Electronic effects on radiation damage inα-iron:A molecular dynamics study

Iron(Fe)-based alloys,which have been widely used as structural materials in nuclear reactors,can significantly change their microstructure properties and macroscopic properties under high flux neutron irradiation during operation,thus,the problems associated with the safe operation of nuclear reactors have been put forward naturally.In this work,a molecular dynamics simulation approach combined with electronic effects is developed for investigating the primary radiation damage process inα-Fe.Specifically,the influence of electronic effects on the collision cascade in Fe is systematically evaluated based on two commonly used interatomic potentials for Fe.The simulation results reveal that both electronic stopping(ES)and electron-phonon coupling(EPC)can contribute to the decrease of the number of defects in the thermal spike phase.The application of ES reduces the number of residual defects after the cascade evolution,whereas EPC has a reverse effect.The introduction of electronic effects promotes the formation of the dispersive subcascade:ES significantly changes the geometry of the damaged region in the thermal spike phase,whereas EPC mainly reduces the extent of the damaged region.Furthermore,the incorporation of electronic effects effectively mitigates discrepancies in simulation outcomes when using different interatomic potentials.

A hierarchically structured tin-cobalt composite with an enhanced electronic effect for high-performance CO_(2) electroreduction in a wide potential range

Earth-abundant and nontoxic Sn-based materials have been regarded as promising catalysts for the electrochemical conversion of CO_(2)to C1 products,e.g.,CO and formate.However,it is still difficult for Snbased materials to obtain satisfactory performance at low-to-moderate overpotentials.Herein,a simple and facile electrospinning technique is utilized to prepare a composite of a bimetallic Sn-Co oxide/carbon matrix with a hollow nanotube structure(Sn Co-HNT).Sn Co-HNT can maintain>90%faradaic efficiencies for C1 products within a wide potential range from-0.6 VRHE to-1.2 VRHE,and a highest 94.1%selectivity towards CO in an H-type cell.Moreover,a 91.2%faradaic efficiency with a 241.3 m A cm^(-2)partial current density for C1 products could be achieved using a flow cell.According to theoretical calculations,the fusing of Sn/Co oxides on the carbon matrix accelerates electron transfer at the atomic level,causing electron deficiency of Sn centers and reversible variation between Co^(2+)and Co^(3+)centers.The synergistic effect of the Sn/Co composition improves the electron affinity of the catalyst surface,which is conducive to the adsorption and stabilization of key intermediates and eventually increases the catalytic activity in CO_(2)electroreduction.This study could provide a new strategy for the construction of oxide-derived catalysts for CO_(2)electroreduction.

Pt-Ni core-shell structure with Pt-skin and electronic effect on catalytic performance

In order to improve the catalytic performance of the nitrobenzene hydrogenation rearrangement to prepare p-aminophenol,a bimetallic Pt-Ni/C(PNC)catalyst was synthesized.Taking advantage of the synergistic effect of Ni and Pt to enhance product selectivity and catalytic performance stability,the electrons in Ni are moved to Pt by the electron effect,which affects the catalyst’s ability to activate H_(2)as well as the amount of hydrogen activated.Furthermore,due to the strong Pt(5d)-Ni(3d)coupling effect,Ni can effectively maintain Pt stability in the acidic system and reduce Pt dissolution.The stability of the PNC can be found to be greatly enhanced compared to the Pt/C(PC)catalyst,and p-aminophenol selectivity is greatly enhanced,showing excellent catalytic performance.

Electronic Effect of Carbon Support on Pt Catalyst Supported on Graphite Intercalation Compound

Graphite intercalation compounds（GIC） were tested as an experimental model for studying the electronic effect of carbon support on the catalytic activity and poisoning tolerance of Pt catalyst for direct methanol fuel cells. The GIC samples with different intercalation degrees were prepared by electrolyzing graphite flake in H2SO4 for varying the periods of time. The GIC-supported Pt catalyst was deposited electrochemically. The catalytic activity and poisoning tolerance of the GIC-supported Pt catalysts were evaluated. It was found that GIC with sulfate anion as intercalate was able to catalyze methanol electrooxidation, which could be related to the positive charges generated on the graphite layer upon intercalation. As intercalation degree increased, the catalytic activity of the GIC-supported Pt catalyst decreased while the poisoning tolerance improved. This suggests that electron donation from support to catalyst had great effect on both catalytic activity and poisoning tolerance of Pt catalyst. And intercalation can be adopted as another important way to make modification on carboneous catalyst support.

ELECTRONIC EFFECTS OF POLYFLUORINATED SUBSTITUENTS ON THE POLYMERIZATION AND THE PROPERTIES OF POLYTHIOPHENES

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the electrochemical polymerization of thiophene monomers and properties of the obtained polymers were analyzed. The introduction of a fluoroether functional group at the 3-position of the thiophene ring leads to an increase of the oxidation potential of the monomer and to a decrease of the conductivity of the resulting polymers, even with the use of a CH2 group as spacer. Conversely, the presence of an oxygen atom directly at the 3-position of the thiophene ring, which offsets the negative withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conducting polythiophenes.

The Spatial and Electronic Effects of Substituent Groups on the Thermal Curing of Bio-Based Benzoxazines

To explore the influence of substituent groups on thermally induced curing,eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were synthesized.The thermal curing of these bio-based benzoxazines was studied in detail.Combined with the curing reaction kinetics,simulation and calculation of Highest Occupied Molecular and Lowest Unoccupied Molecular values,the spatial and electronic effects of different substituent groups on the curing of benzoxazine was explored.It was found that when the substituent was located at the position directly connected to the N atom,the steric hindrance effect of the group was dominant.When the substituent group was located on the benzene ring connected to the O atom,both the electronic effect and the spatial effect influenced the curing of benzoxazine.When an electron-withdrawing group was connected ortho position to the O atom,the curing reaction was promoted due to the decreased electron cloud density of O-on the oxazine ring,making the C-O bond easier to break.When an electron-donating group was connected to the meta position of the O atom it also promoted the curing reaction,possibly because it increased the electron cloud density of the+CH2 reaction site and thereby facilitated electrophilic substitution via attack of+CH2 on the cross linking reaction centre.This work provides a deeper understanding of how spatial and electronic effects of substituents affect the curing of benzoxazine.

Carbonate-induced enhancement of phenols degradation in CuS/peroxymonosulfate system: A clear correlation between this enhancement and electronic effects of phenols substituents

This study investigated the enhancement effects of dissolved carbonates on the peroxymonosulfate-based advanced oxidation process with CuS as a catalyst.It was found that the added CO_(3)^(2−)increased both the catalytic activity and the stability of the catalyst.Under optimized reaction conditions in the presence of CO_(3)^(2−),the degradation removal of 4-methylphenol(4-MP)within 2 min reached 100%,and this was maintained in consecutivemulti-cycle experiments.The degradation rate constant of 4-MP was 2.159 min^(−1),being 685%greater than that in the absence of CO_(3)^(2−)(0.315 min−1).The comparison of dominated active species and 4-MP degradation pathways in both CO_(3)^(2−)-free and CO_(3)^(2−)-containing systems suggested thatmore CO_(3)·^(−)/^(1)O_(2) was produced in the case of CO_(3)^(2−)deducing an electron transfer medium,which tending to react with electron-richmoieties.Meanwhile,Characterization by X-ray photoelectron spectroscopic and cyclic voltammetrymeasurement verified CO_(3)^(2−)enabled the effective reduction of Cu^(2+)to Cu^(+).By investigating the degradation of 11 phenolics with different substituents,the dependence of degradation kinetic rate constant of the phenolics on their chemical structures indicated that there was a good linear relationship between the Hammett constantsσp of the aromatic phenolics and the logarithm of k in the CO_(3)^(2−)-containing system.This work provides a new strategy for efficient removal of electron-rich moieties under the driving of carbonate being widely present in actual water bodies.

Selectivity switching between CO and formate for CO_(2) reduction on Sb modified amorphous ZnO by electronic effect

The adjustable intermediate binding capacity in electrocatalytic carbon dioxide(CO_(2))reduction is critical for varying the reaction pathways to desired products.Herein,we first report the synthesis of boron-doped amorphous zinc oxide with(B-a-ZnO-Sb)or without antimony nanoparticles embedding(B-a-ZnO)via one-step wet chemical method,which is easy to scale up by enlarging the vessel and increasing feeding.Sb successfully realizes the product switching from CO on B-a-ZnO to formate on B-a-ZnOSb.Both experimental and theoretical results reveal that Sb weakens the charge interaction on Zn atoms.Based on the moderate adsorption of*COOH and strong adsorption of*OCHO and*HCOOH for B-a-ZnO,the foreign Sb weakens the adsorption of these intermediates and brings about a favor formate production instead of CO.This work points out a new direction for the synthesis of amorphous ZnO-based catalysts and provides advanced insights into the aimed selectivity switch for CO_(2)reduction by electronic effect.

Influence of Electronic Effect on Methane Catalytic Combustion over PdNi/Al2O3

A series of PdNi/Al2O3 catalysts with different compositions was prepared by co-reduction method. The influence of Ni amount on the catalytic combustion of methane was studied. X-ray diffractometry and X-ray photo- electron spectroscopy were employed to characterize the dispersion and electronic state of the active phase. Tempe- rature-programmed oxidation was carried out to study the thermal stability affected by Ni doping. It has been demon- strated that Ni addition changed particle size and oxidation state of PdOx. The results indicate that the promotion of Ni to the Pd/Al2O3 resulted from both size effect and electronic effect. In addition, the thermal stability of the Ni-doped catalysts were enhanced.

Electronic effect on the optical properties and sensing ability of AIEgens with ESIPT process based on salicylaldehyde azine

Two novel AIE-active salicylaldehyde azine(SAA) derivatives with a typical excited-state intramolecular proton transfer(ESIPT) process are prepared by introducing electron-withdrawing and donating groups at para-position of phenolic hydroxyl group(CN-SAA and TPA-SAA). The effect of the proton activity in SAA framework on their optical behaviors is investigated spectroscopically. The results from NMR and solvation measurements show that the proton of phenolic hydroxyl group has higher activity when there are electron-withdrawing groups, and the absorption and fluorescence spectra in buffers with different pH also provide the same results. After inviting F. as a nucleophilic probe, this proton activity difference in CN-SAA and TPA-SAA becomes more obvious. The potential application of both molecules is investigated. TPA-SAA exhibits good quantitative sensing ability towards F. with a fluorescence "turn-on" mode, whereas the aggregates of TPA-SAA can selectively and sensitively detect Cu2+ in aqueous solution. From these results, a structure-property relationship is established: the occurrence of ESIPT process will become much easier when linking electron-withdrawing groups at the para-position of phenolic hydroxyl group(e.g., CN-SAA),and it is better to introduce electron-donating groups to enhance the sensing ability towards ions(e.g., TPA-SAA). This work will provide guidance for further design and preparation of AIE-active luminogens with ESIPT process for sensing applications.

Effect of Chemical Doping on the Electronic Transport Properties of Tailoring Graphene Nanoribbons

The electronic transport properties of a molecular junction based on doping tailoring armchair-type graphene nanoribbons（AGNRs）with different widths are investigated by applying the non-equilibrium Green＇s function formalism combined with first-principles density functional theory.The calculated results show that the width and doping play significant roles in the electronic transport properties of the molecular junction.A higher current can be obtained for the molecular junctions with the tailoring AGNRs with W=11.Furthermore,the current of boron-doped tailoring AGNRs with widths W=7 is nearly four times larger than that of the undoped one,which can be potentially useful for the design of high performance electronic devices.

Electronic Structure Effect on Model Cluster for L1_2 Structure of Al_3Ti Intermetallic Compound with an Addition of Alloying Elements Fe, Ni and Cu

By use of self-consistent field Xα scattered-wave (SCF-Xα-SW) method, the electronic structure was calculated for four models of Ti4Al14X (X=Al, Fe, Ni and Cu) clusters. The Ti4Al14X cluster was developed based on L12 Al3Ti-base intermetallic compound. The results are presented using the density of states (DOS) and one-electron properties, such as relative binding tendency between the atom and the model cluster, and hybrid bonding tendency between the alloying element and the host atoms. By comparing the four models of Ti4Al14X cluster, the effect of the Fe, Ni or Cu atom on the physical properties of Al3Ti-based L12 intermetallic compounds is analyzed. The results indicate that the addition of the Fe, Ni or Cu atom intensifies the relative binding tendency between Ti atom and Ti4Al14X cluster. It was found that the Fermi level (EF) lies in a maximum in the DOS for Ti4Al14Al cluster; on the contrary, the EF comes near a minimum tn the DOS for Ti4Al14X (X=Fe, Ni and Cu) cluster. Thus the L12 crystal structure for binary Al3Ti alloy is unstable, and the addition of the Fe, Ni or Cu atom to Al3Ti is benefical to stabilize L12 crystal structure. The calculation also shows that the Fe, Ni or Cu atom strengthens the hybrid bonding tendency between the central atom and the host atoms for Ti4Al14X cluster and thereby may lead to the constriction of the lattice of Al3Ti-base intermetallic compounds.

Bismuth Effects on Electronic Levels in GaSb(Bi)/AlGaSb Quantum Wells Probed by Infrared Photoreflectance

GaSb（Bi）/Alo.2Gao.sSb single quantum wells are characterized by a Fourier transform infrared spectrometer- based photoreflectance method at 77K. Spatially direct and indirect transitions between the electronic levels at and above the effective band gap are well resolved. The shifts of the electronic levels with Bi incorporation are identified quantitatively. The results show that the upshift of the valence band edge is clarified to be dominant, while the Bi-induced downshift of the conduction band edge does exist and contributes to the band gap reduction in the GaSbBi quantum-well layer by （29±6）%.

Effect of Chirality on the Electronic Transport Properties of the Thioxanthene-Based Molecular Switch

Based on the nonequilibrium Green function method and density functional theory calculations, we theoretically investigate the effect of chirality on the electronic transport properties of thioxanthene-based molecular switch. The molecule comprises the switch which can exhibit different chiralities, that is, cis-form and trans-form by ultraviolet or visible irradiation. The results clearly reveal that the switching behaviors can be realized when the molecule converts between cis-form and trans-form. ~urthermore, the on-off ratio can be modulated by the chirality of the carbon nanotube electrodes. The maximum on-off ratio can reach 109 at 0.4 V for the armchair junction, suggesting potential applications of this type of junctions in future design of functional molecular devices.

Size Effect on the Raman Spectra and Electronic Structure of the Glycine-alanine Oligopeptide Chains

A theoretical study on oligopeptide chains of glycine-alanine by density functional theory（DFT） is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G（d） level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues（glycine or alanine） at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.

Effects of N on Electronic and Mechanical Properties of H-Type SiC

Structural, electronic and mechanical properties of the nH-SiC （n = 2, 4, 6, 8 and 10） polytypes are calculated by using the first-principles calculations based on the density-functional theory approach. The optimized lattice parameters of nH-SiC are in good agreement with the experimental data. The mechanical properties, including elastic constants, bulk modulus, Young＇s modulus, shear modulus and Poisson＇s ratio, are calculated. The analysis of elastic properties indicates that the effects of n on the mechanical properties of the five nil-SiC structures have no difference. The indirect band gap relationship for the live polytypes is Ebg2H 〉 Ebg4H 〉 Ebg6H 〉 Ebg10H 〉 EbgsH.

Structural and Kinetics Understanding of Support Effects in Pd-Catalyzed Semi-Hydrogenation of Acetylene

In this study,the support effects on the Pd-catalyzed semi-hydrogenation of acetylene have been investigated from the structural and kinetic perspectives.According to the results of kinetic analysis and X-ray photoelectron spectroscopy,hydrogen temperature-programmed reduction,temperature-programmed hydride decomposition,and in situ X-ray diffraction measurements,using carbon nanotubes as support for Pd nanocatalysts with various sizes instead of a-Al_(2)O_(3) decreases the Pd^(0)3d binding energy and suppresses the formation of undesirable palladium hydride species,thus increasing the ethylene yield.Furthermore,X-ray absorption spectroscopy,high-resolution transmission electron microscopy,and C_(2)H_(4) temperature-programmed desorption studies combined with density-functional theory calculations reveal the existence of a unique Pd local environment,containing subsurface carbon atoms,that produces positive geometric effects on the acetylene conversion reaction.Therefore,tailoring the Pd local environment and electronic properties represents an effective strategy for the fabrication and design of highly active and selective Pd semi-hydrogenation catalysts.

Numerical investigation on electron effects in the mass transfer of the plasma species in aqueous solution

The objective of this work is to contribute an understanding of the effects of electrons in the plasmas on the mass transfer of plasma species in aqueous solution by means of the numerical simulation based on a one-dimensional diffusion-reaction model.The plasma species are divided into two groups,i.e.electrons and the other species,and the mass transfer in the three scenarios has been simulated,including the systematic calculations of the depth distributions of five major reactive species,OH,O3,HO2,O2^-,and H2O2.In the three scenarios,the particles considered to enter into aqueous solution are all the plasma species(the scenario Ⅰ,where the mass transfer of plasma species is a result due to the synergy of the electrons and the other plasma species),the other species(the scenario Ⅱ),and only electrons in plasma species(the scenario Ⅲ),respectively.The detailed analyses on the difference between the depth distributions of each reactive species in these three scenarios show the following conclusions.The electrons play an important role in the mass transfer of plasma species in aqueous solution and the synergy of the electrons and the other plasma species(the electron-species synergy)presents its different effects on the mass transfer.The vast majority of H2O2 are generated from a series of the electronrelated reactions in aqueous solution,which is hardly affected by the electron-species synergy.Compared to the results when only the electrons enter into the liquid region,the electron-species synergy evidently weakens the generation of O2^-,O3,and OH,but promotes to produce HO2.

Nonadiabatic Effect on the Rescattering Trajectories of Electrons in Strong Laser Field Ionization Process

The important features of the rescattering trajectories in strong field ionization process such as the cutoff of the return energy at 3.17Up and that of the final energy at 10Up are obtained, based on the adiabatic approximation in which the initial momentum of the electron is assumed to be zero. We theoretically study the nonadiabatic effect by assuming a nonzero initial momentum on the rescattering trajectories based on the semiclassical simpleman model. We show that the nonzero initial momentum will modify both the maximal return energy at collision and the final energy after backward scattering, but in different ways for odd and even number of return trajectories. The energies are increased for even number of returns but are decreased for odd number of returns when the nonzero （positive or negative） initial momentum is applied.

Giant Volume Magnetostriction Caused by Itinerant Electron Metamagnetic Transition and Pronounced Invar Effects in La(Fe_xSi_(1-x))_(13) Compounds

A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_C for x=0.88 is huge of about 1.5%, which is caused by a large magnetic moment induced by the IEM transition. These compounds have a possibility for practical applications as giant magnetostrictive materials. Pronounced Invar effects bring about a negative thermal expansion below TC, closely correlated with the negative mode-mode coupling among spin fluctuations.