Modulation of Electronic States in Bimetallic-doped Nitrogen-Carbon Based Nanoparticles for Enhanced Oxygen Reduction Kinetics

Controlling the local electronic structure of active ingredients to improve the adsorption desorption characteristics of oxygen-containing intermediates over the electrochemical liquid-solid interfaces is a critical challenge in the field of oxygen reduction reaction(ORR)catalysis.Here,we offer a simple approach for modulating the electronic states of metal nanocrystals by bimetal co-doping into carbon-nitrogen substrate,allowing us to modulate the electronic structure of catalytic active centers.To test our strategy,we designed a typical bimetallic nanoparticle catalyst(Fe-Co NP/NC)to flexibly alter the reaction kinetics of ORR.Our results from synchrotron Xray absorption spectroscopy and X-ray photoelectron spectroscopy showed that the co-doping of iron and cobalt could optimize the intrinsic charge distribution of Fe-Co NP/NC catalyst,promoting the oxygen reduction kinetics and ultimately achieving remarkable ORR activity.Consequently,the carefully designed Fe-Co NP/NC exhibits an ultra-high kinetic current density at the operating voltage(71.94 mA/cm^(2)at 0.80 V),and the half-wave potential achieves 0.915 V,which is obviously better than that of the corresponding controls including Fe NP/NC,Co NP/NC.Our findings provide a unique perspective for optimizing the electronic structure of active centers to achieve higher ORR catalytic activity and faster kinetics.

Microenvironment and electronic state modulation of Pd nanoparticles within MOFs for enhancing low-temperature activity towards DCPD hydrogenation

Precise control of the local environment and electronic state of the guest is an important method of controlling catalytic activity and reaction pathways.In this paper,guest Pd NPs were introduced into a series of host UiO-67 MOFs with different functional ligands and metal nodes,the microenvironment and local electronic structure of Pd is modulated by introducing bipyridine groups and changing metal nodes(Ce_(6)O_(6) or Zr_(6)O_(6)).The bipyridine groups not only promoted the dispersion Pd NPs,but also facilitated electron transfer between Pd and UiO-67 MOFs through the formation of Pd-N bridges.Compared with Zr6 clusters,the tunability and orbital hybridisation of the 4f electronic structure in the Ce_(6) clusters modulate the electronic structure of Pd through the construction of the Ce-O-Pd interfaces.The optimal catalyst Pd/UiO-67(Ce)-bpy presented excellent low-temperature activity towards dicyclopentadiene hydrogenation with a conversion of>99% and a selectivity of>99%(50℃,10 bar).The results show that the synergy of Ce-O-Pd and Pd-N promotes the formation of active Pd^(δ+),which not only enhances the adsorption of H_(2) and electron-rich C=C bonds,but also contributes to the reduction of proton migration distance and improves proton utilization efficiency.These results provide valuable insights for investigating the regulatory role of the host MOFs,the nature of host-guest interactions,and their correlation with catalytic performance.

Electron density measurement by the three boundary channels of HCOOH laser interferometer on the HL-3 tokamak

Far-infrared(FIR)interferometer is widely used to measure the electron density in the magnetically confined fusion plasma devices.A new FIR laser interferometer with a total of 13 channels(8 horizontal channels and 5 oblique channels)is under development on the HL-3tokamak by using the formic-acid laser(HCOOH,f=694 GHz).In order to investigate the boundary electron density activity during the divertor discharge,three horizontal interferometry channels located at Z=-97,-76,76.5 cm have been successfully developed on HL-3 in 2023,and put into operation in recent experimental campaign,with a time resolution of<1.0μs and lineintegrated electron density resolution of~7.0×10^(16) m^(-2).This paper mainly focuses on the optical design of the three-channel interferometry system,as well as optical elements and recent experimental result on HL-3.

Density of excess modes below the first phonon mode in four-dimensional glasses

Glasses are known to possess low-frequency excess modes beyond the Debye prediction.For decades,it has been assumed that evolution of low-frequency density of excess modes D(ω) with frequency ω follows a power-law scaling:D(ω)~ω~γ.However,it remains debated on the value of γ at low frequencies below the first phonon-like mode in finitesize glasses.Early simulation studies reported γ=4 at low frequencies in two-(2D),three-(3D),and four-dimensional(4D)glasses,whereas recent observations in 2D and 3D glasses suggested γ=3.5 in a lower-frequency regime.It is uncertain whether the low-frequency scaling of D(ω)~ω^(3.5) could be generalized to 4D glasses.Here,we conduct numerical simulation studies of excess modes at frequencies below the first phonon-like mode in 4D model glasses.It is found that the system size dependence of D(ω) below the first phonon-like mode varies with spatial dimensions:D(ω) increases in2D glasses but decreases in 3D and 4D glasses as the system size increases.Furthermore,we demonstrate that the ω^(3.5)scaling,rather than the ω~4 scaling,works in the lowest-frequency regime accessed in 4D glasses,regardless of interaction potentials and system sizes examined.Therefore,our findings in 4D glasses,combined with previous results in 2D and 3D glasses,suggest a common low-frequency scaling of D(ω)~ ω^3.5) below the first phonon-like mode across different spatial dimensions,which would inspire further theoretical studies.

Electronic structure and spin state regulation of vanadium nitride via a sulfur doping strategy toward flexible zinc-air batteries

Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity due to the weak adsorption ability to O-containing species.Here,the S-doped VN anchored on N,S-doped multi-dimensional carbon(S-VN/Co/NS-MC)was constructed using the solvothermal and in-situ doping methods.Incorporating sulfur atoms into VN species alters the electron spin state of vanadium in the S-VN/Co/NS-MC for regulating the adsorption energy of vanadium sites to oxygen molecules.The introduced sulfur atoms polarize the V 3d_(z)^(2) electrons,shifting spin-down electrons closer to the Fermi level in the S-VN/Co/NS-MC.Consequently,the introduction of sulfur atoms into VN species enhances the adsorption energy of vanadium sites for oxygen molecules.The*OOH dissociation transitions from being unspontaneous on the VN surface to a spontaneous state on the S-doped VN surface.Then,the ORR barrier on the S-VN/Co/NS-MC surface is reduced.The S-VN/Co/NS-MC demonstrates a higher half-wave potential and limiting current density compared to the VN/Co/N-MC.The S-VN/Co/NS-MC-based liquid ZABs display a power density of 195.7 m W cm^(-2),a specific capacity of 815.7 m A h g^(-1),and a cycling stability exceeding 250 h.The S-VN/Co/NS-MC-based flexible ZABs are successfully employed to charge both a smart watch and a mobile phone.This approach holds promise for advancing the commercial utilization of VN-based catalysts in ZABs.

Analyzing the surface passivity effect of germanium oxynitride:a comprehensive approach through first principles simulation and interface state density

High-purity germanium(HPGe)detectors,which are used for direct dark matter detection,have the advantages of a low threshold and excellent energy resolution.The surface passivation of HPGe has become crucial for achieving an extremely low energy threshold.In this study,first-principles simulations,passivation film preparation,and metal oxide semiconductor(MOS)capacitor characterization were combined to study surface passivation.Theoretical calculations of the energy band structure of the -H,-OH,and -NH_(2) passivation groups on the surface of Ge were performed,and the interface state density and potential with five different passivation groups with N/O atomic ratios were accurately analyzed to obtain a stable surface state.Based on the theoretical calculation results,the surface passivation layers of the Ge_(2)ON_(2) film were prepared via magnetron sputtering in accordance with the optimum atomic ratio structure.The microstructure,C-V,and I-V electrical properties of the layers,and the passivation effect of the Al/Ge_(2)ON_(2)/Ge MOS were characterized to test the interface state density.The mean interface state density obtained by the Terman method was 8.4×10^(11) cm^(-2) eV^(-1).The processing of germanium oxynitrogen passivation films is expected to be used in direct dark matter detection of the HPGe detector surface passivation technology to reduce the detector leakage currents.

Charge self-consistent dynamical mean field theory calculations incombination with linear combination of numerical atomic orbitalsframework based density functional theory

We present a formalism of charge self-consistent dynamical mean field theory(DMFT)in combination with densityfunctional theory(DFT)within the linear combination of numerical atomic orbitals(LCNAO)framework.We implementedthe charge self-consistent DFT+DMFT formalism by interfacing a full-potential all-electron DFT code with threehybridization expansion-based continuous-time quantum Monte Carlo impurity solvers.The benchmarks on several 3d,4fand 5f strongly correlated electron systems validated our formalism and implementation.Furthermore,within the LCANOframework,our formalism is general and the code architecture is extensible,so it can work as a bridge merging differentLCNAO DFT packages and impurity solvers to do charge self-consistent DFT+DMFT calculations.

Diagnosing ratio of electron density to collision frequency of plasma surrounding scaled model in a shock tube using low-frequency alternating magnetic field phase shift

A non-contact low-frequency(LF)method of diagnosing the plasma surrounding a scaled model in a shock tube is proposed.This method utilizes the phase shift occurring after the transmission of an LF alternating magnetic field through the plasma to directly measure the ratio of the plasma loop average electron density to collision frequency.An equivalent circuit model is used to analyze the relationship of the phase shift of the magnetic field component of LF electromagnetic waves with the plasma electron density and collision frequency.The applicable range of the LF method on a given plasma scale is analyzed.The upper diagnostic limit for the ratio of the electron density(unit:m^(-3))to collision frequency(unit:Hz)exceeds 1×10^(11),enabling an electron density to exceed 1×10^(20)m^(-3)and a collision frequency to be less than 1 GHz.In this work,the feasibility of using the LF phase shift to implement the plasma diagnosis is also assessed.Diagnosis experiments on shock tube equipment are conducted by using both the electrostatic probe method and LF method.By comparing the diagnostic results of the two methods,the inversion results are relatively consistent with each other,thereby preliminarily verifying the feasibility of the LF method.The ratio of the electron density to the collision frequency has a relatively uniform distribution during the plasma stabilization.The LF diagnostic path is a loop around the model,which is suitable for diagnosing the plasma that surrounds the model.Finally,the causes of diagnostic discrepancy between the two methods are analyzed.The proposed method provides a new avenue for diagnosing high-density enveloping plasma.

The nature of electron density enhancement over a wide altitude range during ionosphere heating experiments at EISCAT

During the course of ionospheric heating experiments, researchers at the European Incoherent Scatter Scientific Association (EISCAT) observed an apparent electron density enhancement. The enhancement extended over a wide range of altitudes, above the reflection altitude of the high-frequency pump wave. However, whether this enhancement actually corresponds to a true enhancement in electron density remains an open question. When the dispersion relation of ion acoustic waves is followed, the frequency ratio of the enhanced ion line to the background ion line suggests that the profile of the effective ion mass may have remained unchanged. Furthermore, the solar radio flux and ion drift velocity indicate no significant changes in the ion species and their densities. In conclusion, the electron density enhancement observed at EISCAT should not, in fact, be considered a true enhancement.

Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Investigation of the structural, electronic and mechanical properties of CaO–SiO_(2) compound particles in steel based on density functional theory

CaO–SiO_(2)compounds compromise one of the most common series of oxide particles in liquid steels, which could significantly affect the service performance of the steels as crack initiation sites. However, the structural, electronic, and mechanical properties of the compounds in CaO–SiO_(2)system are still not fully clarified due to the difficulties in the experiments. In this study, a thorough investigation of these properties of CaO–SiO_(2)compound particles in steels was conducted based on first-principles density functional theory. Corresponding phases were determined by thermodynamic calculation, including gamma dicalcium silicate(γ-C2S), alpha-prime(L) dicalcium silicate(αL′-C2S), alpha-prime(H) dicalcium silicate(αH′-C2S), alpha dicalcium silicate(α-C2S), rankinite(C3S2), hatrurite(C3S), wollastonite(CS), and pseudowollastonite(Ps-CS). The results showed that the calculated crystal structures of the eight phases agree well with the experimental results. All the eight phases are stable according to the calculated formation energies, and γ-C2S is the most stable. O atom contributes the most to the reactivity of these phases. The Young’s modulus of the eight phases is in the range of 100.63–132.04 GPa. Poisson’s ratio is in the range of0.249–0.281. This study provided further understanding concerning the CaO–SiO_(2)compound particles in steels and fulfilled the corresponding property database, paving the way for inclusion engineering and design in terms of fracture-resistant steels.

Optical spectroscopy of CrO and electronic states of the Cr group metal monoxides

All of the experimentally known electronic states of the Cr group metal monoxides(Cr O,Mo O,and WO)have been presented in the paper.The optical spectra of the Cr O molecule have been investigated in the gas phase through a combination of the laser-induced fluorescence(LIF)excitation and single-vibronic-level(SVL)emission spectroscopy in the supersonic expansion.The rotational constants of the vibronic electronic states,including X^(5)Π_(-1)(v=0–3),B^(5)Π_(-1)(v=0–10),and B~5Π_1(v=1,5),and the vibrational constants of the spin–orbit components X^(5)Π_(-1,0,1)have been obtained.The molecular constants of the Mo O and WO molecules have been summarized by reviewing the previous spectroscopic studies,and a comprehensive energy level diagram of the Cr group metal monoxides has been constructed.By comparing the electronic configurations,bond lengths,and vibrational frequencies of all the transition metal monoxides in the ground electronic state,the significance of the relativistic effect in the bonding of the 5d transition metal monoxides has been discussed.The related spectroscopic data of the Cr O molecule are available at https://doi.org/10.57760/sciencedb.j00113.00085.

Local density of optical states calculated by the mode spectrum in stratified media

The local density of optical states(LDOS)is an important physical concept,which can characterize the spontaneous emission of microcavities.In order to calculate the LDOS,the relationship between the mode spectrum and the LDOS is established.Then,based on the transfer matrix method and the effective resonator model,the leaky loss of the leaky mode and the mode spectrum in the one-dimensional photonic bandgap crystal waveguide are calculated,results of which indicate that the mode spectrum can characterize the leaky loss of the leaky mode.At last,the density of optical states(DOS),and the LDOS in each layer are calculated.The partial DOS and the partial LDOS in the quantum well,related to the fundamental leaky mode,can be used to find out the optimal location of the quantum well in the defect layer to couple more useful photons into the lasing mode for lasers.

Study of Electronic Density of States: Zintl Alloys

In the present work the electronic density of states of liquid,viz.,Zintli alloys,have been studied only at the composition of their maximum resistivity to have an elementary idea about the behaviors of the alloys with respect to nearly free electron behavior.The study reveals that the anomalous electronic behavior of liquid Li-Pb,Na-Pb,Li-Sn,and Na-Sn can be attributed to the preferential ordering of unlike atoms.

Density functional theory study of influence of impurity on electronic properties and reactivity of pyrite

The electronic property of pyrite supercell containing As,Se,Te,Co or Ni hetero atoms were calculated using density functional theory（DFT）,and the reactivities of pyrite with oxygen and xanthate were discussed by frontier orbital methods.The cell volume expands due to the presence of impurity.Co and Ni mainly affect the bands near Fermi levels,while As mainly affects the shallow and deep valence bands,and Se and Te mainly affect the deep valence bands.Electronic density analysis suggests that there exists a strong covalent interaction between hetero atom and its surrounding atoms.By frontier orbital calculation,it is suggested that As,Co and Ni have greater influence on the HOMO and LUMO of pyrite than Se and Te.In addition,pyrite containing As,Co or Ni is easier to oxidize by oxygen than pyrite containing Se or Te,and pyrite containing Co or Ni has greater interaction with collector.These are in agreement with the observed pyrite practice.

Density Functional Theory Study on Electronic and Magnetic Properties of Mn-doped （MgO）n （n=2-10） Clusters

We study the geometries, stabilities, electronic and magnetic properties of （MgO）n （n=2-10） clusters doped with a single Mn atom using the density functional theory with the gener- alized gradient approximation. The optimized geometries show that the impurity Mn atom prefers to replace the Mg atom which has low coordination number in all the lowest-energy MnMgn-1On （n=2-10） structures. The stability analysis clearly represents that the average binding energies of the doped clusters are larger than those of the corresponding pure （MgO）n clusters. Maximum peaks of the second order energy differences are observed for MnMg~_1On clusters at n=6, 9, implying that these clusters exhibit higher stability than their neighboring clusters. In addition, all the Mn-doped Mg clusters exhibit high total magnetic moments with the exception of MnMgO2 which has 3.00μB. Their magnetic behavior is attributed to the impurity Mn atom, the charge transfer modes, and the size of MnMgn- 1On clusters.

Discrete vortex bound states with a van Hove singularity in the vicinity of the Fermi level

A theoretical study on discrete vortex bound states is carried out near a vortex core in the presence of a van Hove singularity(VHS) near the Fermi level by solving Bogoliubov–de Gennes(Bd G) equations. When the VHS lies exactly at the Fermi level and also at the middle of the band, a zero-energy state and other higher-energy states whose energy ratios follow integer numbers emerge. These discrete vortex bound state peaks undergo a splitting behavior when the VHS or Fermi level moves away from the middle of the band. Such splitting behavior will eventually lead to a new arrangement of quantized vortex core states whose energy ratios follow half-odd-integer numbers.

Scheme for the excitation of thorium-229 nuclei based on electronic bridge excitation

Thorium-229 possesses the lowest first nuclear excited state,with an energy of approximately 8 eV.The extremely narrow linewidth of the first nuclear excited state,with an uncertainty of 53 THz,prevents direct laser excitation and realization of the nuclear clock.We present a proposal using the Coulomb crystal of a linear chain formed by229Th^(3+)ions,where the nuclei of229Th3+ions in the ion trap are excited by the electronic bridge(EB)process.The 7 P1∕2state of the thorium-229 nuclear ground state is chosen for EB excitation.Using the two-level optical Bloch equation under experimental conditions,we calculate that 2 out of 36 prepared thorium ions in the Coulomb crystal can be excited to the first nuclear excited state,and it takes approximately 2 h to scan over an uncertainty of 0.22 eV.Taking advantage of the transition enhancement of EB and the long stability of the Coulomb crystal,the energy uncertainty of the first excited state can be limited to the order of 1 GHz.

Analysis of Anomalous Enhancement in TEC and Electron Density in the China Region Prior to the 17 March 2015 Geomagnetic Storm Based on Ground and Space Observations

Total Electron Content(TEC)and electron density enhancement were observed on the day before 17 March 2015 great storm in the China Region.Observations from ground-and space-based instruments are used to investigate the temporal and spatial evolution of the pre-storm enhancement.TEC enhancement was observed from 24°N to 30°N after 10:00 UT at 105°E,110°E and 115°E longitudes on March 16.The maximum magnitude of TEC enhancement was more than 10 TECU and the maximal relative TEC enhancement exceeded 30%.Compared with geomagnetic quiet days,the electron density of Equatorial Ionization Anomaly(EIA)northern peak from Swarm A/C satellites on March 16 was larger and at higher latitudes.NmF2 enhanced during 11:30—21:00 UT at Shaoyang Station and increased by 200%at~16:00 UT.However,TEC and electron density enhancement were not accompanied by a significant change of hmF2.Most research has excluded some potential mechanisms as the main driving factors for storm-time density enhancements by establishing observational constraints.In this paper,we observed pre-storm enhancement in electron density at different altitudes and Equatorial Electrojet(EEJ)strength results derived from ground magnetometers observations suggest an enhanced eastward electric field from the E region probably played a significant role in this event.

Electronic structure and optical properties of In-doped SrTiO3 by density function theory

The effect of In doping on the electronic structure and optical properties of SrTiO3 is investigated by the first-principles calculation of plane wave ultra-soft pseudo-potential based on the density function theory （DFT）. The calculated results reveal that due to the hole doping, the Fermi level shifts into valence bands （VBs） for SrTi1-x InxO3 with x = 0.125 and the system exhibits p-type degenerate semiconductor features. It is suggested according to the density of states （DOS） of SrTi0.875In0.125O3 that the band structure of p-type SrTIO3 can be described by a rigid band model. At the same time, the DOS shifts towards high energies and the optical band gap is broadened. The wide band gap, small transition probability and weak absorption due to the low partial density of states （PDOS） of impurity in the Fermi level result in the optical transparency of the film. The optical transmittance of In doped SrTiO3 is higher than 85% in a visible region, and the transmittance improves greatly. And the cut-off wavelength shifts into a blue-light region with the increase of In doping concentration.