Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts.Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance,simultaneously provide a radical analysis of the interrelationship between structure and activity.In this review,the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized.Firstly,the synthetic strategies,characterization,dynamics and types of single atoms coupled with clusters/nanoparticles are introduced,and then the key factors controlling the structure of the composite catalysts are discussed.Next,several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated.Eventually,the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.

Multifunctional Film Assembled from N‑Doped Carbon Nanofiber with Co–N_(4)–O Single Atoms for Highly Efficient Electromagnetic Energy Attenuation

Single-atom materials have demonstrated attractive physicochemical characteristics.However,understanding the relationships between the coordination environment of single atoms and their properties at the atomic level remains a considerable challenge.Herein,a facile waterassisted carbonization approach is developed to fabricate well-defined asymmetrically coordinated Co–N_(4)–O sites on biomass-derived carbon nanofiber(Co–N_(4)–O/NCF)for electromagnetic wave(EMW)absorption.In such nanofiber,one atomically dispersed Co site is coordinated with four N atoms in the graphene basal plane and one oxygen atom in the axial direction.In-depth experimental and theoretical studies reveal that the axial Co–O coordination breaks the charge distribution symmetry in the planar porphyrin-like Co–N_(4) structure,leading to significantly enhanced dielectric polarization loss relevant to the planar Co–N_(4) sites.Importantly,the film based on Co–N_(4)–O/NCF exhibits light weight,flexibility,excellent mechanical properties,great thermal insulating feature,and excellent EMW absorption with a reflection loss of−45.82 dB along with an effective absorption bandwidth of 4.8 GHz.The findings of this work offer insight into the relationships between the single-atom coordination environment and the dielectric performance,and the proposed strategy can be extended toward the engineering of asymmetrically coordinated single atoms for various applications.

Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)_(2)Nanosheets with Promoted Hydrogen Absorption in Hydrogen Evolution

Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates,which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts.In this work,Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)_(2)nanosheet arrays.Based on the X-ray absorption fine structure analysis and first-principles calculations,Pt SA was bonded with Ni sites of amorphous Ni(OH)_(2),rather than conventional O sites,resulting in negatively charged Pt^(δ-).In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms,which were the essential intermediate for alkaline hydrogen evolution reaction.The hydrogen spillover process was revealed from amorphous Ni(OH)_(2)that effectively cleave the H-O-H bond of H_(2)O and produce H atom to the Pt SA sites,leading to a low overpotential of 48 mV in alkaline electrolyte at-1000 mA cm^(-2)mg^(-1)_(Pt),evidently better than commercial Pt/C catalysts.This work provided new strategy for the control-lable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.

Microwave electrometry with Rydberg atoms in a vapor cell using microwave amplitude modulation

We have theoretically and experimentally studied the dispersive signal of the Rydberg atomic electromagneticallyinduced transparency(EIT)Autler–Townes(AT)splitting spectra obtained using amplitude modulation of the microwave(MW)electric field.In addition to the two zero-crossing points interval△f_(zeros),the dispersion signal has two positive maxima with an interval defined as the shoulder interval△f_(sho),which is theoretically expected to be used to measure a much weaker MW electric field.The relationship of the MW field strength E_(MW)and△f_(sho)is experimentally studied at the MW frequencies of 31.6 GHz and 9.2 GHz respectively.The results show that△f_(sho)can be used to characterize the much weaker E_(MW)than that of△f_(zeros)and the traditional EIT–AT splitting interval△f_(m);the minimum E_(MW)measured by△f_(sho)is about 30 times smaller than that by△f_(m).As an example,the minimum E_(MW)at 9.2 GHz that can be characterized by△f_(sho)is 0.056 mV/cm,which is the minimum value characterized by the frequency interval using a vapor cell without adding any auxiliary fields.The proposed method can improve the weak limit and sensitivity of E_(MW)measured by the spectral frequency interval,which is important in the direct measurement of weak E_(MW).

Research of caged dynamics of clusters center atoms in Pd_(82)Si_(18) amorphous alloy

To date,there is still a lack of a comprehensive explanation for caged dynamics which is regarded as one of the intricate dynamic behaviors in amorphous alloys.This study focuses on Pd_(82)Si_(18)as the research object to further elucidate the underlying mechanism of caged dynamics from multiple perspectives,including the cage's lifetime,atomic local environment,and atomic potential energy.The results reveal that Si atoms exhibit a pronounced cage effect due to the hindrance of Pd atoms,resulting in an anomalous peak in the non-Gaussian parameters.An in-depth investigation was conducted on the caged dynamics differences between fast and slow Si atoms.In comparison to fast Si atoms,slow Si atoms were surrounded by more Pd atoms and occupied lower potential energy states,resulting in smaller diffusion displacements for the slow Si atoms.Concurrently,slow Si atoms tend to be in the centers of smaller clusters with coordination numbers of 9 and 10.During the isothermal relaxation process,clusters with coordination numbers 9 and 10 have longer lifetimes,suggesting that the escape of slow Si atoms from their cages is more challenging.The findings mentioned above hold significant implications for understanding the caged dynamics.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Optical PAM-4/PAM-8 generation via dual-Raman process in Rydberg atoms

A scheme of optical four-level pulse amplitude modulation(PAM-4) is proposed based on dual-Raman process in Rydberg atoms. A probe field counter-propagates with a dual-Raman field which drives the ground and the excited states transition, respectively, and the Rydberg transition is driven by a microwave(MW) field. A gain peak appears in the probe transmission and is sensitive to the MW field strength. Optical PAM-4 can be achieved by encoding an MW signal and decoding the magnitude of a probe signal. Simulation results show that the differential nonlinearity and the integral nonlinearity of the proposed scheme can be reduced by 5 times and 6 times, respectively, compared with the counterparts of previous scheme, and the ratio of level separation mismatch is close to the ideal value 1. Moreover, the scheme is extended to optical PAM-8 signal, which may further improve the spectral efficiency.

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.

Physics package based on intracavity laser cooling ^(87)Rb atoms for space cold atom microwave clock

This article proposes a new physics package to enhance the frequency stability of the space cold atom clock with the advantages of a microgravity environment. Clock working processes, including atom cooling, atomic state preparation,microwave interrogation, and transition probability detection, are integrated into the cylindrical microwave cavity to achieve a high-performance and compact physics package for the space cold atom clock. We present the detailed design and ground-test results of the cold atom clock physics package in this article, which demonstrates a frequency stability of 1.2×10^(-12) τ^(-1/2) with a Ramsey linewidth of 12.5 Hz, and a better performance is predicted with a 1 Hz or a narrower Ramsey linewidth in microgravity environment. The miniaturized cold atom clock based on intracavity cooling has great potential for achieving space high-precision time-frequency reference in the future.

Geometric properties of the first singlet S-wave excited state of two-electron atoms near the critical nuclear charge

The geometric structure parameters and radial density distribution of 1s2s1S excited state of the two-electron atomic system near the critical nuclear charge Z_(c)were calculated in detail under tripled Hylleraas basis set.Contrary to the localized behavior observed in the ground and the doubly excited 2p^(23)Pe states,for this state our results identify that while the behavior of the inner electron increasingly resembles that of a hydrogen-like atomic system,the outer electron in the excited state exhibits diffused hydrogen-like character and becomes perpendicular to the inner electron as nuclear charge Z approaches Z_(c).This study provides insights into the electronic structure and stability of the two-electron system in the vicinity of the critical nuclear charge.

Efficient loading of cesium atoms in a magnetic levitated dimple trap

We report a detailed study of magnetically levitated loading of ultracold ^(133)Cs atoms in a dimple trap.The atomic sample was produced in a combined red-detuned optical dipole trap and dimple trap formed by two small waist beams crossing a horizontal plane.The magnetic levitation for the ^(133)Cs atoms forms an effective potential for a large number of atoms in a high spatial density.Dependence of the number of atoms loaded and trapped in the dimple trap on the magnetic field gradient and bias field is in good agreement with the theoretical analysis.This method has been widely used to obtain the Bose–Einstein condensation atoms for many atomic species.

Simulation of space heavy-ion induced primary knock-on atoms in bipolar devices

Bipolar junction transistors(BJTs) are often used in spacecraft due to their excellent working characteristics. However,the complex space radiation environment induces primary knock-on atoms(PKAs) in BJTs through collisions, resulting in hard-to-recover displacement damage and affecting the performance of electronic components. In this paper, the properties of PKAs induced by typical space heavy ions(C, N, O, Fe) in BJTs are investigated using Monte Carlo simulations. The simulated results show that the energy spectrum of ion-induced PKAs is primarily concentrated in the low-energy range(17eV–100eV) and displays similar features across all tested ions. The PKAs induced by the collision of energetic ions have large forward scattering angles, mainly around 88°. Moreover, the distribution of PKAs within a transistor as a function of depth displays a peak characteristic, and the peak position is linearly proportional to the incident energy at a certain energy range. These simulation outcomes serve as crucial theoretical support for long-term semiconductor material defect evolution and ground testing of semiconductor devices.

All-electron basis sets for H to Xe specific for ZORA calculations:Applications in atoms and molecules

A segmented basis set of quadruple zeta valence quality plus polarization functions(QZP)for H through Xe was developed to be used in conjunction with the ZORA Hamiltonian.This set was augmented with diffuse functions to describe electrons farther away from the nuclei adequately.Using the ZORA-CCSD(T)/QZP-ZORA theoretical model,atomic ionization energies and bond lengths,harmonic vibrational frequencies,and atomization energies of some molecules were calculated.The addition of core-valence corrections has been shown to improve the agreement between theoretical and experimental results for molecular properties.For atomization energies,a similar observation emerges when considering spin-orbit couplings.With the augmented QZP-ZORA set,static mean dipole polarizabilities of a set of atoms were calculated and compared with previously published recommended and experimental values.Performance evaluations of the ZORA and Douglas–Kroll–Hess Hamiltonians were made for each property studied.

Improved Plasmonic Hot‑Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad‑Spectrum Photocatalytic H_(2)Evolution

ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.

Fine and hyperfine structures of pionic helium atoms

The fine and hyperfine structures of pionic helium metastable states is calculated within the formalism of the Breit-Pauli Hamiltonian by using the variationally generated wave functions in Hylleraas coordinates.Our results not only verify the existing values of Hori et al.[Phys.Rev.A 89,042515(2014)]for the fine structure of π^(4)He^(+),but also determine the hyperfine structure of π^(3)He^(+).

High efficient Raman sideband cooling and strong three-body recombination of atoms

We report a highly efficient three-dimensional degenerated Raman sideband cooling(3D dRSC)that enhances the loading of a magnetically levitated optical dipole trap,and observe the strong atom loss due to the three-body recombination.The 3D dRSC is implemented to obtain 5×10^(7)Cs atoms with the temperature of~480 nK.The cold temperature enables 1.8×10^(7)atoms loaded into a crossed dipole trap with an optimized excessive levitation magnetic gradient.Compared to the loading of atoms from a bare magneto-optical trap or the gray-molasses cooling,there is a significant increase in the number of atoms loaded into the optical dipole trap.We derive for the three-body recombination coefficient of L_(3)=7.73×10^(-25)cm^(6)/s by analyzing the strong atom loss at a large scattering length of 1418 Bohr radius,and discover the transition from the strong three-body loss to the dominant one-body loss.Our result indicates that the lifetime of atoms in the optical dipole trap is finally decided by the one-body loss after the initial strong three-body loss.

Investigation of cyclohexane catalytic degradation driven by N atoms from N_(2)discharges

The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.

Electric field intensity measurement by using doublet electromagnetically induced transparency of cold Rb Rydberg atoms

We demonstrate a simple method to measure electric field intensity by using doublet electromagnetically induced transparency(EIT) spectra of cold Rb Rydberg atoms, where the frequency of the coupling laser does not need to be locked. Based on the Stark splitting of the Rb Rydberg state, 10D_(3/2), under electric fields and the corresponding calculated polarizabilities, the real electric field intensity is calculated using the difference in radio-frequency diffraction between two acousto-optic modulators, which acts as a frequency criterion that allows us to measure the electrical field without locking the coupling laser. The value measured by this simple method shows a good agreement with our previous work [Opt.Express 29 1558(2021)] where the frequency of the coupling laser needs to be locked with an additional EIT spectrum based on atom vapor and a proportional–integral–differential feedback circuit. Our presented method can also be extended to the measurement of electric field based on hot Rydberg atom vapor, which has application in industry.

Single atoms transferring between a magneto-optical trap and a far-off-resonance optical dipole trap

Based on our work on single cesium atoms trapped in a large-magnetic-gradient vapour-cell magneto-optical trap （MOT）, the signal-to-noise ratio （SNR） is remarkably improved. Also a far-off-resonance optical dipole trap （FORT） formed by a strongly-focused 1064 nm single frequency Nd：YVO4 laser beam is introduced. One cesium atom is prepared in the MOT, and then it can transfer successfully between the MOT and the FORT which is overlapped with the MOT. Utilizing the effective transfer, the lifetime of single atoms trapped in the FORT is measured to be 6.9± 0.3 s. Thus we provide a system where the atomic qubit can be coherently manipulated.

Identification of the Intrinsic Dielectric Properties of Metal Single Atoms for Electromagnetic Wave Absorption

Atomically dispersed metals on N-doped carbon supports(M-N_(xCs)) have great potential applications in various fields.However,a precise understanding of the definitive relationship between the configuration of metal single atoms and the dielectric loss properties of M-N_(xCs) at the atomic-level is still lacking.Herein,we report a general approach to synthesize a series of three-dimensional(3D)honeycomb-like M-N_xC(M=Mn,Fe,Co,Cu,or Ni) containing metal single atoms.Experimental results indicate that 3D M-N_(xCs) exhibit a greatly enhanced dielectric loss compared with that of the NC matrix.Theoretical calculations demonstrate that the density of states of the d orbitals near the Fermi level is significantly increased and additional electrical dipoles are induced due to the destruction of the symmetry of the local microstructure,which enhances conductive loss and dipolar polarization loss of 3D M-N_(xCs),respectively.Consequently,these 3D M-N_(xCs) exhibit excellent electromagnetic wave absorption properties,outperforming the most commonly reported absorbers.This study systematically explains the mechanism of dielectric loss at the atomic level for the first time and is of significance to the rational design of high-efficiency electromagnetic wave absorbing materials containing metal single atoms.