Ionization potentials and electron affinities of Cux (n = 2-7) atomic clusters with the optimal geom etries have been calculated by use of SC F-Xa-SW method and Slater's transition state theory. Theo retical calc...Ionization potentials and electron affinities of Cux (n = 2-7) atomic clusters with the optimal geom etries have been calculated by use of SC F-Xa-SW method and Slater's transition state theory. Theo retical calcuIations show that the ionization potentiaIs and electron affinities of Cu. (n = 2-7) atom ic clusters have a sharp even / odd alternation with increasing their sizes, which are related to the electronic structure of Cun atomic clusters. The theoretical results are consistent with the related ex perimental ones.展开更多
The interaction between intense femtosecond laser pulses and hydrogen atomic clusters is studied by a simplified Coulomb explosion model. The dependences of average proton kinetic energy on cluster size, pulse duratio...The interaction between intense femtosecond laser pulses and hydrogen atomic clusters is studied by a simplified Coulomb explosion model. The dependences of average proton kinetic energy on cluster size, pulse duration, laser intensity and wavelength are studied respectively. The calculated results indicate that the irradiation of a femtosecond laser of longer wavelength on hydrogen atomic clusters may be a simple, economical way to produce highly kinetic hydrogen ions. The phenomenon suggests that the irradiation of femtosecond laser of longer wavelength on deuterium atomic clusters may be easier than that of shorter wavelength to drive nuclear fusion reactions. The product of the laser intensity and the squared laser wavelength needed to make proton energy saturated as a function of the squared cluster radius is also investigated. The proton energy distribution calculated is also shown and compared with the experimental data. Our results are in agreement with the experimental results fairly well.展开更多
We exploited a hydrogen-passivated germanium atomic cluster（Ge10H16） as a model to study the mechanism of lithium alloying with germanium. Based on the density functional theory, the electronic and crystal structure...We exploited a hydrogen-passivated germanium atomic cluster（Ge10H16） as a model to study the mechanism of lithium alloying with germanium. Based on the density functional theory, the electronic and crystal structures of lithium-alloyed Ge10H16 were investigated. The theoretical results indicate that the alloying of lithium with Ge10H16 will weaken the germanium-hydrogen bond and repel the closest germanium atom away from the alloyed lithium atom. Based on the maps of the electron density distribution, the nature of the lithium-germanium chemical bond was analyzed. Moreover, the diffusion process of the lithium on the Ge10H16 cluster was detected, which suggested that there is a close relationship between the diffusion barriers and the coordination number around the lithium atom.展开更多
The Fe-N_(4) motif is regarded as a leading non-precious metal catalyst for the oxygen reduction reaction(ORR)with the potential to replace platinum(Pt),yet achieving or surpassing the performance of Ptbased catalysts...The Fe-N_(4) motif is regarded as a leading non-precious metal catalyst for the oxygen reduction reaction(ORR)with the potential to replace platinum(Pt),yet achieving or surpassing the performance of Ptbased catalysts remains a significant challenge.In this study,we introduce a modification strategy employing homogeneous few-atom Fe_(3) cluster to regulate the spin polarization of Fe-N_(4).Experimental research and theoretical calculations show that the incorporation of the Fe_(3) cluster significantly enhances the adsorption of Fe-N_(4) motif toward OH ligands,leading to a structural transformation from a squareplanar field(Fe-N_(4))to a square-pyramid field structure(Fe(OH)-N_(4)).This structural transformation reduces the spin polarization of 3dxz,3dyz,and 3dz 2 orbitals of Fe-N_(4),resulting in a decrease in unpaired electrons within 3d orbitals.As a result,this modulation leads to moderate adsorption/desorption energies of reaction intermediates,thereby facilitating the ORR process.Moreover,the in-situ spectroscopy confirms that the desorption of OH^(*) on Fe_(3)/Fe(OH)-NC motif is more favorable compared to atomic Fe-NC,indicating a lower energy barrier for ORR.Consequently,the Fe_(3)/Fe-NC catalyst demonstrates outstanding ORR performance with a half-wave potential of 0.836 V vs.reversible hydrogen electrode(RHE)in 0.1 mol L^(−1) HClO_(4) solution and 0.936 V vs.RHE in 0.1 mol L^(−1) KOH solution,even surpassing commercial Pt/C catalyst.It also exhibits excellent Zn-air battery efficiency.Our study introduces a novel approach to modulating the electronic structure of single atoms catalysts by leveraging the robust interaction between single atoms and atomic clusters.展开更多
Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clus...Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.展开更多
Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still r...Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still remains a great challenge.In this work,Fe atom clusters(Fe_(AC))modified by high-density Cu single atoms(Cu_(SA))in a N,S-doped porous carbon substrate(Fe_(AC)/Cu_(SA)@NCS)is reported for enhanced ORR electrocatalysis.Fe_(AC)/Cu_(SA)@NCS exhibits excellent ORR performance with a half-wave potential(E_(1/2))of 0.911 V,a high four-electron process selectivity and excellent stability.The ORR performance is also verified in the Fe_(AC)/Cu_(SA)@NCS-based Zn-air battery,which shows a high peak power density of 192.67 mW cm^(-2),a higher specific capacity of 808.3 mAh g^(-1)and impressive charge-discharge cycle stability.Moreover,density functional theory calculations show that Cu single atoms synergistically modulate the electronic structure Fe active atoms in Fe atomic clusters,reducing the energy barrier of the rate-determining step(i.e.,*OH desorption)on Fe_(AC)/Cu_(SA)@NCS.This work provides an effective way to regulate the electronic structure of Fe-based catalysts and optimize their electrocatalytic activity based on the introduction of a second metal source.展开更多
Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomic...Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomically dispersed NiO_(x)cluster supported on Pt-based high-index facets(NiO_(x)/Pt)is proposed to build O-bridged Pt–Ni dual sites.Strikingly,the obtained NiO_(x)/Pt dual sites show 4.97 times specific activity higher than that of commercial Pt/C(0.35 mA cm^(-2)),as well as outstanding CO-tolerance and durability.The advanced electrochemical in-situ characterizations reveal that the NiO_(x)/Pt can accelerate rapid dehydroxylation and C–C bondcleavage over the Pt–Ni dual sites.Theoretical calculations disclose that the atomically dispersed NiO_(x)species can lower the adsorption/reaction energy barriers of intermediates.This tactic provides a promising methodology on regulating the surface synergistic sites via engineering atomically dispersed oxide site.展开更多
Oxidation of CO into CO2 is a major solution to reduce CO emission into the atmosphere and to remove CO in fuel gas cleanup.Furthermore,CO oxidation serves as a prototypical reaction for heterogeneous catalysis.This r...Oxidation of CO into CO2 is a major solution to reduce CO emission into the atmosphere and to remove CO in fuel gas cleanup.Furthermore,CO oxidation serves as a prototypical reaction for heterogeneous catalysis.This review provides an overview and an update on how to study catalytic CO oxidation at a strictly molecular level by performing wellcontrolled gas-phase experiments in combination with quantum chemistry calculations.The advances in the unique catalytic reactivity of single-atom cluster catalysts are emphasized.The catalytically active sites and various mechanistic aspects in the redox couples N2O/CO and O2/CO for the seemingly simple oxidation reaction are described.展开更多
Single-atom catalysts,featuring some of the most unique activities,selectivity,and high metal utilization,have been extensively studied over the past decade.Given their high activity,selectivity,especially towards sma...Single-atom catalysts,featuring some of the most unique activities,selectivity,and high metal utilization,have been extensively studied over the past decade.Given their high activity,selectivity,especially towards small molecules or key intermediate conversions,they can be synergized together with other active species(typically other single atoms,atomic clusters,or nanoparticles)in either tandem or parallel or both,leading to much better performance in complex catalytic processes.Although there have been reports on effectively combining the multiple components into one single catalytic entity,the combination and synergy between single atoms and other active species have not been reviewed and examined in a systematic manner.Herein,in this overview,the key synergistic interactions,binary complementary effects,and the bifunctional functions of single atoms with other active species are defined and discussed in detail.The integration functions of their marriages are in-vestigated with particular emphasis on the homogeneous and heterogeneous combinations,spatial distribution,synthetic strategies,and the thus-derived outstanding catalytic performance,together with new light shined on the catalytic mechanisms by zooming in several case studies.The dynamic nature of each of the active species and in particular their interactions in such new catalytic entities in the heterogeneous electrocatalytic processes are visited,on the basis of the in situ/operando evidence.Last,we feature the current chal-lenges and future perspectives of these integrated catalytic entities that can offer guidance for advanced catalyst design by the rational combination and synergy of binary or multiple active species.展开更多
Based on the theory of micro-inhomogeneity of liquid metal,a calculation model is established for the quantitative description of the structural information of metal melts.Only by thermophysical property parameters an...Based on the theory of micro-inhomogeneity of liquid metal,a calculation model is established for the quantitative description of the structural information of metal melts.Only by thermophysical property parameters and basic structural parameters of solid metal,can this model produce the main information of melt structure,including the relative concentration of active atoms,size of atomic clusters and number of short-range order atoms.Based on this model,the main structural information of Al and Ni melts in the not high range above the liquidus is calculated,with results in good agreement with experimental values.Besides,analyzed is the influence of superheating temperature and atomic number on the melt structural information of the first (IA) and second main group (IIA) elements.With temperature increasing,melt structural information regularly changes for both IA and IIA elements.With the atomic number increasing,melt structural information of IA elements changes regularly,for the crystal structures of the IA elements are all of bcc lattice type.However,no notable regular change of melt structural information for IIA elements has been found,mainly because the lattice type of IIA elements is of hcp-fcc-bcc transition.The present work presents an effective way for better understanding metal melt structure and for forecasting the change of the physical property of metal melts.展开更多
The present study explored a new method to improve the catalytic activity of non-precious metals, especially in electrochemical reactions. Highly ionized Fe plasma produced by arc discharge was uniformly deposited on ...The present study explored a new method to improve the catalytic activity of non-precious metals, especially in electrochemical reactions. Highly ionized Fe plasma produced by arc discharge was uniformly deposited on a porous carbon substrate and formed atomic clusters on the carbon surface. The as-prepared FeO~/C material was tested as a cathode material in a rechargeable Li-02 battery under different current rates. The results showed significant improvement in battery performance in terms of both cycle life and reaction rate. Furthermore, X-ray diffraction （XRD） and scanning electron microscopy （SEM） results showed that the as-prepared cathode material stabilized the cathode and reduced side reactions and that the current rate was a critical factor in the nucleation of the discharge products.展开更多
The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal s...The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal stability and earliest stage evolution of the local atomic clusters show no strong correlation with their initial short-range orders,and this leads to an observation of a novel symmetry convergence phenomenon,which can be understood as an atomic structure manifestation of the ergodicity.Furthermore,in our system we have quantitatively proved that the crucial factor for the thermal stability against crystallization exhibited by the metallic glass is not the total amount of icosahedral clusters,but the degree of global connectivity among them.展开更多
Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored ...Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.展开更多
Nanometer-sized metal clusters were prepared inside single crystalline MgO films by vacuum co-deposition of metals and MgO. The atomic structure was studied by high-resolution electron microscopy (HREM) and nm-area el...Nanometer-sized metal clusters were prepared inside single crystalline MgO films by vacuum co-deposition of metals and MgO. The atomic structure was studied by high-resolution electron microscopy (HREM) and nm-area electron diffraction. The size of the clusters is ranging from 1 nm to 3 nm without those larger than 5 nm, and most of them have definite epitaxial orientations with the MgO matrix films. The character of the composite films is very much useful for the studies of various kinds of physical properties with anisotroPy. The physical properties such as electric transport, magnetic, optical absorption, sintering and catalytic ones were thus measured on the same samples analyzed by HREM by using high sensitivity apparatus with interest of clarifying the retationship between the atomic structure and physical properties展开更多
This paper proposes a scheme for implementing the teleportation of an arbitrary unknown two-atom state by using a cluster state of four identical 2-level atoms as quantum channel in a thermal cavity. The two distinct ...This paper proposes a scheme for implementing the teleportation of an arbitrary unknown two-atom state by using a cluster state of four identical 2-level atoms as quantum channel in a thermal cavity. The two distinct advantages of the present scheme are： （i） The discrimination of 16 orthonormal cluster states in the standard teleportation protocol is transformed into the discrimination of single-atom states. Consequently, the discrimination difficulty of states is degraded. （ii） The scheme is insensitive to the cavity field state and the cavity decay for the thermal cavity is only virtually excited when atoms interact with it. Thus, the scheme is more feasible.展开更多
Protons with very high kinetic energy of about lOkeV and the saturation effect of proton energy for laser intensity have been observed in the interaction of an ultrashort intense laser pulse with large-sized hydrogen ...Protons with very high kinetic energy of about lOkeV and the saturation effect of proton energy for laser intensity have been observed in the interaction of an ultrashort intense laser pulse with large-sized hydrogen dusters. Including the cluster-size distribution as well as the laser-intensity distribution on the focus spot, the theoretical calculations based on a simplified Coulomb explosion model have been compared with our experimental measurements, which are in good agreement with each other.展开更多
We propose an experimentally feasible scheme for preparing a four-atom cluster state in a thermal cavity. In the scheme, the cavity field is only virtually excited and the photon-number-dependent part in the effective...We propose an experimentally feasible scheme for preparing a four-atom cluster state in a thermal cavity. In the scheme, the cavity field is only virtually excited and the photon-number-dependent part in the effective Hamiltonian is cancelled so that the system is insensitive to the cavity decay and the thermal field. At the same time, the scheme can be generalized to prepare n-atom cluster states with the success probability 100%. In addition, using the four-atom cluster state, we also propose a simpler scheme for implementing a remote-controlled not gate （CNOT） without the Bell states measurement.展开更多
Environment-friendly energy storage and conversion technologies,such as metal-air batteries and fuel cells,are considered promising approaches to address growing environmental concerns.The oxygen reduction reaction(OR...Environment-friendly energy storage and conversion technologies,such as metal-air batteries and fuel cells,are considered promising approaches to address growing environmental concerns.The oxygen reduction reaction(ORR)is the core of renewable energy conversion technology and plays an irreplaceable role in this fundamental issue.However,the complex multi-reaction process of the ORR presents a bottleneck that limits efforts to accelerate its kinetics.Traditionally,Pt and Pt-based catalysts are regarded as a good choice to improve the sluggish kinetics of the ORR.However,because Pt-based catalysts are expensive and have low durability,their use to resolve the energy crisis and current environmental challenges is impractical.Hence,exploring low-cost,highly active,and durable ORR catalysts as potential alternatives to commercial Pt/C is an urgent undertaking.Atomic cluster catalysts(ACCs)may be suitable alternatives to commercial Pt/C catalysts owing to their ultra-high atomic utilization efficiency,unique electronic structure,and stable nanostructures.However,despite the significant progress achieved in recent years,ACCs remain unusable for practical applications.In this study,a facile plasma bombing method combined with an acid washing strategy is proposed to fabricate an atomic Co cluster-decorated porous carbon supports catalyst(CoAC/NC)showing improved ORR performance.The typical atomic cluster features of the resultant CoAC/NC catalyst are confirmed using comprehensive characterization techniques.The CoAC/NC catalyst exhibits considerable ORR activity with a half-wave potential of as high as 0.887 V(versus a reversible hydrogen electrode(RHE)),which is much higher than that of a commercial Pt/C catalyst.More importantly,the CoAC/NC catalyst displays excellent battery performance when applied to a Zn-air battery,showing a peak power density of 181.5 mW·cm^(-2)and long discharge ability(over 67 h at a discharge current density of 5 mA·cm^(-2)).The desirable ORR performance of the fabricated CoAC/NC catalyst could be mainly attributed to the high atom utilization efficiency and stable active sites endowed by the unique Co atomic clusters,as well as synergistic effects between the neighboring Co atoms of these clusters.Moreover,the high specific surface area and wide pore distribution of the catalyst offer abundant accessible active sites for the ORR.This work not only provides an outstanding alternative to commercial Pt catalysts for the ORR but also offers new insights into the rational design and practical application of ACCs.展开更多
The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H...The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H- and Zr3O7H- are observed after the reaction. Den-sity functional theory calculations indicate that the hydrogen abstraction is favorable in the reaction of Zr2O5- with C2H6, which supports that the observed Zr2O5H- and Zr3O7H- are due to hydrogen atom abstraction from the alkane molecules. This work shows a newpossible pathway in the reaction of zirconium oxide cluster anions with alkane molecules.展开更多
Neutrons （2.45MeV） from deuterium cluster fusion induced by the intense femtosecond （3Ors） laser pulse are experimentally demonstrated. The average neutron yield 103 per shot is obtained. It is found that the yiel...Neutrons （2.45MeV） from deuterium cluster fusion induced by the intense femtosecond （3Ors） laser pulse are experimentally demonstrated. The average neutron yield 103 per shot is obtained. It is found that the yield slightly increases with the increasing laser spot size. No neutron can be observed when the laser intensity I 〈 4.3 × 10^15 W/cm^2.展开更多
文摘Ionization potentials and electron affinities of Cux (n = 2-7) atomic clusters with the optimal geom etries have been calculated by use of SC F-Xa-SW method and Slater's transition state theory. Theo retical calcuIations show that the ionization potentiaIs and electron affinities of Cu. (n = 2-7) atom ic clusters have a sharp even / odd alternation with increasing their sizes, which are related to the electronic structure of Cun atomic clusters. The theoretical results are consistent with the related ex perimental ones.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10575046 and 10775062)
文摘The interaction between intense femtosecond laser pulses and hydrogen atomic clusters is studied by a simplified Coulomb explosion model. The dependences of average proton kinetic energy on cluster size, pulse duration, laser intensity and wavelength are studied respectively. The calculated results indicate that the irradiation of a femtosecond laser of longer wavelength on hydrogen atomic clusters may be a simple, economical way to produce highly kinetic hydrogen ions. The phenomenon suggests that the irradiation of femtosecond laser of longer wavelength on deuterium atomic clusters may be easier than that of shorter wavelength to drive nuclear fusion reactions. The product of the laser intensity and the squared laser wavelength needed to make proton energy saturated as a function of the squared cluster radius is also investigated. The proton energy distribution calculated is also shown and compared with the experimental data. Our results are in agreement with the experimental results fairly well.
基金financially supported by the Projects of Undergraduate Innovation&entrepreneurship Training Plans of Quanzhou Normal University(No.201310399008)Quanzhou‘‘Tong-Jiang Scholar"program,Fujian‘‘MinJiang Scholar"program,program for New Century Excellent Talents in University(No.NCET-13-0879)the Education and Scientific Research Foundation(Class A)for Young Teachers of Education Bureau of Fujian Province,China(No.JA13263)
文摘We exploited a hydrogen-passivated germanium atomic cluster（Ge10H16） as a model to study the mechanism of lithium alloying with germanium. Based on the density functional theory, the electronic and crystal structures of lithium-alloyed Ge10H16 were investigated. The theoretical results indicate that the alloying of lithium with Ge10H16 will weaken the germanium-hydrogen bond and repel the closest germanium atom away from the alloyed lithium atom. Based on the maps of the electron density distribution, the nature of the lithium-germanium chemical bond was analyzed. Moreover, the diffusion process of the lithium on the Ge10H16 cluster was detected, which suggested that there is a close relationship between the diffusion barriers and the coordination number around the lithium atom.
基金supported by the Key Research and Development Projects of Shaanxi Province(2023GXLH-007)the National Natural Science Foundation of China(22408286 and 62105292)+8 种基金the Scientific and Technological Project of Yunnan Precious Metals Laboratory(YPML-20240502043)China Postdoctoral Science Foundation(2022M712501)the Special Projects on Regional Collaborative innovation-SCO Science and Technology Partnership Programthe International Science and Technology Cooperation Program(2022E01056)the Fundamental Research Funds for the Central Universities(xhj032021001-04)Shccig-Qinling Programsupported by the Natural Science Basic Research Program of Shaanxi(2024JC-YBQN-0504)Shaanxi Fundamental Science Research Project for Mathematics and Physics(22JSQ004 and 22JSY015)the Young Talent Fund of Xi’an Association for Science and Technology(959202313020)。
文摘The Fe-N_(4) motif is regarded as a leading non-precious metal catalyst for the oxygen reduction reaction(ORR)with the potential to replace platinum(Pt),yet achieving or surpassing the performance of Ptbased catalysts remains a significant challenge.In this study,we introduce a modification strategy employing homogeneous few-atom Fe_(3) cluster to regulate the spin polarization of Fe-N_(4).Experimental research and theoretical calculations show that the incorporation of the Fe_(3) cluster significantly enhances the adsorption of Fe-N_(4) motif toward OH ligands,leading to a structural transformation from a squareplanar field(Fe-N_(4))to a square-pyramid field structure(Fe(OH)-N_(4)).This structural transformation reduces the spin polarization of 3dxz,3dyz,and 3dz 2 orbitals of Fe-N_(4),resulting in a decrease in unpaired electrons within 3d orbitals.As a result,this modulation leads to moderate adsorption/desorption energies of reaction intermediates,thereby facilitating the ORR process.Moreover,the in-situ spectroscopy confirms that the desorption of OH^(*) on Fe_(3)/Fe(OH)-NC motif is more favorable compared to atomic Fe-NC,indicating a lower energy barrier for ORR.Consequently,the Fe_(3)/Fe-NC catalyst demonstrates outstanding ORR performance with a half-wave potential of 0.836 V vs.reversible hydrogen electrode(RHE)in 0.1 mol L^(−1) HClO_(4) solution and 0.936 V vs.RHE in 0.1 mol L^(−1) KOH solution,even surpassing commercial Pt/C catalyst.It also exhibits excellent Zn-air battery efficiency.Our study introduces a novel approach to modulating the electronic structure of single atoms catalysts by leveraging the robust interaction between single atoms and atomic clusters.
基金supported by the Start-Up Research Funding of Fujian Normal University(No.Y0720326K13)the National Natural Science Foundation of China(Nos.22103035 and 22033005)+2 种基金the National Key R&D Program of China(No.2022YFA1503900)Shenzhen Science and Technology Program(No.RCYX20231211090357078)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.
基金financially supported by the National Natural Science Foundation of China(No.22278042)the National Natural Science Foundation of Jiangsu Province(No.BK20240567)+2 种基金the Introduction and Cultivation of Leading Innovative Talents Foundation of Changzhou,Jiangsu Province(No.CQ20220093)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.24KJD530001)the Open Project Program of Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science(No.M2024-7),MOE
文摘Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still remains a great challenge.In this work,Fe atom clusters(Fe_(AC))modified by high-density Cu single atoms(Cu_(SA))in a N,S-doped porous carbon substrate(Fe_(AC)/Cu_(SA)@NCS)is reported for enhanced ORR electrocatalysis.Fe_(AC)/Cu_(SA)@NCS exhibits excellent ORR performance with a half-wave potential(E_(1/2))of 0.911 V,a high four-electron process selectivity and excellent stability.The ORR performance is also verified in the Fe_(AC)/Cu_(SA)@NCS-based Zn-air battery,which shows a high peak power density of 192.67 mW cm^(-2),a higher specific capacity of 808.3 mAh g^(-1)and impressive charge-discharge cycle stability.Moreover,density functional theory calculations show that Cu single atoms synergistically modulate the electronic structure Fe active atoms in Fe atomic clusters,reducing the energy barrier of the rate-determining step(i.e.,*OH desorption)on Fe_(AC)/Cu_(SA)@NCS.This work provides an effective way to regulate the electronic structure of Fe-based catalysts and optimize their electrocatalytic activity based on the introduction of a second metal source.
基金supported by the National Natural Science Foundation of China(22305101)the Natural Science Foundation of Jiangsu Province(BK20231032)+1 种基金the Fundamental Research Funds for the Central Universities(JUSRP123020)Startup Funding at Jiangnan University(1045219032220100).
文摘Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomically dispersed NiO_(x)cluster supported on Pt-based high-index facets(NiO_(x)/Pt)is proposed to build O-bridged Pt–Ni dual sites.Strikingly,the obtained NiO_(x)/Pt dual sites show 4.97 times specific activity higher than that of commercial Pt/C(0.35 mA cm^(-2)),as well as outstanding CO-tolerance and durability.The advanced electrochemical in-situ characterizations reveal that the NiO_(x)/Pt can accelerate rapid dehydroxylation and C–C bondcleavage over the Pt–Ni dual sites.Theoretical calculations disclose that the atomically dispersed NiO_(x)species can lower the adsorption/reaction energy barriers of intermediates.This tactic provides a promising methodology on regulating the surface synergistic sites via engineering atomically dispersed oxide site.
基金This work was financially supported by the National Natural Science Foundation of China(21773253).
文摘Oxidation of CO into CO2 is a major solution to reduce CO emission into the atmosphere and to remove CO in fuel gas cleanup.Furthermore,CO oxidation serves as a prototypical reaction for heterogeneous catalysis.This review provides an overview and an update on how to study catalytic CO oxidation at a strictly molecular level by performing wellcontrolled gas-phase experiments in combination with quantum chemistry calculations.The advances in the unique catalytic reactivity of single-atom cluster catalysts are emphasized.The catalytically active sites and various mechanistic aspects in the redox couples N2O/CO and O2/CO for the seemingly simple oxidation reaction are described.
基金JW and team thank the support of MOE,Singapore(MOE2018-T2-2-095),for research conducted at the National University of Singapore.
文摘Single-atom catalysts,featuring some of the most unique activities,selectivity,and high metal utilization,have been extensively studied over the past decade.Given their high activity,selectivity,especially towards small molecules or key intermediate conversions,they can be synergized together with other active species(typically other single atoms,atomic clusters,or nanoparticles)in either tandem or parallel or both,leading to much better performance in complex catalytic processes.Although there have been reports on effectively combining the multiple components into one single catalytic entity,the combination and synergy between single atoms and other active species have not been reviewed and examined in a systematic manner.Herein,in this overview,the key synergistic interactions,binary complementary effects,and the bifunctional functions of single atoms with other active species are defined and discussed in detail.The integration functions of their marriages are in-vestigated with particular emphasis on the homogeneous and heterogeneous combinations,spatial distribution,synthetic strategies,and the thus-derived outstanding catalytic performance,together with new light shined on the catalytic mechanisms by zooming in several case studies.The dynamic nature of each of the active species and in particular their interactions in such new catalytic entities in the heterogeneous electrocatalytic processes are visited,on the basis of the in situ/operando evidence.Last,we feature the current chal-lenges and future perspectives of these integrated catalytic entities that can offer guidance for advanced catalyst design by the rational combination and synergy of binary or multiple active species.
基金supported by the National Basic Research Program of China (Grant No. 2007CB613702)International Cooperation Program in Science and Technology (Grant No. 2007DFC50090)
文摘Based on the theory of micro-inhomogeneity of liquid metal,a calculation model is established for the quantitative description of the structural information of metal melts.Only by thermophysical property parameters and basic structural parameters of solid metal,can this model produce the main information of melt structure,including the relative concentration of active atoms,size of atomic clusters and number of short-range order atoms.Based on this model,the main structural information of Al and Ni melts in the not high range above the liquidus is calculated,with results in good agreement with experimental values.Besides,analyzed is the influence of superheating temperature and atomic number on the melt structural information of the first (IA) and second main group (IIA) elements.With temperature increasing,melt structural information regularly changes for both IA and IIA elements.With the atomic number increasing,melt structural information of IA elements changes regularly,for the crystal structures of the IA elements are all of bcc lattice type.However,no notable regular change of melt structural information for IIA elements has been found,mainly because the lattice type of IIA elements is of hcp-fcc-bcc transition.The present work presents an effective way for better understanding metal melt structure and for forecasting the change of the physical property of metal melts.
文摘The present study explored a new method to improve the catalytic activity of non-precious metals, especially in electrochemical reactions. Highly ionized Fe plasma produced by arc discharge was uniformly deposited on a porous carbon substrate and formed atomic clusters on the carbon surface. The as-prepared FeO~/C material was tested as a cathode material in a rechargeable Li-02 battery under different current rates. The results showed significant improvement in battery performance in terms of both cycle life and reaction rate. Furthermore, X-ray diffraction （XRD） and scanning electron microscopy （SEM） results showed that the as-prepared cathode material stabilized the cathode and reduced side reactions and that the current rate was a critical factor in the nucleation of the discharge products.
基金supported by the National Natural Science Foundation of China (Grant Nos. 52031016 and 11804027)the China Scholarship Council for financial support during part of this work
文摘The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal stability and earliest stage evolution of the local atomic clusters show no strong correlation with their initial short-range orders,and this leads to an observation of a novel symmetry convergence phenomenon,which can be understood as an atomic structure manifestation of the ergodicity.Furthermore,in our system we have quantitatively proved that the crucial factor for the thermal stability against crystallization exhibited by the metallic glass is not the total amount of icosahedral clusters,but the degree of global connectivity among them.
文摘Heterogeneous catalysts with ultra-small clusters and atomically dispersed(USCAD)active sites have gained increasing attention in recent years.However,developing USCAD catalysts with high-density metal sites anchored in porous nanomaterials is still challenging.Here,through the template-free S-assisted pyrolysis of low-cost Fe-salts with melamine(MA),porous alveolate Fe/g-C3N4 catalysts with high-density(Fe loading up to 17.7 wt%)and increased USCAD Fe sites were synthesized.The presence of a certain amount of S species in the Fe-salts/MA system plays an important role in the formation of USCAD S-Fe-salt/CN catalysts;the S species act as a"sacrificial carrier"to increase the dispersion of Fe species through Fe-S coordination and generate porous alveolate structure by escaping in the form of SO2 during pyrolysis.The S-Fe-salt/CN catalysts exhibit greatly promoted activity and reusability for degrading various organic pollutants in advanced oxidation processes compared to the corresponding Fe-salt/CN catalysts,due to the promoted accessibility of USCAD Fe sites by the porous alveolate structure.This S-assisted method exhibits good feasibility in a large variety of S species(thiourea,S powder,and NH4SCN)and Fe salts,providing a new avenue for the low-cost and large-scale synthesis of high-density USCAD metal/g-C3N4 catalysts.
文摘Nanometer-sized metal clusters were prepared inside single crystalline MgO films by vacuum co-deposition of metals and MgO. The atomic structure was studied by high-resolution electron microscopy (HREM) and nm-area electron diffraction. The size of the clusters is ranging from 1 nm to 3 nm without those larger than 5 nm, and most of them have definite epitaxial orientations with the MgO matrix films. The character of the composite films is very much useful for the studies of various kinds of physical properties with anisotroPy. The physical properties such as electric transport, magnetic, optical absorption, sintering and catalytic ones were thus measured on the same samples analyzed by HREM by using high sensitivity apparatus with interest of clarifying the retationship between the atomic structure and physical properties
基金supported by the Program for New Century Excellent Talents at the University of China (Grant No NCET-06-0554)the National Natural Science Foundation of China (Grant Nos 60677001 and 10747146)+3 种基金the Science-Technology Fund of AnhuiProvince for Outstanding Youth of China (Grant No 06042087)the Key Fund of the Ministry of Education of China (Grant No 206063)the Natural Science Foundation of Guangdong Province of China (Grant Nos 06300345 and 7007806)Natural Science Foundation of Hubei Province of China (Grant No 2006ABA354)
文摘This paper proposes a scheme for implementing the teleportation of an arbitrary unknown two-atom state by using a cluster state of four identical 2-level atoms as quantum channel in a thermal cavity. The two distinct advantages of the present scheme are： （i） The discrimination of 16 orthonormal cluster states in the standard teleportation protocol is transformed into the discrimination of single-atom states. Consequently, the discrimination difficulty of states is degraded. （ii） The scheme is insensitive to the cavity field state and the cavity decay for the thermal cavity is only virtually excited when atoms interact with it. Thus, the scheme is more feasible.
基金Supported by the National Natural Science Foundation of China under Grant No 10535070.
文摘Protons with very high kinetic energy of about lOkeV and the saturation effect of proton energy for laser intensity have been observed in the interaction of an ultrashort intense laser pulse with large-sized hydrogen dusters. Including the cluster-size distribution as well as the laser-intensity distribution on the focus spot, the theoretical calculations based on a simplified Coulomb explosion model have been compared with our experimental measurements, which are in good agreement with each other.
基金Project supported by the National Natural Science Foundation （Grant No 10574022）, and the Funds of the Natural Science of Fujian Province, China （Grant No Z0512006）.
文摘We propose an experimentally feasible scheme for preparing a four-atom cluster state in a thermal cavity. In the scheme, the cavity field is only virtually excited and the photon-number-dependent part in the effective Hamiltonian is cancelled so that the system is insensitive to the cavity decay and the thermal field. At the same time, the scheme can be generalized to prepare n-atom cluster states with the success probability 100%. In addition, using the four-atom cluster state, we also propose a simpler scheme for implementing a remote-controlled not gate （CNOT） without the Bell states measurement.
文摘Environment-friendly energy storage and conversion technologies,such as metal-air batteries and fuel cells,are considered promising approaches to address growing environmental concerns.The oxygen reduction reaction(ORR)is the core of renewable energy conversion technology and plays an irreplaceable role in this fundamental issue.However,the complex multi-reaction process of the ORR presents a bottleneck that limits efforts to accelerate its kinetics.Traditionally,Pt and Pt-based catalysts are regarded as a good choice to improve the sluggish kinetics of the ORR.However,because Pt-based catalysts are expensive and have low durability,their use to resolve the energy crisis and current environmental challenges is impractical.Hence,exploring low-cost,highly active,and durable ORR catalysts as potential alternatives to commercial Pt/C is an urgent undertaking.Atomic cluster catalysts(ACCs)may be suitable alternatives to commercial Pt/C catalysts owing to their ultra-high atomic utilization efficiency,unique electronic structure,and stable nanostructures.However,despite the significant progress achieved in recent years,ACCs remain unusable for practical applications.In this study,a facile plasma bombing method combined with an acid washing strategy is proposed to fabricate an atomic Co cluster-decorated porous carbon supports catalyst(CoAC/NC)showing improved ORR performance.The typical atomic cluster features of the resultant CoAC/NC catalyst are confirmed using comprehensive characterization techniques.The CoAC/NC catalyst exhibits considerable ORR activity with a half-wave potential of as high as 0.887 V(versus a reversible hydrogen electrode(RHE)),which is much higher than that of a commercial Pt/C catalyst.More importantly,the CoAC/NC catalyst displays excellent battery performance when applied to a Zn-air battery,showing a peak power density of 181.5 mW·cm^(-2)and long discharge ability(over 67 h at a discharge current density of 5 mA·cm^(-2)).The desirable ORR performance of the fabricated CoAC/NC catalyst could be mainly attributed to the high atom utilization efficiency and stable active sites endowed by the unique Co atomic clusters,as well as synergistic effects between the neighboring Co atoms of these clusters.Moreover,the high specific surface area and wide pore distribution of the catalyst offer abundant accessible active sites for the ORR.This work not only provides an outstanding alternative to commercial Pt catalysts for the ORR but also offers new insights into the rational design and practical application of ACCs.
基金This work was supported by the Chinese Academy of Sciences （Hundred Talents Fund）, the National Natural Science Foundation of China （No.20703048 and No.20803083）, and the Center of Molecular Science Foundation of Institute of Chemistry, Chinese Academy of Sciences （No.CMS-LX200902）.
文摘The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H- and Zr3O7H- are observed after the reaction. Den-sity functional theory calculations indicate that the hydrogen abstraction is favorable in the reaction of Zr2O5- with C2H6, which supports that the observed Zr2O5H- and Zr3O7H- are due to hydrogen atom abstraction from the alkane molecules. This work shows a newpossible pathway in the reaction of zirconium oxide cluster anions with alkane molecules.
基金Supported by the National Natural Science Foundation of China under Grant No 10535030, and the Key Foundation of China Academy of Engineering Physics under Grant No 2006Z0202.
文摘Neutrons （2.45MeV） from deuterium cluster fusion induced by the intense femtosecond （3Ors） laser pulse are experimentally demonstrated. The average neutron yield 103 per shot is obtained. It is found that the yield slightly increases with the increasing laser spot size. No neutron can be observed when the laser intensity I 〈 4.3 × 10^15 W/cm^2.
