Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept ...Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.展开更多
We theoretically study the charge order and orbital magnetic properties of a new type of antiferromagnetic kagome metal FeGe.Based on first-principles density functional theory calculations,we study the electronic str...We theoretically study the charge order and orbital magnetic properties of a new type of antiferromagnetic kagome metal FeGe.Based on first-principles density functional theory calculations,we study the electronic structures,Fermi-surface quantum fluctuations,as well as phonon properties of the antiferromagnetic kagome metal FeGe.It is found that charge density wave emerges in such a system due to a subtle cooperation between electron-electron interactions and electron–phonon couplings,which gives rise to an unusual scenario of interaction-triggered phonon instabilities,and eventually yields a charge density wave(CDW)state.We further show that,in the CDW phase,the ground-state current density distribution exhibits an intriguing star-of-David pattern,leading to flux density modulation.The orbital fluxes(or current loops)in this system emerge as a result of the subtle interplay between magnetism,lattice geometries,charge order,and spin-orbit coupling(SOC),which can be described by a simple,yet universal,tight-binding theory including a Kane-Mele-type SOC term and a magnetic exchange interaction.We further study the origin of the peculiar step-edge states in FeGe,which sheds light on the topological properties and correlation effects in this new type of kagome antiferromagnetic material.展开更多
The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in ele...The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.展开更多
We propose an optical image watermarking scheme based on orbital angular momentum(OAM)holography.Multiple topological charges(TCs,l)of OAM,as multiple cryptographic sub-keys,are embedded into the host image along with...We propose an optical image watermarking scheme based on orbital angular momentum(OAM)holography.Multiple topological charges(TCs,l)of OAM,as multiple cryptographic sub-keys,are embedded into the host image along with the watermark information.Moreover,the Arnold transformation is employed to further enhance the security and the scrambling time(m)is also served as another cryptographic key.The watermark image is embedded into the host image by using the discrete wavelet transformation(DWT)and singular value decomposition(SVD)methods.Importantly,the interference image is utilized to further enhance security.The imperceptibility of our proposed method is analyzed by using the peak signal-to-noise ratio(PSNR)and the histogram of the watermarked host image.To demonstrate robustness,a series of attack tests,including Gaussian noise,Poisson noise,salt-and-pepper noise,JPEG compression,Gaussian lowpass filtering,cropping,and rotation,are conducted.The experimental results show that our proposed method has advanced security,imperceptibility,and robustness,making it a promising option for optical image watermarking applications.展开更多
Orbital angular momentum(OAM)holography has become a promising technique in information encryption,data storage and opto-electronic computing,owing to the infinite topological charge of one single OAM mode and the ort...Orbital angular momentum(OAM)holography has become a promising technique in information encryption,data storage and opto-electronic computing,owing to the infinite topological charge of one single OAM mode and the orthogonality of different OAM modes.In this paper,we propose a novel OAM hologram generation method based on a densely connected U-net(DCU),where the densely connected convolution blocks(DCB)replace the convolution blocks of the U-net.Importantly,the reconstruction process of the OAM hologram is integrated into DCU as its output layer,so as to eliminate the requirement to prepare training data for the OAM hologram,which is required by conventional neural networks through an iterative algorithm.The experimental and simulation results show that the OAM hologram can rapidly be generated with the well-trained DCU,and the reconstructed image's quality from the generated OAM hologram is significantly improved in comparison with those from the Gerchberg-Saxton generation method,the Gerchberg-Saxton based generation method and the U-net method.In addition,a 10-bit OAM multiplexing hologram scheme is numerically demonstrated to have a high capacity with OAM hologram.展开更多
Orbital angular momentum(OAM), as a new degree of freedom, has recently been applied in holography technology.Due to the infinite helical mode index of OAM mode, a large number of holographic images can be reconstruct...Orbital angular momentum(OAM), as a new degree of freedom, has recently been applied in holography technology.Due to the infinite helical mode index of OAM mode, a large number of holographic images can be reconstructed from an OAM-multiplexing hologram. However, the traditional design of an OAM hologram is constrained by the helical mode index of the selected OAM mode, for a larger helical mode index OAM mode has a bigger sampling distance, and the crosstalk is produced for different sampling distances for different OAM modes. In this paper, we present the design of the OAM hologram based on a Bessel–Gaussian beam, which is non-diffractive and has a self-healing property during its propagation. The Fourier transform of the Bessel–Gaussian beam is the perfect vortex mode that has the fixed ring radius for different OAM modes. The results of simulation and experiment have demonstrated the feasibility of the generation of the OAM hologram with the Bessel–Gaussian beam. The quality of the reconstructed holographic image is increased, and the security is enhanced. Additionally, the anti-interference property is improved owing to its self-healing property of the Bessel-OAM holography.展开更多
We theoretically studied the dynamic properties of the skyrmion driven by electromagnetic(EM)waves with spin angular momentum(SAM)and orbital angular momentum(OAM)using micromagnetic simulations.First,the guiding cent...We theoretically studied the dynamic properties of the skyrmion driven by electromagnetic(EM)waves with spin angular momentum(SAM)and orbital angular momentum(OAM)using micromagnetic simulations.First,the guiding centers of the skyrmion driven by EM waves with SAM,i.e.,left-handed and right-handed circularly polarized EM waves,present circular trajectories,while present elliptical trajectories under linear EM waves driving due to the superposition of oppositely polarized wave components.Second,the trajectories of the skyrmion driven by EM waves with OAM demonstrate similar behavior to that driven by linearly polarized EM waves.Because the wave vector intensity varies with the phase for both linearly polarized EM waves and EM waves with OAM,the angular momentum is transferred to the skyrmion non-uniformly,while the angular momentum is transferred to the skyrmion uniformly for left-handed and right-handed circularly polarized EM driving.Third,the dynamic properties of the skyrmion driven by EM waves with both SAM and OAM are investigated.It is found that the dynamic trajectories exhibit more complex behavior due to the contributions or competition of SAM and OAM.We investigate the characteristics of intrinsic gyration modes and frequency-dependent trajectories.Our research may provide insight into the dynamic properties of skyrmion manipulated by EM waves with SAM or OAM and provide a method for controlling skyrmion in spintronic devices.展开更多
Fractional orbital angular momentum(OAM) vortex beams present a promising way to increase the data throughput in optical communication systems. Nevertheless, high-precision recognition of fractional OAM with different...Fractional orbital angular momentum(OAM) vortex beams present a promising way to increase the data throughput in optical communication systems. Nevertheless, high-precision recognition of fractional OAM with different propagation distances remains a significant challenge. We develop a convolutional neural network(CNN)method to realize high-resolution recognition of OAM modalities, leveraging asymmetric Bessel beams imbued with fractional OAM. Experimental results prove that our method achieves a recognition accuracy exceeding 94.3% for OAM modes, with an interval of 0.05, and maintains a high recognition accuracy above 92% across varying propagation distances. The findings of our research will be poised to significantly contribute to the deployment of fractional OAM beams within the domain of optical communications.展开更多
Two-dimensional(2D)van der Waals magnetic materials have promising and versatile electronic and magnetic properties in the 2D limit,indicating a considerable potential to advance spintronic applications.Theoretical pr...Two-dimensional(2D)van der Waals magnetic materials have promising and versatile electronic and magnetic properties in the 2D limit,indicating a considerable potential to advance spintronic applications.Theoretical predictions thus far have not ascertained whether monolayer VCl_(3) is a ferromagnetic(FM)or anti-FM monolayer;this also remains to be experimentally verified.We theoretically investigate the influence of potential factors,including C_(3) symmetry breaking,orbital ordering,epitaxial strain,and charge doping,on the magnetic ground state.Utilizing first-principles calculations,we predict a collinear type-Ⅲ FM ground state in monolayer VCl_(3) with a broken C_(3) symmetry,wherein only the former two of three t_(2g)orbitals(a_(1g),e_(g2)^(π)and e_(g1)^(π))are occupied.The atomic layer thickness and bond angles of monolayer VCl_(3) undergo abrupt changes driven by an orbital ordering switch,resulting in concomitant structural and magnetic phase transitions.Introducing doping to the underlying Cl atoms of monolayer VCl_(3) without C_(3) symmetry simultaneously induces in-and out-of-plane polarizations.This can achieve a multiferroic phase transition if combined with the discovered adjustments of magnetic ground state and polarization magnitude under strain.The establishment of an orbital-ordering driven regulatory mechanism can facilitate deeper exploration and comprehension of magnetic properties of strongly correlated systems in monolayer VCl_(3).展开更多
The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing...The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing CO_(2) to C_(2+)products,the instability of Cu^(+)species,which tend to reduce to Cu~0 at cathodic potentials during CO_(2) reduction,poses a significant challenge.Here,we report the development of SmCu_(2)O and investigate the influence of f-d orbital hybridization on the CO_(2) reduction reaction (CO_(2)RR).Supported by density functional theory (DFT) calculations,our experimental results demonstrate that hybridization between Sm^(3+)4f and Cu^(+)3d orbitals not only improves the adsorption of *CO intermediates and increases CO coverage to stabilize Cu^(+) but also facilitates CO_(2) activation and lowers the energy barriers for CAC coupling.Notably,Sm-Cu_(2)O achieves a Faradaic efficiency for C_(2)H_(4) that is 38%higher than that of undoped Cu_(2)O.Additionally,it sustains its catalytic activity over an extended operational period exceeding 7 h,compared to merely 2 h for the undoped sample.This research highlights the potential of fd orbital hybridization in enhancing the efficacy of copper-based catalysts for CO_(2)RR,pointing towards a promising direction for the development of durable,high-performance electrocatalysts for sustainable chemical synthesis.展开更多
Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has gar...Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.展开更多
Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction ...Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction due to thermodynamic instability,which has resulted in conflicting reports within the literature regarding its role.To clarify this point,we propose a strategy consisting of modulating the electronic orbital occupancy to suppress the extensive loss of Fe atoms during the OER process.Theoretical calculations,in-situ X-ray photoelectron spectroscopy,molecular dynamics simulations,and a series of characterization showed that the stable presence of Fe not only accelerates the electron transfer process but also optimizes the reaction barriers of the oxygen evolution intermediates,promoting the phase transition of Fe_(5)Ni_(4)S_(8)to highly active catalytic species.The modulated Fe_(5)Ni_(4)S_(8)-based pre-catalysts exhibit improved OER activity and long-term durability.This study provides a novel perspective for understanding the role of Fe in the OER process.展开更多
The ability to overcome the negative effects,induced by obstacles and turbulent atmosphere,is a core challenge of long-distance information transmission,and it is of great significance in free-space optical communicat...The ability to overcome the negative effects,induced by obstacles and turbulent atmosphere,is a core challenge of long-distance information transmission,and it is of great significance in free-space optical communication.The spatial-coherence structure,that characterizes partially coherent fields,provides a new degree of freedom for carrying information.However,due to the influence of the complex transmission environment,the spatial-coherence structure is severely damaged during the propagation path,which undoubtedly limits its ability to transmit information.Here,we realize the robust far-field orbital angular momentum(OAM)transmission and detection by modulating the spatial-coherence structure of a partially coherent vortex beam with the help of the cross-phase.The cross-phase enables the OAM information,quantified by the topological charge,hidden in the spatial-coherence structure can be stably transmitted to the far field and can resist the influence of obstructions and turbulence within the communication link.This is due to the self-reconstruction property of the spatial-coherence structure embedded with the cross-phase.We demonstrate experimentally that the topological charge information can be recognized well by measuring the spatial-coherence structure in the far field,exhibiting a set of distinct and separated dark rings even under amplitude and phase perturbations.Our findings open a door for robust optical signal transmission through the complex environment and may find application in optical communication through a turbulent atmosphere.展开更多
Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To c...Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.展开更多
Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecul...Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.展开更多
In this paper, we propose a measurement-device-independent quantum-key-distribution（MDI-QKD） protocol using orbital angular momentum（OAM） in free space links, named the OAM-MDI-QKD protocol. In the proposed protoc...In this paper, we propose a measurement-device-independent quantum-key-distribution（MDI-QKD） protocol using orbital angular momentum（OAM） in free space links, named the OAM-MDI-QKD protocol. In the proposed protocol,the OAM states of photons, instead of polarization states, are used as the information carriers to avoid the reference frame alignment, the decoy-state is adopted to overcome the security loophole caused by the weak coherent pulse source, and the high efficient OAM-sorter is adopted as the measurement tool for Charlie to obtain the output OAM state. Here, Charlie may be an untrusted third party. The results show that the authorized users, Alice and Bob, could distill a secret key with Charlie＇s successful measurements, and the key generation performance is slightly better than that of the polarization-based MDI-QKD protocol in the two-dimensional OAM cases. Simultaneously, Alice and Bob can reduce the number of flipping the bits in the secure key distillation. It is indicated that a higher key generation rate performance could be obtained by a high dimensional OAM-MDI-QKD protocol because of the unlimited degree of freedom on OAM states. Moreover,the results show that the key generation rate and the transmission distance will decrease as the growth of the strength of atmospheric turbulence（AT） and the link attenuation. In addition, the decoy states used in the proposed protocol can get a considerable good performance without the need for an ideal source.展开更多
The light＇s orbital angular momentum （OAM） is a consequence of the spiral flow of the electromagnetic energy. In this paper, an analysis of light beams with OAM used for free space optics （FSO） is conducted. The ...The light＇s orbital angular momentum （OAM） is a consequence of the spiral flow of the electromagnetic energy. In this paper, an analysis of light beams with OAM used for free space optics （FSO） is conducted. The basic description and conception of light＇s OAM are reviewed. Both encoding information into OAM states of single light beam and encoding information into spatial structure of the mixed optical vortex with OAM are discussed, and feasibility to improve the FSO＇s performance of security and obstruction of line of sight is examined.展开更多
基金financially supported by the National Natural Science Foundation of China(21972068,22072067,22232004)the High-level Talents Project of Jinling Institute of Technology(jit-b-202164)。
文摘Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.
基金supported by the National Natural Science Foundation of China(Grant No.12174257)the National Key R&D program of China(Grant No.2020YFA0309601)+1 种基金the Science and Technology Commission of the Shanghai Municipality(Grant No.21JC1405100)the Start-Up Grant of ShanghaiTech University。
文摘We theoretically study the charge order and orbital magnetic properties of a new type of antiferromagnetic kagome metal FeGe.Based on first-principles density functional theory calculations,we study the electronic structures,Fermi-surface quantum fluctuations,as well as phonon properties of the antiferromagnetic kagome metal FeGe.It is found that charge density wave emerges in such a system due to a subtle cooperation between electron-electron interactions and electron–phonon couplings,which gives rise to an unusual scenario of interaction-triggered phonon instabilities,and eventually yields a charge density wave(CDW)state.We further show that,in the CDW phase,the ground-state current density distribution exhibits an intriguing star-of-David pattern,leading to flux density modulation.The orbital fluxes(or current loops)in this system emerge as a result of the subtle interplay between magnetism,lattice geometries,charge order,and spin-orbit coupling(SOC),which can be described by a simple,yet universal,tight-binding theory including a Kane-Mele-type SOC term and a magnetic exchange interaction.We further study the origin of the peculiar step-edge states in FeGe,which sheds light on the topological properties and correlation effects in this new type of kagome antiferromagnetic material.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087)the Postdoctoral Research Foundation of China(Grant No.2022M721360)the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。
文摘The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.
基金Project supported by the National Natural Science Foundation of China(Grant No.62375140)the Natural Science Foundation of Suqian,Jiangsu Province,China(Grant No.S202108)+1 种基金the Open Research Fund of the National Laboratory of Solid State Microstructures(Grant No.M36055)the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(Grant No.KYCX21-0745)。
文摘We propose an optical image watermarking scheme based on orbital angular momentum(OAM)holography.Multiple topological charges(TCs,l)of OAM,as multiple cryptographic sub-keys,are embedded into the host image along with the watermark information.Moreover,the Arnold transformation is employed to further enhance the security and the scrambling time(m)is also served as another cryptographic key.The watermark image is embedded into the host image by using the discrete wavelet transformation(DWT)and singular value decomposition(SVD)methods.Importantly,the interference image is utilized to further enhance security.The imperceptibility of our proposed method is analyzed by using the peak signal-to-noise ratio(PSNR)and the histogram of the watermarked host image.To demonstrate robustness,a series of attack tests,including Gaussian noise,Poisson noise,salt-and-pepper noise,JPEG compression,Gaussian lowpass filtering,cropping,and rotation,are conducted.The experimental results show that our proposed method has advanced security,imperceptibility,and robustness,making it a promising option for optical image watermarking applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.62375140 and 61871234)the Open Research Fund of National Laboratory of Solid State Microstructures(Grant No.M36055).
文摘Orbital angular momentum(OAM)holography has become a promising technique in information encryption,data storage and opto-electronic computing,owing to the infinite topological charge of one single OAM mode and the orthogonality of different OAM modes.In this paper,we propose a novel OAM hologram generation method based on a densely connected U-net(DCU),where the densely connected convolution blocks(DCB)replace the convolution blocks of the U-net.Importantly,the reconstruction process of the OAM hologram is integrated into DCU as its output layer,so as to eliminate the requirement to prepare training data for the OAM hologram,which is required by conventional neural networks through an iterative algorithm.The experimental and simulation results show that the OAM hologram can rapidly be generated with the well-trained DCU,and the reconstructed image's quality from the generated OAM hologram is significantly improved in comparison with those from the Gerchberg-Saxton generation method,the Gerchberg-Saxton based generation method and the U-net method.In addition,a 10-bit OAM multiplexing hologram scheme is numerically demonstrated to have a high capacity with OAM hologram.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.62375140 and 62001249)the Open Research Fund of the National Laboratory of Solid State Microstructures (Grant No.M36055)。
文摘Orbital angular momentum(OAM), as a new degree of freedom, has recently been applied in holography technology.Due to the infinite helical mode index of OAM mode, a large number of holographic images can be reconstructed from an OAM-multiplexing hologram. However, the traditional design of an OAM hologram is constrained by the helical mode index of the selected OAM mode, for a larger helical mode index OAM mode has a bigger sampling distance, and the crosstalk is produced for different sampling distances for different OAM modes. In this paper, we present the design of the OAM hologram based on a Bessel–Gaussian beam, which is non-diffractive and has a self-healing property during its propagation. The Fourier transform of the Bessel–Gaussian beam is the perfect vortex mode that has the fixed ring radius for different OAM modes. The results of simulation and experiment have demonstrated the feasibility of the generation of the OAM hologram with the Bessel–Gaussian beam. The quality of the reconstructed holographic image is increased, and the security is enhanced. Additionally, the anti-interference property is improved owing to its self-healing property of the Bessel-OAM holography.
文摘We theoretically studied the dynamic properties of the skyrmion driven by electromagnetic(EM)waves with spin angular momentum(SAM)and orbital angular momentum(OAM)using micromagnetic simulations.First,the guiding centers of the skyrmion driven by EM waves with SAM,i.e.,left-handed and right-handed circularly polarized EM waves,present circular trajectories,while present elliptical trajectories under linear EM waves driving due to the superposition of oppositely polarized wave components.Second,the trajectories of the skyrmion driven by EM waves with OAM demonstrate similar behavior to that driven by linearly polarized EM waves.Because the wave vector intensity varies with the phase for both linearly polarized EM waves and EM waves with OAM,the angular momentum is transferred to the skyrmion non-uniformly,while the angular momentum is transferred to the skyrmion uniformly for left-handed and right-handed circularly polarized EM driving.Third,the dynamic properties of the skyrmion driven by EM waves with both SAM and OAM are investigated.It is found that the dynamic trajectories exhibit more complex behavior due to the contributions or competition of SAM and OAM.We investigate the characteristics of intrinsic gyration modes and frequency-dependent trajectories.Our research may provide insight into the dynamic properties of skyrmion manipulated by EM waves with SAM or OAM and provide a method for controlling skyrmion in spintronic devices.
基金supported by the National Natural Science Foundation of China (Grant Nos.12174338 and 11874321)。
文摘Fractional orbital angular momentum(OAM) vortex beams present a promising way to increase the data throughput in optical communication systems. Nevertheless, high-precision recognition of fractional OAM with different propagation distances remains a significant challenge. We develop a convolutional neural network(CNN)method to realize high-resolution recognition of OAM modalities, leveraging asymmetric Bessel beams imbued with fractional OAM. Experimental results prove that our method achieves a recognition accuracy exceeding 94.3% for OAM modes, with an interval of 0.05, and maintains a high recognition accuracy above 92% across varying propagation distances. The findings of our research will be poised to significantly contribute to the deployment of fractional OAM beams within the domain of optical communications.
基金supported by the National Key Research and Development Program of China(Grant Nos.2018YFE0202700 and 2023YFA1406500)the National Natural Science Foundation of China(Grant Nos.11974422 and 12104504)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB30000000)Fundamental Research Funds for the Central Universities,and Research Funds of Renmin University,China(Grant No.22XNKJ30)supported by the Outstanding Innovative Talents Cultivation Funded Programs 2023 of Renmin University,China。
文摘Two-dimensional(2D)van der Waals magnetic materials have promising and versatile electronic and magnetic properties in the 2D limit,indicating a considerable potential to advance spintronic applications.Theoretical predictions thus far have not ascertained whether monolayer VCl_(3) is a ferromagnetic(FM)or anti-FM monolayer;this also remains to be experimentally verified.We theoretically investigate the influence of potential factors,including C_(3) symmetry breaking,orbital ordering,epitaxial strain,and charge doping,on the magnetic ground state.Utilizing first-principles calculations,we predict a collinear type-Ⅲ FM ground state in monolayer VCl_(3) with a broken C_(3) symmetry,wherein only the former two of three t_(2g)orbitals(a_(1g),e_(g2)^(π)and e_(g1)^(π))are occupied.The atomic layer thickness and bond angles of monolayer VCl_(3) undergo abrupt changes driven by an orbital ordering switch,resulting in concomitant structural and magnetic phase transitions.Introducing doping to the underlying Cl atoms of monolayer VCl_(3) without C_(3) symmetry simultaneously induces in-and out-of-plane polarizations.This can achieve a multiferroic phase transition if combined with the discovered adjustments of magnetic ground state and polarization magnitude under strain.The establishment of an orbital-ordering driven regulatory mechanism can facilitate deeper exploration and comprehension of magnetic properties of strongly correlated systems in monolayer VCl_(3).
基金Financial support from the National Natural Science Foundation of China(grant nos.22379006,21575016,U20A20154,22279005)from the National Program for Support of Top-notch Young Professionals is gratefully acknowledged。
文摘The electrocatalytic conversion of CO_(2) into valuable chemical feedstocks using renewable electricity offers a compelling strategy for closing the carbon loop.While copper-based materials are effective in catalyzing CO_(2) to C_(2+)products,the instability of Cu^(+)species,which tend to reduce to Cu~0 at cathodic potentials during CO_(2) reduction,poses a significant challenge.Here,we report the development of SmCu_(2)O and investigate the influence of f-d orbital hybridization on the CO_(2) reduction reaction (CO_(2)RR).Supported by density functional theory (DFT) calculations,our experimental results demonstrate that hybridization between Sm^(3+)4f and Cu^(+)3d orbitals not only improves the adsorption of *CO intermediates and increases CO coverage to stabilize Cu^(+) but also facilitates CO_(2) activation and lowers the energy barriers for CAC coupling.Notably,Sm-Cu_(2)O achieves a Faradaic efficiency for C_(2)H_(4) that is 38%higher than that of undoped Cu_(2)O.Additionally,it sustains its catalytic activity over an extended operational period exceeding 7 h,compared to merely 2 h for the undoped sample.This research highlights the potential of fd orbital hybridization in enhancing the efficacy of copper-based catalysts for CO_(2)RR,pointing towards a promising direction for the development of durable,high-performance electrocatalysts for sustainable chemical synthesis.
基金supported by the National Key R&D Program of China(No.2021YFB2800700)National Natural Science Foundation of China(Nos.12274210,62227820,and 12174183)+1 种基金Partial support is from NSF of Jiangsu Province(No.BK20220006)the Fundamental Research Funds for the Central Universities and Jiangsu Key Laboratory of Advanced Techniques for Manipulating Electromagnetic Waves。
文摘Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.
基金financially supported by the Scientific and Technological Development Program of Jilin Province(20220201138GX)the support of the National Key R&D Program of China(No.2022YFA1503801)+1 种基金CAS Project for Young Scientists in Basic Research(No.YSBR-022)the Young Cross Team Project of CAS(No.JCTD-2021-14)。
文摘Ni-Fe-based catalysts are considered to be among the most active catalysts for the oxygen evolution reaction(OER)under alkaline conditions,with Fe playing a crucial role.However,Fe leaching occurs during the reaction due to thermodynamic instability,which has resulted in conflicting reports within the literature regarding its role.To clarify this point,we propose a strategy consisting of modulating the electronic orbital occupancy to suppress the extensive loss of Fe atoms during the OER process.Theoretical calculations,in-situ X-ray photoelectron spectroscopy,molecular dynamics simulations,and a series of characterization showed that the stable presence of Fe not only accelerates the electron transfer process but also optimizes the reaction barriers of the oxygen evolution intermediates,promoting the phase transition of Fe_(5)Ni_(4)S_(8)to highly active catalytic species.The modulated Fe_(5)Ni_(4)S_(8)-based pre-catalysts exhibit improved OER activity and long-term durability.This study provides a novel perspective for understanding the role of Fe in the OER process.
基金National Key Research and Development Program of China (2022YFA1404800,2019YFA0705000)National Natural Science Foundation of China (12104264,12192254,92250304,and 12374311)+2 种基金China Postdoctoral Science Foundation (2022T150392)Natural Science Foundation of Shandong Province (ZR2021QA014 and ZR2023YQ006)Qingchuang Science and Technology Plan of Shandong Province (2022KJ246).
文摘The ability to overcome the negative effects,induced by obstacles and turbulent atmosphere,is a core challenge of long-distance information transmission,and it is of great significance in free-space optical communication.The spatial-coherence structure,that characterizes partially coherent fields,provides a new degree of freedom for carrying information.However,due to the influence of the complex transmission environment,the spatial-coherence structure is severely damaged during the propagation path,which undoubtedly limits its ability to transmit information.Here,we realize the robust far-field orbital angular momentum(OAM)transmission and detection by modulating the spatial-coherence structure of a partially coherent vortex beam with the help of the cross-phase.The cross-phase enables the OAM information,quantified by the topological charge,hidden in the spatial-coherence structure can be stably transmitted to the far field and can resist the influence of obstructions and turbulence within the communication link.This is due to the self-reconstruction property of the spatial-coherence structure embedded with the cross-phase.We demonstrate experimentally that the topological charge information can be recognized well by measuring the spatial-coherence structure in the far field,exhibiting a set of distinct and separated dark rings even under amplitude and phase perturbations.Our findings open a door for robust optical signal transmission through the complex environment and may find application in optical communication through a turbulent atmosphere.
基金supported by the National Natural Science Foundation of China(Grant No.11174175)the Tsinghua University Initiative Scientific Research Program,China
文摘Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.
基金Project supported by the Foundation of Henan Educational Committee, China (Grant No. 2011A140015)
文摘Electron density distributions of 2-aminoethanol （2AE） and 2-amino-l-propanol （2AP） are calculated in both the coordinate and the momentum spaces using the B3LYP/TZVP method. Using the dual space analysis, molecular orbital signatures of the methyl substituent in 2AP are identified with respect to 2AE. Relaxations of the geometry and the valence orbital in 2AP are found to be due to the insertion of the methyl group. Five orbitals, not four orbitals, are identified as the methyl signatures. They are orbital 5a in the core shell, orbitals 9a and 10a in the inner valence shell, and orbitals 15a and 16a in the outer valence. In the inner valence shell, the attachment of methyl to 2AE causes a splitting of its orbital 8a into orbitals 9a and 10a of 2AP, whereas in the outer valence shell, the methyl group results in the insertion of an additional orbital pair of 15a and 16a. The frontier molecular orbitals 21a, 20a, and 19a are found to have no significant role in the methylation of 2AE.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61271238 and 61475075)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.20123223110003)+7 种基金the Natural Science Research Foundation for Universities of Jiangsu Province of China(Grant No.11KJA510002)the Open Research Fund of Key Laboratory of Broadband Wireless Communication and Sensor Network TechnologyMinistry of EducationChina(Grant No.NYKL2015011)the Innovation Program of Graduate Education of Jiangsu ProvinceChina(Grant No.KYLX0810)partially supported by Qinglan Project of Jiangsu ProvinceChina
文摘In this paper, we propose a measurement-device-independent quantum-key-distribution（MDI-QKD） protocol using orbital angular momentum（OAM） in free space links, named the OAM-MDI-QKD protocol. In the proposed protocol,the OAM states of photons, instead of polarization states, are used as the information carriers to avoid the reference frame alignment, the decoy-state is adopted to overcome the security loophole caused by the weak coherent pulse source, and the high efficient OAM-sorter is adopted as the measurement tool for Charlie to obtain the output OAM state. Here, Charlie may be an untrusted third party. The results show that the authorized users, Alice and Bob, could distill a secret key with Charlie＇s successful measurements, and the key generation performance is slightly better than that of the polarization-based MDI-QKD protocol in the two-dimensional OAM cases. Simultaneously, Alice and Bob can reduce the number of flipping the bits in the secure key distillation. It is indicated that a higher key generation rate performance could be obtained by a high dimensional OAM-MDI-QKD protocol because of the unlimited degree of freedom on OAM states. Moreover,the results show that the key generation rate and the transmission distance will decrease as the growth of the strength of atmospheric turbulence（AT） and the link attenuation. In addition, the decoy states used in the proposed protocol can get a considerable good performance without the need for an ideal source.
文摘The light＇s orbital angular momentum （OAM） is a consequence of the spiral flow of the electromagnetic energy. In this paper, an analysis of light beams with OAM used for free space optics （FSO） is conducted. The basic description and conception of light＇s OAM are reviewed. Both encoding information into OAM states of single light beam and encoding information into spatial structure of the mixed optical vortex with OAM are discussed, and feasibility to improve the FSO＇s performance of security and obstruction of line of sight is examined.
