Local coordination and electronic interactions of Pd/MXene via dual‐atom codoping with superior durability for efficient electrocatalytic ethanol oxidation

Catalyst design relies heavily on electronic metal‐support interactions,but the metal‐support interface with an uncontrollable electronic or coordination environment makes it challenging.Herein,we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction(EOR)catalysis.The doped B and N atoms from dimethylamine borane(DB)occupy the position of the Ti_(3)C_(2)lattice to anchor the supported Pd nanoparticles.The electrons transfer from the support to B atoms,and then to the metal Pd to form a stable electronic center.A strong electronic interaction can be produced and the d‐band center can be shifted down,driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support.As‐obtained Pd/DB–Ti_(3)C_(2)exhibits superior durability to its counterpart(∼14.6%retention)with 91.1%retention after 2000 cycles,placing it among the top single metal anodic catalysts.Further,in situ Raman and density functional theory computations confirm that Pd/DB–Ti_(3)C_(2)is capable of dehydrogenating ethanol at low reaction energies.

Capturing the non-equilibrium state in light–matter–free-electron interactions through ultrafast transmission electron microscopy

Ultrafast transmission electron microscope(UTEM) with the multimodality of time-resolved diffraction, imaging,and spectroscopy provides a unique platform to reveal the fundamental features associated with the interaction between free electrons and matter. In this review, we summarize the principles, instrumentation, and recent developments of the UTEM and its applications in capturing dynamic processes and non-equilibrium transient states. The combination of the transmission electron microscope with a femtosecond laser via the pump–probe method guarantees the high spatiotemporal resolution, allowing the investigation of the transient process in real, reciprocal and energy spaces. Ultrafast structural dynamics can be studied by diffraction and imaging methods, revealing the coherent acoustic phonon generation and photoinduced phase transition process. In the energy dimension, time-resolved electron energy-loss spectroscopy enables the examination of the intrinsic electronic dynamics of materials, while the photon-induced near-field electron microscopy extends the application of the UTEM to the imaging of optical near fields with high real-space resolution. It is noted that light–free-electron interactions have the ability to shape electron wave packets in both longitudinal and transverse directions, showing the potential application in the generation of attosecond electron pulses and vortex electron beams.

Strong metal–support interaction boosts the electrocatalytic hydrogen evolution capability of Ru nanoparticles supported on titanium nitride

Ruthenium(Ru)has been regarded as one of the most promising alternatives to substitute Pt for catalyzing alkaline hydrogen evolution reaction(HER),owing to its inherent high activity and being the cheapest platinum-group metal.Herein,based on the idea of strong metal–support interaction(SMSI)regulation,Ru/TiN catalysts with different degrees of TiN overlayer over Ru nanoparticles were fabricated,which were applied to the alkaline electrolytic water.Characterizations reveal that the TiN overlayer would gradually encapsulate the Ru nanoparticles and induce more electron transfer from Ru nanoparticles to TiN support by the Ru–N–Ti bond as the SMSI degree increased.Further study shows that the exposed Ru–TiN interfaces greatly promote the H_(2) desorption capacity.Thus,the Ru/TiN-300 with a moderate SMSI degree exhibits excellent HER performance,with an overpotential of 38 mV at 10 mA cm^(−2).Also,due to the encapsulation role of TiN overlayer on Ru nanoparticles,it displays super long-term stability with a very slight potential change after 24 h.This study provides a deep insight into the influence of the SMSI effect between Ru and TiN on HER and offers a novel approach for preparing efficient and stable HER electrocatalysts through SMSI engineering.

Skin‑Inspired Ultra‑Tough Supramolecular Multifunctional Hydrogel Electronic Skin for Human–Machine Interaction

Multifunctional supramolecular ultra-tough bionic e-skin with unique durability for human–machine interaction in complex scenarios still remains challenging.Herein,we develop a skininspired ultra-tough e-skin with tunable mechanical properties by a physical cross-linking salting-freezing-thawing method.The gelling agent(β-Glycerophosphate sodium:Gp)induces the aggregation and binding of PVA molecular chains and thereby toughens them(stress up to 5.79 MPa,toughness up to 13.96 MJ m^(−3)).Notably,due to molecular self-assembly,hydrogels can be fully recycled and reprocessed by direct heating(100°C for a few seconds),and the tensile strength can still be maintained at about 100%after six recoveries.The hydrogel integrates transparency(>60%),super toughness(up to 13.96 MJ m^(−3),bearing 1500 times of its own tensile weight),good antibacterial properties(E.coli and S.aureus),UV protection(Filtration:80%–90%),high electrical conductivity(4.72 S m^(−1)),anti-swelling and recyclability.The hydrogel can not only monitor daily physiological activities,but also be used for complex activities underwater and message encryption/decryption.We also used it to create a complete finger joint rehabilitation system with an interactive interface that dynamically presents the user’s health status.Our multifunctional electronic skin will have a profound impact on the future of new rehabilitation medical,human–machine interaction,VR/AR and the metaverse fields.

Effects of electron–optical phonon interactions on the polaron energy in a wurtzite ZnO/Mg_xZn_(1-x)O quantum well

We investigated the properties of polarons in a wurtzite ZnO/MgxZn1-xO quantum well by adopting a modified Lee–Low–Pines variational method, giving the ground state energy, transition energy, and phonon contributions from various optical-phonon modes to the ground state energy as functions of the well width and Mg composition. In our calculations, we considered the effects of confined optical phonon modes, interface-optical phonon modes, and half-space phonon modes, as well as the anisotropy of the electron effective band mass, phonon frequency, and dielectric constant. Our numerical results indicate that the electron–optical phonon interactions importantly affect the polaronic energies in the ZnO/MgxZn1-xO quantum well. The electron–optical phonon interactions decrease the polaron energies. For quantum wells with narrower wells, the interface optical phonon and half-space phonon modes contribute more to the polaronic energies than the confined phonon modes. However, for wider quantum wells, the total contribution to the polaronic energy mainly comes from the confined modes. The contributions of the various phonon modes to the transition energy change differently with increasing well width. The contribution of the half-space phonons decreases slowly as the QW width increases, whereas the contributions of the confined and interface phonons reach a maximum at d ≈ 5.0 nm and then decrease slowly. However,the total contribution of phonon modes to the transition energy is negative and increases gradually with the QW width of d.As the composition x increases, the total contribution of phonons to the ground state energies increases slowly, but the total contributions of phonons to the transition energies decrease gradually. We analyze the physical reasons for these behaviors in detail.

Electron–acoustic phonon interaction and mobility in stressed rectangular silicon nanowires

We investigate the effects of pre-stress and surface tension on the electron–acoustic phonon scattering rate and the mobility of rectangular silicon nanowires. With the elastic theory and the interaction Hamiltonian for the deformation potential, which considers both the surface energy and the acoustoelastic effects, the phonon dispersion relation for a stressed nanowire under spatial confinement is derived. The subsequent analysis indicates that both surface tension and pre-stress can dramatically change the electron–acoustic phonon interaction. Under a negative（positive） surface tension and a tensile（compressive） pre-stress, the electron mobility is reduced（enhanced） due to the decrease（increase） of the phonon energy as well as the deformation-potential scattering rate. This study suggests an alternative approach based on the strain engineering to tune the speed and the drive current of low-dimensional electronic devices.

Properties of ground state and anomalous quantum fluctuations in one-dimensional polaron-soliton systems-the effects of electron-two-phonon interaction and non-adiabatic quantum correlations

Based on the Holstein model Hamiltonian of one-dimensional molecular crystals, by making use of the expansion approach of the correlated squeezed-coherent states of phonon instead of the two-phonon coherent state expansion scheme, the properties of the ground state and the anomalous quantum fluctuations are investigated in a strongly coupled electron-phonon system with special consideration of the electron-two-phonon interaction. The effective renormalization （ai） of the displacement of the squeezed phonons with the effect of the squeezed-coherent states of phonon and both the electron-displaced pbonon and the polaron-squeezed phonon correlations have been combined to obtain the anomalous quantum fluctuations for the corrections of the coherent state. Due to these non-adiabatic correlations, the effective displacement parameter ai is larger than the ordinary parameter ai （0） In comparison with the electron-one-phonon interaction （g） corrected as oig, we have found the electron-two-phonon interaction （gl） corrected as ai2gi is enhanced significantly. For this reason, the ground state energy （E（2）） contributed by the electron-two-phonon interaction is more negative than the single-phonon case （E01）） and the soliton solution is more stable. At the same time, the effects of the electron-two-phonon interaction greatly increase the polaron energy and the quantum fluctuations. Furthermore, in a deeper level, we have considered the effect of the polaron-squeezed phonon correlation （f-correlation）. Since this correlation parameter f 〉 1, this effect will strengthen the electron-one and two-phonon interactions by fai9 and f2ai2g1, respectively. The final results show that the ground state energy and the polaron energy will appear more negative further and the quantum fluctuations will gain further improvement.

Electron-Phonon Interaction in Small Systems

The effects of electron-phonon interaction have to be taken into account for the physical process in a small system of condensed matters.The electron-phonon interaction in a I-D finite lattice system has been analyzed.The relation between the electron-phonon interaction and the symmetric properties of electronic states and phonons are considered,the transition probabilities are discussed.

Electron-Phonon Interaction in an Annular Quantum Dot

The confined longitudinal-optical （LO） phonon and surface-optical （SO） phonon modes of a free-standing annular cylindrical quantum dot are derived within the framework of dielectric continuum approximation. It is found that there exist two types of SO phonon modes： top SO （TSO） mode and side SO（SSO） mode in a cylindrical quantum annulus. Numerical calculation on CdS annulus system has been performed. Results reveal that the two different solutions of SSO mode distribute mainly at the inner or outer surfaces of the annulus. The dispersion relations and the coupling intensions of phonons in a quantum annulus are compared with those in a cylindrical quantum dot. It is found that the dispersion relations of the two different structures are similar, but the coupling intension of the phonon-electron interaction in quantum annulus is larger than that in quantum dot. The Hamiltonians describing the free phonon modes and their interactions with electrons in the system are also derived.

PERSISTENT CURRENT IN A ONE-DIMENSIONAL MESOSCOPIC RING WITH ELECTRON-PHONON INTERACTION IN THE LATTICE MODEL

A new non-perturbative method is used to discuss the persistent current in a one-dimensional mesoscopic ring threaded by a flux φ with electron-phonon interaction in the lattice model. The current is periodic in φ with a flux quantum φ 0 and the electron-phonon interaction suppresses the persistent current. By considering the contributions of many-phonon correlations, we could obtain more accurate results.

Influence of electron–phonon interaction on the properties of transport through double quantum dot with ferromagnetic leads

Electronic transport through a vibrating double quantum dot （DQD） in contact with noncollinear ferromagnetic （FM） leads is investigated. The state transition between the two dots of the DQD is excited by an AC microwave driving field. The corresponding currents and differential conductance are calculated in the Coulomb blockade regime by means of the Born-Markov master equation. It is shown that the interplay between electrons and phonons gives rise to phonon-assisted tunneling resonances and Franck-Condon blockade under certain conditions. In noncollinear magnetic configurations, spin-blockade effects are also observed, and the angle of polarization has some influence on the transport characteristics.

Dynamic Deformation Electron-Phonon Interaction in Disordered Bulk Semiconductor

We present our theoretical investigations on the effects of disorder on the electron-phonon interaction in semiconducting GaAs system. Both the temperature (T) and disorder (electron mean free path l) dependences of the electron-phonon scattering rate have been determined. On consideration of the dynamic screening, we find a significant change in the temperature exponent as well as the pre factor from the earlier reported temperature power law dependence result ?T6 obtained under static screening. Also the dynamic screening makes a noticeable change in the character of the dependence of scattering rate on the mean free path from the static screening result.

Influence of the Interaction Between Phonons and Coulomb Potential on the Properties of a Bound Polaron in a Quantum Dot

The properties of a bound polaron in a parabolic quantum dot with weak electron-LO-phonon coupling under a Coulomb field are studied. The ground state energy of the bound polaron is derived by using a linear combination operator and the perturbation method. The influence of the interaction between phonons with different wave vectors in the recoil process on the ground state energy of the bound polaron is discussed. Numerical calculations are performed,and the results show that the ground state energy increases significantly as the effective confinement length of the quantum dot decreases,considering of the interaction between phonons. When l0〉1.0, the influence of the interaction between phonons on the ground state energy cannot be ignored.

Electron Momentum Spectroscopy of Valence Orbitals of n-Propyl Iodide： Spin-Orbit Coupling Effect and Intramolecular Orbital Interaction

The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.

Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

Electronic interaction between single Pt atom and vacancies on boron nitride nanosheets and its influence on the catalytic performance in the direct dehydrogenation of propane

The electronic metal-support interaction(EMSI)is one of most intriguing phenomena in heterogeneous catalysis.In this work,this subtle effect is clearly demonstrated by density functional theory(DFT)calculations of single Pt atom supported on vacancies in a boron nitride nanosheet.Moreover,the relation between the EMSI and the performance of Pt in propane direct dehydrogenation(PDH)is investigated in detail.The charge state and partial density of states of single Pt atom show distinct features at different anchoring positions,such as boron and nitrogen vacancies(Bvac and Nvac,respectively).Single Pt atom become positively and negatively charged on Bvac and Nvac,respectively.Therefore,the electronic structure of Pt can be adjusted by rational deposition on the support.Moreover,Pt atoms in different charge states have been shown to have different catalytic abilities in PDH.The DFT calculations reveal that Pt atoms on Bvac(Pt-Bvac)have much higher reactivity towards reactant/product adsorption and C–H bond activation than Pt supported on Nvac(Pt-Nvac),with larger adsorption energy and lower barrier along the reaction pathway.However,the high reactivity of Pt-Bvac also hinders propene desorption,which could lead to unwanted deep dehydrogenation.Therefore,the results obtained herein suggest that a balanced reactivity for C–H activation in propane and propene desorption is required to achieve optimum yields.Based on this descriptor,a single Pt atom on a nitrogen vacancy is considered an effective catalyst for PDH.Furthermore,the deep dehydrogenation of the formed propene is significantly suppressed,owing to the large barrier on Pt-Nvac.The current work demonstrates that the catalytic properties of supported single Pt atoms can be tuned by rationally depositing them on a boron nitride nanosheet and highlights the great potential of single-atom catalysis in the PDH reaction.

Storm-Time Evolution of Energetic Electron Pitch Angle Distributions by Wave-Particle Interaction

The quasi-pure pitch-angle scattering of energetic electrons driven by field-aligned propagating whistler mode waves during the 9～15 October 1990 magnetic storm at L≈ 3 ～ 4 is studied, and numerical calculations for energetic electrons in gyroresonance with a band of frequency of whistler mode waves distributed over a standard Gaussian spectrum is performed. It is found that the whistler mode waves can efficiently drive energetic electrons from the larger pitchangles into the loss cone, and lead to a flat-top distribution during the main phase of geomagnetic storms. This result perhaps presents a feasible interpretation for observation of time evolution of the quasi-isotropic pitch-angle distribution by Combined Release and Radiation Effects Satellite （CRRES） spacecraft at L ≈ 3 ～ 4.

Superthermal Electron Produced in Relativistic Laser-Plasma Interaction

The dynamics of a relativistic electron submitted to an intense, plane wave, linearly polarized laser field is reviewed. Based on the dynamics, the temperature of the electron in the laser field is delined and calculated. It is found that the calculated temperature fits the first temperature observed in the experiment by Malka et al. A model to evaluate the electron temperature by taking the electron-ion scattering into account is proposed. It is found that when I ≥ 4.0 × 101s W/cm2 the electron temperature by considering the scattering, T hs, is evidently larger than the electron temperature without considering the scattering, Th. This result is in favor of explaining the two-temperature distribution of the electron energy observed in the experiment by Malka et al.

Ultrafast Electron Transfer in All-Small-Molecule Photovoltaic Blends Promoted by Intermolecular Interactions in Cyanided Donors

Cyano substitution has been established as a viable approach to optimize the performance of all-small-molecule organic solar cells.However,the effect of cyano substitution on the dynamics of photo-charge generation remains largely unexplored.Here,we report an ultrafast spectroscopic study showing that electron transfer is markedly promoted by enhanced intermolecular charge-transfer interaction in all-small-molecule blends with cyanided donors.The delocalized excitations,arising from intermolecular interaction in the moiety of cyano-substituted donor,undergo ultrafast electron transfer with a lifetime of∼3 ps in the blend.In contrast,some locally excited states,surviving in the film of donor without cyano substitution,are not actively involved in the charge separation.These findings well explain the performance improvement of devices with cyanided donors,suggesting that manipulating intermolecular interaction is an efficient strategy for device optimization.