Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric ...Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.展开更多
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 smal...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.展开更多
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 enh...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.展开更多
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 st...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.展开更多
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 basi...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.展开更多
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...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.展开更多
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 m...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).展开更多
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 excit...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.展开更多
Strategically designing the electrocatalytic system and cleverly inducing strain is an effective approach to balance the cost and activity of Pt-based electrocatalysts for industrial-scale hydrogen production.Herein,w...Strategically designing the electrocatalytic system and cleverly inducing strain is an effective approach to balance the cost and activity of Pt-based electrocatalysts for industrial-scale hydrogen production.Herein,we present a unipolar pulsed electrodeposition(UPED) strategy to induce strain in the Ni lattice by introducing trace amounts of Pt single atoms(SAs)(0.22 wt%).The overpotential decreased by 183 mV at 10 mA cm^(-2) in 1.0 M KOH after introducing trace amounts of Pt_(SAs).The industrial electrolyzer,assembled with Pt_(SAs)Ni cathode and a commercial NiFeO_(x) anode,requires a cell voltage of 1.90 V to attain 1 A cm^(-2) of current density and remains stable for 280 h,demonstrating significant potential for practical applications.Spherical aberration corrected scanning transmission electron microscopy(AC-STEM),X-ray absorption(XAS),and geometric phase analysis(GPA) indicate that the introduction of trace amounts of Pt SAs induces tensile strain in the Ni lattice,thereby altering the local electronic structure and coordination environment around cubic Ni for enhancing the water decomposition kinetics and fundamentally changing the reaction pathway.The doping-strain strategy showcases conformational relationships that could offer new ideas to construct efficient hydrogen evolution reaction(HER) electrocatalysts for industrial hydrogen production in the future.展开更多
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 coll...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.展开更多
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 ...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.展开更多
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 objec...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.展开更多
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...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.展开更多
Metalated covalent organic frameworks(COFs)for 2D and 3D topologies are continuously being developed,whereas metalated COFs with 1D topologies are still in their infancy.Here,a novel 1D phenanthroline-based COF contai...Metalated covalent organic frameworks(COFs)for 2D and 3D topologies are continuously being developed,whereas metalated COFs with 1D topologies are still in their infancy.Here,a novel 1D phenanthroline-based COF containing 4,4-(1,10-phenanthroline-2,9-diyl)bis[benzaldehyde](PBA)is reported(PAD-COF).Subsequently,a metalated 1D COF,Co SAS/PAD-COF,is constructed using the bidentate ligand properties of PBA and anchoring the single Co atoms in PAD-COF through a post-synthetic modification strategy.This complex significantly improved the photocatalytic performance of PAD-COF,and the CO yield of the optimized Co SAS/PAD-COF was stable at 3091µmol g^(-1) h^(-1) with a selectivity of 93%,which is approximately 43.7 times that of the original PAD-COF.Experimental and theoretical results demonstrate the excellent CO_(2) photoreduction activity of Co SAS/PAD-COF owing to the synergistic effect of single Co catalytic sites and PAD-COF.Among them,PAD-COF,as the host,adsorbs CO_(2) molecules and loads single Co atoms.Meanwhile,Co atoms function as catalytic sites and promote the adsorp-tion and activation of CO_(2),while reducing the reaction energy barrier formed by the*COOH intermediates.Therefore,this unique metalated 1D COF provides a fresh approach to photocatalytic CO_(2) reduction.展开更多
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 ...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.展开更多
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 st...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.展开更多
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,b...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.展开更多
Single-atom catalysts(SACs)have gained substantial attention because of their exceptional catalytic properties.However,the high surface energy limits their synthesis,thus creating significant challenges for further de...Single-atom catalysts(SACs)have gained substantial attention because of their exceptional catalytic properties.However,the high surface energy limits their synthesis,thus creating significant challenges for further development.In the last few years,metal–organic frameworks(MOFs)have received significant consideration as ideal candidates for synthesizing SACs due to their tailorable chemistry,tunable morphologies,high porosity,and chemical/thermal stability.From this perspective,this review thoroughly summarizes the previously reported methods and possible future approaches for constructing MOF-based(MOF-derived-supported and MOF-supported)SACs.Then,MOF-based SAC's identification techniques are briefly assessed to understand their coordination environments,local electronic structures,spatial distributions,and catalytic/electrochemical reaction mechanisms.This review systematically highlights several photocatalytic and electrocatalytic applications of MOF-based SACs for energy conversion and storage,including hydrogen evolution reactions,oxygen evolution reactions,O_(2)/CO_(2)/N_(2) reduction reactions,fuel cells,and rechargeable batteries.Some light is also shed on the future development of this highly exciting field by highlighting the advantages and limitations of MOF-based SACs.展开更多
Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reactio...Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reaction(HOR).Herein,we describe the synthesis of a Pt single electrocatalyst inside single-walled carbon nanotubes(SWCNTs)via a redox reaction.Characterizations via electron microscopy,X-ray photoelectron microscopy,and X-ray absorption spectroscopy show the single-atom nature of the Pt.The electrochemical behavior of the sample to hydrogen and oxygen was investigated using the advanced floating electrode technique,which minimizes mass transport limitations and gives a thorough insight into the activity of the electrocatalyst.The single-atom samples showed higher HOR activity than state-of-the-art 30%Pt/C while almost no oxygen reduction reaction activity in the proton exchange membrane fuel cell operating range.The selective activity toward HOR arose as the main fingerprint of the catalyst confinement in the SWCNTs.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:11974136,12174272。
文摘Chirality is one of the fundamental properties of molecules traditionally con-structed from atoms.Here,we report for thefirst time the successful construction of asymmetric chiral structures utilizing highly symmetric endohedral metallo-fullerene superatoms based on their own bonding properties.Specifically,stable mirror-symmetric sinister and rectus structures are obtained by selecting a super-atom capable of forming four chemical bonds as the chiral center.Further analysis shows that the chiral vibration frequency of superatomic assemblies can be as low as a few wavenumbers,which greatly expands the range of chiral spectra com-pared to atom-based molecules.We term this type of chirality based on superatoms as“superatomic-based chirality”.It is anticipated that this work will significantly expand the variety of chiral structures at the atomic level.
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.62020106014,62175140,12034012,and 92165106)the Natural Science Young Foundation of Shanxi Province(Grant No.202203021212376).
文摘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.
基金financially supported by the National Natural Science Foundation of China(22279036)the Innovation Talent Recruitment Base of New Energy Chemistry Device(B21003)the Fundamental Research Funds for the Central Universities(no.2019kfyRCPY100).
文摘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.
基金Project supported by the Space Application System of China Manned Space Programthe Youth Innovation Promotion Association,CAS。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant Nos.12074295,12304271,and 12104420).
文摘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.
基金supported by National Natural Science Foundation of China(52373221,U1910208,52250119)the National Key R&D Program of China(2020YFA0710403)the Scientific Research Fund of Hunan Provincial Education Department(NO.23B0114).
文摘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.
基金Project supported by Beijing Natural Science Foundation(Grant No.1212014)the National Key Research and Development Program of China(Grant Nos.2017YFA0304900 and 2017YFA0402300)+4 种基金the National Natural Science Foundation of China(Grant Nos.11604334,11604177,and U2031125)the Key Research Program of the Chinese Academy of Sciences(Grant No.XDPB08-3)the Open Research Fund Program of the State Key Laboratory of Low-Dimensional Quantum Physics(Grant No.KF201807)the Fundamental Research Funds for the Central UniversitiesYouth Innovation Promotion Association CAS。
文摘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).
基金Project supported by the Shandong Natural Science Foundation,China (Grant No. ZR2021LLZ006)the National Natural Science Foundation of China (Grant Nos. 61675118 and 12274123)+1 种基金the Taishan Scholars Program of Shandong Province,China (Grant No. ts20190936)the Shandong University of Science and Technology Research Fund,China(Grant No. 2015TDJH102)。
文摘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.
基金National Natural Science Foundation of China (grants U22A20418, 22075196, and 21878204)Research Project Supported by Shanxi Scholarship Council of China (2022-050)。
文摘Strategically designing the electrocatalytic system and cleverly inducing strain is an effective approach to balance the cost and activity of Pt-based electrocatalysts for industrial-scale hydrogen production.Herein,we present a unipolar pulsed electrodeposition(UPED) strategy to induce strain in the Ni lattice by introducing trace amounts of Pt single atoms(SAs)(0.22 wt%).The overpotential decreased by 183 mV at 10 mA cm^(-2) in 1.0 M KOH after introducing trace amounts of Pt_(SAs).The industrial electrolyzer,assembled with Pt_(SAs)Ni cathode and a commercial NiFeO_(x) anode,requires a cell voltage of 1.90 V to attain 1 A cm^(-2) of current density and remains stable for 280 h,demonstrating significant potential for practical applications.Spherical aberration corrected scanning transmission electron microscopy(AC-STEM),X-ray absorption(XAS),and geometric phase analysis(GPA) indicate that the introduction of trace amounts of Pt SAs induces tensile strain in the Ni lattice,thereby altering the local electronic structure and coordination environment around cubic Ni for enhancing the water decomposition kinetics and fundamentally changing the reaction pathway.The doping-strain strategy showcases conformational relationships that could offer new ideas to construct efficient hydrogen evolution reaction(HER) electrocatalysts for industrial hydrogen production in the future.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11974091,51973046,U22B2044,and 21673025)the Open Projects of State Key Laboratory of Intense Pulsed Radiation Simulation and Effect (Grant No.SKLIPR2020)。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.52372283)China Postdoctoral Science Foundation(Grant No.2023M730826)+1 种基金Heilongjiang Postdoctoral Fund(Grant No.LBH-Z23121)Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233425).
文摘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.
基金Project supported by the National Natural Science Foundation of China (Grant No.51701071)the Natural Science Foundation of Hunan Province,China (Grant Nos.2022JJ50115 and 2021JJ30179)the Research Foundation of the Education Bureau of Hunan Province,China (Grant No.22A0522)。
文摘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.
基金supported by the National Natural Science Committee of China-Liaoning Provincial People's Government Joint Fund(U1908204)National Natural Science Foundation of China(21876006,21976009,and 21961160743)+2 种基金Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions(IDHT20190503)Natural Science Foundation of Beijing Municipal Commission of Education(KM201710005004)Development Program for the Youth Outstanding-Notch Talent of Beijing Municipal Commission of Education(CIT&TCD201904019)。
文摘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.
基金National Natural Science Foundation of China,Grant/Award Number:51578224Scientific Research Start-up Project for Advanced Talents in Shenzhen City,Grant/Award Number:6023330001K。
文摘Metalated covalent organic frameworks(COFs)for 2D and 3D topologies are continuously being developed,whereas metalated COFs with 1D topologies are still in their infancy.Here,a novel 1D phenanthroline-based COF containing 4,4-(1,10-phenanthroline-2,9-diyl)bis[benzaldehyde](PBA)is reported(PAD-COF).Subsequently,a metalated 1D COF,Co SAS/PAD-COF,is constructed using the bidentate ligand properties of PBA and anchoring the single Co atoms in PAD-COF through a post-synthetic modification strategy.This complex significantly improved the photocatalytic performance of PAD-COF,and the CO yield of the optimized Co SAS/PAD-COF was stable at 3091µmol g^(-1) h^(-1) with a selectivity of 93%,which is approximately 43.7 times that of the original PAD-COF.Experimental and theoretical results demonstrate the excellent CO_(2) photoreduction activity of Co SAS/PAD-COF owing to the synergistic effect of single Co catalytic sites and PAD-COF.Among them,PAD-COF,as the host,adsorbs CO_(2) molecules and loads single Co atoms.Meanwhile,Co atoms function as catalytic sites and promote the adsorp-tion and activation of CO_(2),while reducing the reaction energy barrier formed by the*COOH intermediates.Therefore,this unique metalated 1D COF provides a fresh approach to photocatalytic CO_(2) reduction.
基金the financial support of Conselho Nacional de Desenvolvimento Científico e Tecnológico and Coordenacao de Aperfeic oamento de Pessoal de Nível Superior (Brazilian Agencies)。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.51708078)Natural Science Foundation of Chongqing(Grant No.CSTB2022NSCQ-MSX0815)+2 种基金Science and Technology Research Program of Chongqing Municipal Education Commission(Grant No.KJQN202200542)the Chongqing Innovative Research Group Project(Grant No.CXQT21015)Foundation of Chongqing Normal University(22XLB022).
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.51871078 and 52071119)Interdisciplinary Research Foundation of HIT(Grant No.IR2021208)+1 种基金State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2022TS38)Heilongjiang Science Foundation(No.LH2020B006).
文摘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.
基金support from the Shenzhen Science and Technology Program(No.KQTD20190929173914967,ZDSYS20220527171401003,and JCYJ20200109110416441).
文摘Single-atom catalysts(SACs)have gained substantial attention because of their exceptional catalytic properties.However,the high surface energy limits their synthesis,thus creating significant challenges for further development.In the last few years,metal–organic frameworks(MOFs)have received significant consideration as ideal candidates for synthesizing SACs due to their tailorable chemistry,tunable morphologies,high porosity,and chemical/thermal stability.From this perspective,this review thoroughly summarizes the previously reported methods and possible future approaches for constructing MOF-based(MOF-derived-supported and MOF-supported)SACs.Then,MOF-based SAC's identification techniques are briefly assessed to understand their coordination environments,local electronic structures,spatial distributions,and catalytic/electrochemical reaction mechanisms.This review systematically highlights several photocatalytic and electrocatalytic applications of MOF-based SACs for energy conversion and storage,including hydrogen evolution reactions,oxygen evolution reactions,O_(2)/CO_(2)/N_(2) reduction reactions,fuel cells,and rechargeable batteries.Some light is also shed on the future development of this highly exciting field by highlighting the advantages and limitations of MOF-based SACs.
基金support from Horizon 2020 program within the ITN FlowcampDZ acknowledges funding from the Wohl Foundation for research for the promotion of UK-Israel research cooperationDZ acknowledges funding from Israel Ministry of Energy(grant#220-11-047).
文摘Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reaction(HOR).Herein,we describe the synthesis of a Pt single electrocatalyst inside single-walled carbon nanotubes(SWCNTs)via a redox reaction.Characterizations via electron microscopy,X-ray photoelectron microscopy,and X-ray absorption spectroscopy show the single-atom nature of the Pt.The electrochemical behavior of the sample to hydrogen and oxygen was investigated using the advanced floating electrode technique,which minimizes mass transport limitations and gives a thorough insight into the activity of the electrocatalyst.The single-atom samples showed higher HOR activity than state-of-the-art 30%Pt/C while almost no oxygen reduction reaction activity in the proton exchange membrane fuel cell operating range.The selective activity toward HOR arose as the main fingerprint of the catalyst confinement in the SWCNTs.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
