Regulating the Electron Localization of Metallic Bismuth for Boosting CO_(2)Electroreduction

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.

Investigation of electron localization in harmonic emission from asymmetric molecular ion

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.

Electron localization in ultrathin films of three-dimensional topological insulators

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.

BiO_(2-x)Nanosheets with Surface Electron Localizations for Efficient Electrocatalytic CO_(2)Reduction to Formate

To enhance the activity and selectivity of electrocatalytic CO_(2)reduction to formate is of great importance from both environmental and economical viewpoints.Herein,the BiO_(2-x)nanosheets with surface electron localizations were constructed and utilized for the efficient CO_(2)-to-formate conversion.The formate Faraday efficiency reaches 99.1%with current density of 12 mA cm^(−2)at^(−1).1 V versus the reversible hydrogen electrode(RHE)in an H-type cell while those in the flow cell are 91.3%and 319 mA cm^(−2)at^(−1).0 V versus RHE,respectively.Theoretical calculations indicate that the electron localization presenting in the BiO_(2-x)nanosheet favors OCHO*intermediate stabilization and suppresses H*intermediate adsorption,thus improving the CO_(2)-to-formate efficiency.The BiO_(2-x)electrocatalyst is nondopant,easily prepared,low-cost,highly active and selective for CO_(2)RR to formate,which has demonstrated potential for application in the Zn-CO_(2)battery.The maximum power density can reach 2.33 mW cm^(−2),and the charge/discharge cycling stability is>100 h(300 cycles)at 4.5 mA cm^(−2).

Collaborative effect between single-atom Re and S vacancy on modulating localized electronic structure of MoS_(2) catalysts for alkaline hydrogen evolution

Optimizing the catalytic activity and stability of molybdenum disulfide (MoS_(2)) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic structure of active sites plays a crucial role in determining the activity and stability of the catalysts, yet how to construct such localized electronic structure still remains indeterminacy. Enlightened by theoretical prediction, herein, the introduction of both single-atom Re and the adjacent S vacancy in MoS_(2) (denoted as Re-MoS_(2)-Vs) exhibits collaborative effect on regulating the localized electronic structure of active sites (viz. Re-(S, Vs)-Mo). Such regulated electronic structure helps to decrease the energy barrier of the water dissociation and optimize hydrogen adsorption energy for enhancing alkaline HER performance. Most importantly, Mo-S bonds in the above local Re-(S, Vs)-Mo configurations are also strengthened for preventing the leaching of Mo and S atoms and then ensuring the long-time stability. Consequently, the deliberately designed Re-MoS_(2)-Vs with a Re coordination number of ~ 5.0 is experimentally verified to exhibit a comparable electrocatalytic performance and robust operational stability over 120 h. This strategy provides a promising guidance for modulating the electronic structure of MoS_(2) based catalysts via double-tuning atomic-scale local configuration for HER applications.

Nature of the Ga-Ga bonding in Na_2[Arx~*GaGaArx~*](Arx~*=C_6H_3 -2,6-(C_6H_5)_2):Electron localization function analysis

The nature of the Ga-Ga bonding in Na2[Arx＊GaGaArx＊] （Arx＊ = C6H3-2,6-（C6Hs）2） has been investigated and compared with that of in Hz[Arx＊GaGaArx＊] using electron localization function （ELF） and orbital analysis. The calculation results show that in Na2[Arx＊GaGaArx＊], the Ga-Ga interaction is a non-classical triple bond, the heart of Na2[Arx＊GaGaArx＊] is the Ga2Na2 cluster rather than a simple Ga-Ga bond, and the contribution of the sodium atoms to the short Ga-Ga bond length is considerable. As the two sodium atoms are substituted by two hydrogen atoms, the Ga-Ga bond is replaced by two 3-center, 2-electron （3c-2e） Ga-H-Ga covalent bridged bonding.

Multidimensional defects tailoring local electron and Mg^(2+) diffusion channels for boosting magnesium storage performance of WO_(3)/MoO_(2)

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.

Changes of Calmodulin Distribution in the Embryo Sac of Oryza sativa Before and After Fertilization: an Immunogold Electron Microscope Study

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.

Effects of Electron Beam Local Postweld Heat Treatment on Microstructure and Properties of 30CrMnSiNi2A Steel Welded Joints

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.

3D Finite Element Numerical Simulation of Residual Stresses on Electron Beam Welded BT20 Plates

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.

Local electron mean energy profile of positive primary streamer discharge with pin-plate electrodes in oxygen nitrogen mixtures

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.

Microstructure and fatigue crack growth behaviour of electron beam welding in 30CrMnSiNi2A steel

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.

NUMERICAL ANALYSIS OF RESIDUAL STRESSES IN TITANIUM ALLOY DURING ELECTRON BEAM LOCAL POST-WELD HEAT TREATMENT

The distributions of temperature and residual stresses in thin plates of BT20titanium alloy are numerically analyzed by three-dimensional finite element software duringelectron beam welding and electron beam local post-weld heat treatment (EBLPWHT). Combined withnumerical calculating results, the effects of different EBLPWHT mode and parameters, including heattreating position, heating width and heating time, on the distribution of welding residual stressesare analyzed. The results show that, the residual tensile stresses in weld center can be largelydecreased when the weld is heat treated at back preface of the plate. The numerical results alsoindicated that the magnitude of the residual longitudinal stresses of the weld and the zone vicinityof the weld is decreased, and the range of the residual longitudinal stresses is increased alongwith the increase of heating width and heating time.

Oxygen vacancies with localized electrons direct a functionalized separator toward dendrite-free and high loading LiFePO_(4)for lithium metal batteries

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.

Spin Noise Spectroscopy in N-GaAs:Spin Relaxation of Localized Electrons

Spin noise spectroscopy （SNS） of electrons in n-doped bulk GaAs is studied as functions of temperature and the probe-laser energy. Experimental results show that the SNS signal comes from localized electrons in the donor band. The spin relaxation time of electrons~ which is retrieved from the SNS measurement, depends on the probe light energy and temperature, and it can be ascribed to the variation of electron localization degree.

Influence of Superathermal Electrons oll Central Plasma Relaxation Oscillations during Localized Electron Cyclotron Heating on the HL-1M Tokamak

During initial studies of ECRH in the HL-1M tokamak, non-standard central MHD activities,such as saturated sawtooth, partially saturated sawtooth, double sawtooth, and the strong m = 1 bursts have been observed while changing the heating location, the ECRH power, the plasma density. Complete suppression of sawtooth is achieved for the duration of the ECRH, when the heating power is applied on the high-field side of low-density plasma, and exceeds a threshold value of power. The m = 1 bursts riding on the ramp phase of sawtooth can only be excited when the ECRH location is near the q = 1 surface on the high field side. The conditions under which the various relaxation activities are produced or suppressed are described. Experimental results imply that the energetic electrons generated during ECRH are responsible for the modification/or stabilization/or excitation of the instability. Near the q = 1 surface, the passing electrons play the role of reducing the shear and tending to stabilize the sawtooth activity, while the barely-trapped electrons play the role of enhancing or driving an internal kink instability.

LOCALIZED STUDIES ON ELECTRONIC STRUCTURE AND CHEMICAL BOND FOR [NCCuS_2MoS_2]^(2-) CLUSTER

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.

LOCALIZED INDO STUDY OF THE ELECTRONIC STRUCTURE OF Sc(Sc_6Cl_(12)Co)

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.

LOCALIZED MOLECULAR ORBITAL STUDY ON ELECTRONIC STRUCTURES OF BOWL-SHAPED AROMATIC HYDROCARBONS

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.

A DFT+U study of the structures and reactivities of polar CeO_2(100) surfaces

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.