lattice position with two local electronic states of La_(3)Sb_(1-x)Ta_xO_(7):Bi^(3+)(0≤x≤1.0)materials based on the different temperature-dependent emission behaviors,benefiting from the highlysensitive and regulable emission to the coordination environment of Bi^(3+).The structural and spectral results demonstrate that the emission tremendously shifted from green to blue with 68 nm and the intensity was enhanced 2.6 times.Especially,the visual dual-wavelength emitting from two emission centers was presented by increasing the Ta^(5+)substitution concentration to 20%or 25%,mainly originating from the two local electronic states around the Bi^(3+)emission center.Significantly,the dual-wavelength with different thermal-quenching performance provided high-temperature sensitivity and good discrimination signals for optical thermometry in the range between 303 and 493 K.The maximum relative sensitivity reached 2.64%/K(La_(3)Sb_(0.8)Ta_(0.2)O_(7):0.04Bi^(3+)@383 K)and 1.91%/K(La_(3)Sb_(0.75)Ta_(0.25)O_(7):0.04Bi^(3+)@388 K).This work reveals a rational design strategy of different local electronic states around the singledoping multiple emission centers towards practical applications,such as luminescence thermometry and white LED lighting.
基金financial support from the National Natural Science Foundation of China (Nos. 21421004, 21573067, 91545103)Program of Shanghai Academic Research Leader (No. 17XD1401400)
文摘Titanium dioxide（TiO2） is one of the most widely studied transition metal oxides, especially for its unique performances in heterogeneous photocatalysis. Different phases of TiO2 have been found to exhibit different photo-activities, though the origins are still not fully understood. In this work, we use the density functional theory（DFT） calculations, corrected by on-site Coulomb and long-range dispersion interactions, to study the adsorptions of nitric oxide（NO） and oxygen（O2） molecules on the clean and hydrogenated anatase TiO2（101） surfaces. We also compare the detailed calculated results regarding their structural, energetic and electronic properties with those obtained at rutile TiO2（110）. It has been found that the behaviors of the surface localized electrons being transferred from adsorbed H, as well as the adsorption behaviors of NO and O2 are quite different at the two surfaces, which can be attributed to their characteristic local bonding structures around the surface hydroxyl. These results may also help explain the different photocatalytic activities of these two main facets of anatase and rutile TiO2
