Atomic spin gyroscopes are promising candidates for next-generation inertial navigation due to extremely high theoretical precision,relatively small size among atomic gyroscopes,and promising potential for miniaturiza...Atomic spin gyroscopes are promising candidates for next-generation inertial navigation due to extremely high theoretical precision,relatively small size among atomic gyroscopes,and promising potential for miniaturization.In particular,the spin-exchange relaxation-free(SERF)atomic gyroscope relies on optical pumping to polarize atoms,enabling rotation sensing through the Faraday optical rotation angle(FORA).However,fluctuations in atomic density introduce systematic errors in FORA measurements,limiting long-term stability.We present a data-driven decoupling method that isolates atomic density fluctuations from the FORA signal by modeling spatially resolved light absorption in the vapor cell.The model accounts for the spatial distribution of spin polarization in the pump-light interaction volume,density-dependent relaxation rates,wall-induced relaxation,and polarization diffusion,and is implemented within a finite-element framework.Compared to the conventional Lambert-Beer law,which assumes one-dimensional homogeneity,our approach captures the full threedimensional density and polarization distribution,significantly improving the accuracy of light absorption modeling.The resulting absorption-density maps are used to train a feedforward neural network,yielding a high-precision estimator for atomic density fluctuations.This estimator enables the construction of a decoupling equation that separates the density contribution from the FORA signal.Experimental validation shows that this method improves the bias instability atσ(100 s)of the gyroscope was improved by 73.1%compared to traditional platinum-resistance-based stabilization.The proposed framework is general and can be extended to other optical pumping-based sensors,such as optically pumped magnetometers.展开更多
Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the effica...Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.展开更多
The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify t...The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.展开更多
A new type of asymmetric hydrogen atom abstraction catalysts,originated from the cinchona alkaloid family of natural products,has been successfully developed to access enantioselective epimerizations of meso-diols.Aft...A new type of asymmetric hydrogen atom abstraction catalysts,originated from the cinchona alkaloid family of natural products,has been successfully developed to access enantioselective epimerizations of meso-diols.After undergoing single-electron oxidation,the catalyst fulfills desymmetrization of meso-diols by selectively traping a hydrogen atom from a carbon center,which subsequently recaptures a hydrogen atom via abstraction from a thiol.The publication of this work will have a significant influence in the field of asymmetric radical chemistry.展开更多
In this article,we introduce a new theoretical approach to improve the accuracy of twodimensional(2D)atomic localization within a tripod-type,four-level atomic system by analyzing its transmission spectrum.In this met...In this article,we introduce a new theoretical approach to improve the accuracy of twodimensional(2D)atomic localization within a tripod-type,four-level atomic system by analyzing its transmission spectrum.In this method,the atom interacts with two orthogonal standing-wave fields and a weak probe field.By examining how the weak probe field passes through the system,we can determine the atom position.Our analysis reveals the presence of both double and sharply defined single localized peaks in the transmission spectrum,which correspond to specific positions of the atom.Importantly,we achieve ultra-high-resolution atomic localization with accuracy confined to a region smaller thanλ/32×λ/32.This level of precision is a significant improvement compared to earlier methods,which had lower localization accuracy.The increased precision is due to the complex interaction between the atom and the carefully controlled standing-wave and probe fields,which allows for precise control over the atom's position.The implications of this work are significant,especially for applications like nano-lithography,where precise atomic placement is essential,and for laser cooling technologies,where better atomic localization could lead to more effective cooling processes and improved manipulation of atomic states.展开更多
Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibite...Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C_(3)N_(4),as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe_(0.4)–C_(3)N_(4)/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe_(3)O_(4)/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe_(0.4)–C_(3)N_(4) still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe_(0.4)–C_(3)N_(4) exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O_(2))and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe_(0.4)–C_(3)N_(4)/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O_(2) and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe_(0.4)–C_(3)N_(4)/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.展开更多
The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulat...The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulate the electronic structure of MoS_(2),thereby obtaining a multifunctional catalyst that serves as an efficient sulfur host.The W/V dual single-atomdoped MoS_(2)grown on carbon nanofibers(CMWVS)demonstrates a strong adsorption ability for lithium polysulfides,suppressing the shuttle effects.Additionally,the doping process also results in the phase transition from 2H-MoS_(2)to 1T-MoS_(2)and generates sufficient edge sulfur atoms,promoting the charge/electron transfer and enriching the reaction sites.All these merits contribute to the superior conversion reaction kinetics,leading to the outstanding Li-S battery performance.When fabricated as cathodes by compositing with sulfur,the CMWVS/S cathode delivers a high capacity of 1481.7 mAh g^(-1)at 0.1 C(1 C=1672 mAh g^(-1))and maintains 816.3 m Ah g^(-1)after 1000 cycles at 1.0 C,indicating outstanding cycling stability.Even under a high sulfur loading of 7.9 mg cm^(-2)and lean electrolyte conditions(E/S ratio of 9.0μL mg^(-1)),the cathode achieves a high areal capacity of 8.2 m Ah cm^(-2),showing great promise for practical Li-S battery applications.This work broadens the scope of doping strategies in transition-metal dichalcogenides by tailoring their electronic structures,providing insightful direction for the rational development of high-efficiency electrocatalysts for advanced Li-S battery applications.展开更多
We propose a novel cooling protocol within a triple-Laguerre-Gaussian cavity optomechanical system,which is designed to suppress the thermal vibrations of a rotating mirror to reach its quantum ground state.The system...We propose a novel cooling protocol within a triple-Laguerre-Gaussian cavity optomechanical system,which is designed to suppress the thermal vibrations of a rotating mirror to reach its quantum ground state.The system incorporates two auxiliary cavities and an atomic ensemble coupled to a Laguerre-Gaussian rotational cavity.By carefully selecting system parameters,the cooling process of the rotating mirror is significantly enhanced,while the heating process is effectively suppressed,enabling efficient ground-state cooling even in the unresolved sideband regime.Compared to previous works,our scheme reduces the stringent restrictions on auxiliary systems,making it more experimentally feasible under broader parameter conditions.These findings provide a robust approach for achieving ground-state cooling in mechanical resonators.展开更多
Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationshi...Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationship.However,it is challenging to engineer the coordination configuration of isolated active metal atoms precisely.Herein,we strategically manipulate the coordination number of the Co-N_(x) configuration by simply changing the order of adding the metal precursor toward improved CO_(2)electrolysis performance.Compared with the symmetric Co-N_(4)coordination,the asymmetric Co-N_(3)coordination leads to reinforced Co-N interaction and downshifted 3d orbital energy toward the Fermi level of the active Co sites,promoting the activation of CO_(2)molecules and the formation of critical intermediate^(*)COOH.The as-designed Co-N_(3)SAC displays excellent Faradaic efficiency(FE)of 98.4%for CO_(2)-to-CO conversion at a low potential of-0.80 V,together with decent FE over a wide potential range(-0.50 V to-1.10 V)and high durability.This study presents an ideal platform to manipulate the coordination number of atomically dispersed metal catalysts and provides a fundamental understanding of coordination configurationperformance correlation for CO_(2)electroreduction.展开更多
We developed a model of a quantum Otto engine using two coupled two-level atoms.Based on the platform,we show that frequency detuning and the coupling strength induced by dipoledipole interactions can lead to decohere...We developed a model of a quantum Otto engine using two coupled two-level atoms.Based on the platform,we show that frequency detuning and the coupling strength induced by dipoledipole interactions can lead to decoherence by disrupting coherent energy exchange.We focus on fundamental thermodynamic quantities,including heat absorption,release to heat baths,work done and efficiency.It is noteworthy that the interatomic coupling strength and frequency detuning do not merely affect the shape of the work and the efficiency but ultimately govern its quantitative magnitude.In the field of quantum thermodynamics,we have established an upper bound efficiency that is stricter than the Carnot limit.Moreover,our analysis confirms that quantum coherence enables the system to exceed the efficiency threshold of a classical Otto heat engine.The second law of thermodynamics holds all the while.Our results constitute a step forward in the design of conceptually new quantum thermodynamic devices which take advantage of uniquely quantum resources of quantum coherence.展开更多
Inorganic perovskites,a class of materials with the general formula ABX3,exhibit a wide range of electronic,dielectric,and structural properties,making them pivotal in energy,electronics,and catalysis applications.Acc...Inorganic perovskites,a class of materials with the general formula ABX3,exhibit a wide range of electronic,dielectric,and structural properties,making them pivotal in energy,electronics,and catalysis applications.Accurate atomistic simulations of these materials require accurate interatomic potentials that capture both short-range and long-range interactions.While first-principles methods are of high accuracy,empirical and machine learning potentials remain essential for large-scale simulations.This survey categorizes and reviews the atomic potentials used in inorganic perovskite modeling based on how they treat electrostatic interactions:potentials without charges,potentials with constant charges,and potentials with variable charges.Given the ionic nature of perovskites,we emphasize the importance of charge treatment,and each class of potentials is discussed in detail with representative examples,functional forms,and application scenarios.For comparison,we perform molecular dynamics simulations to calculate the critical temperature for the phase transition of the perovskite CsPbI_(3) with available empirical potentials,highlighting their strengths and limitations in capturing structural evolution.Finally,we outline future directions for developing more accurate and transferable atomic potentials for inorganic perovskites.We hope that this review can serve as a guiding resource for researchers who are starting to perform simulations for inorganic perovskites.展开更多
Rydberg-atom-based superheterodyne receivers integrate self-calibration,high sensitivity,a wide operational frequency range,and phase/frequency resolved detection capabilities,demonstrating broad application prospects...Rydberg-atom-based superheterodyne receivers integrate self-calibration,high sensitivity,a wide operational frequency range,and phase/frequency resolved detection capabilities,demonstrating broad application prospects as nextgeneration microwave receivers.Linear gain and linear dynamic range(LDR)are critical metrics for assessing receiver sensitivity and demodulation fidelity,respectively.We numerically solve the four-level master equation and then employ particle swarm optimization(PSO)algorithm to co-optimize linear gain and LDR in atomic superheterodyne receivers based on balanced homodyne detection.Further,we systematically account for dominant dephasing mechanisms in the simulation,encompassing spontaneous decay,transit dephasing,collision dephasing,laser linewidth dephasing,and Doppler averaging.Homodyne readout utilizes both the real and imaginary parts of polarizability for sensing.In the case of the photon shot noise limit,its signal-to-noise ratio(SNR)expression resembles that of direct optical-intensity readout.However,the inherent coherent subtraction operation in homodyne detection significantly suppresses common-mode noise,while appropriately increasing the reference beam power enhances the gain in practical experiments.Indeed,this co-optimization problem,characterized by a high-dimensional variable space,two objectives,and non-convexity,is well-suited for solution by PSO.In addition,probe and coupling detuning contribute equivalently to polarizability and compensate for each other owing to Doppler averaging,thereby reducing the optimization variable space by one.By adopting a product form of linear gain and LDR as the fitness function,the PSO achieves rapid convergence.Here,the effectiveness of the PSO results is verified via the total harmonic distortion(THD).The relative error-based LDR calculation method we proposed efficiently measures receiver response linearity with consuming fewer computational resources.This research is expected to offer valuable insights into enhancing the performance of Rydberg-atom-based superheterodyne receivers.展开更多
The development of atomically dispersed multi-metallic catalysts is imperative for tailoring catalytic performance and elucidating structure-activity relationships.However,synthesizing such precisely engineered archit...The development of atomically dispersed multi-metallic catalysts is imperative for tailoring catalytic performance and elucidating structure-activity relationships.However,synthesizing such precisely engineered architectures while maintaining atomic dispersion of distinct metal centers remains a formidable challenge due to thermodynamic instability and synthetic complexity.We herein propose a topological confinement pre-anchoring strategy via pre-anchoring spatially resolved Zn/Fe dual-metal sources in a structurally engineered metal-organic framework precursor to synthesize atomically dispersed ZnFe bimetallic single-atom catalysts.Extended X-ray absorption fine structure measurements and X-ray absorption near-edge structure reveal that the atomically dispersed Zn/Fe metal sites and electronic redistribution in ZnFe bimetallic single-atom catalysts.The ultrahigh surface area,hierarchical pore,and synergistic effect between Zn/Fe can greatly favor the exposure of the active site,mass transport,and improvement of intrinsic activity.Consequently,the ZnFe bimetallic single-atom catalyst demonstrates superior oxygen reduction reaction performance,achieving a half-wave potential of 0.86 V and delivering a kinetic current density of 10.1 mA cm^(-2)at 0.85 V versus RHE in 0.1 m KOH electrolyte.These metrics not only surpass those of commercial Pt/C,but also rival the highest-performing catalysts reported to date.The Zn-air battery built with ZnFe bimetallic single-atom catalyst exhibits high power density(278.5 mW cm^(-2))and specific discharging capacities(657 mAh g^(-1)).This work provides a new design pathway for constructing atomically dispersed multi-metal electrocatalysts for high-performance energy-related applications.展开更多
Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achievin...Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.展开更多
The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel sing...The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel single-atom-dispersed S_(2)-FeNC/FeS_(2) nanocluster heterojunction embedded in carbon spheres(SFNC/FeS_(2)) for the electrode material of sodium metal batteries.Interestingly,during the discharging process,the Na^(+) is inserted into FeS_(2) to generate Na_(2)S,as well as the unique electrochemical reaction between S_(2)-FeNC and Na^(+) to form Na_(2)S.Meanwhile,the FeNC can adsorb Na_(2)S and catalyze the conversion from Na_(2)S and Fe to FeS_(2) or from Na_(2)S and FeNC to S_(2)-FeNC for suppressing the shuttle effect and promoting the distinct hybrid reversible electrochemical behavior,which improves performance tremendously.Notably,the SFNC/FeS_(2) electrode delivers a specific capacity of 338.7 mAh g^(-1) after superlong 2000 cycles at a current density of 5.0 A g^(-1) and achieves a high energy density of 430.1 Wh Kg^(-1) at a current density of 0.05 A g^(-1).This work presents a novel approach to studying sodium metal batteries with hybrid behavior for excellent high energy density and cycling stability.展开更多
The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution ...The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.展开更多
Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device appl...Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device applications.Herein,we introduce a novel TiN/TiC-supported Fe SA catalyst(TiNC/Fe-NC)with a hierarchical heterostructure that synergistically enhances Fe-N_(x) site activity and accessibility.The TiNC/Fe-NC catalyst achieves outstanding ORR performances,with half-wave potentials(E_(1/2))of 0.852 V in acidic media and 0.942 V in alkaline media.Theoretical simulations reveal that strong electronic interaction and efficient charge transfer between TiNC and Fe-N_(x) sites optimize the adsorption energetics of key ORR intermediates,driving the enhanced activity.Remarkably,TiNC effectively scavenges reactive oxygen radicals generated at the Fe centers,ensuring exceptional durability with a minimal 28 mV loss in E_(1/2) after 10,000 cycles at 80℃in acid media.In practical applications,TiNC/Fe-NC delivers peak power densities of 306 mW cm^(-2) in zinc-air battery and 732 mW cm^(-2) in proton exchange membrane fuel cells,with remarkable long-term stability.This work establishes TiNC/Fe-NC as a highperformance,durable catalyst for advanced energy storage and conversion technologies.展开更多
Oxide semiconductors(OSs),introduced by the Hosono group in the early 2000s,have evolved from display backplane materials to promising candidates for advanced memory and logic devices.The exceptionally low leakage cur...Oxide semiconductors(OSs),introduced by the Hosono group in the early 2000s,have evolved from display backplane materials to promising candidates for advanced memory and logic devices.The exceptionally low leakage current of OSs and compatibility with three-dimensional(3D)architectures have recently sparked renewed interest in their use in semiconductor applications.This review begins by exploring the unique material properties of OSs,which fundamentally originate from their distinct electronic band structure.Subsequently,we focus on atomic layer deposition(ALD),a core technique for growing excellent OS films,covering both basic and advanced processes compatible with 3D scaling.The basic surface reaction mechanisms—adsorption and reaction—and their roles in film growth are introduced.Furthermore,material design strategies,such as cation selection,crystallinity control,anion doping,and heterostructure engineering,are discussed.We also highlight challenges in memory applications,including contact resistance,hydrogen instability,and lack of p-type materials,and discuss the feasibility of ALD-grown OSs as potential solutions.Lastly,we provide an outlook on the role of ALD-grown OSs in memory technologies.This review bridges material fundamentals and device-level requirements,offering a comprehensive perspective on the potential of ALD-driven OSs for next-generation semiconductor memory devices.展开更多
Defect engineering serves as a cornerstone in the design of high-effciency single-atom catalysts(SACs)for advanced electrocatalytic systems.This study demonstrates oxygen vacancy-induced near-zero-valent Pt SACs ancho...Defect engineering serves as a cornerstone in the design of high-effciency single-atom catalysts(SACs)for advanced electrocatalytic systems.This study demonstrates oxygen vacancy-induced near-zero-valent Pt SACs anchored on TiO2 for efficient hydrogen evolution reaction(HER).Synchrotron spectroscopy and density functional theory calculation reveal that oxygen vacancies create unconventional Pt-Ti coordination while strengthening electronic metal-support interactions.This facilitates substantial electron transfer from TiO2 to Pt,generating a near-zero-valent Pt state with elevated electron density.The modified electronic structure lowers the Pt d-band center,reducing hydrogen intermediate(*H)adsorption energy and optimizing HER kinetics.Moreover,ab initio molecular dynamics and in situ Raman spectra show that the negative charge accumulated at the Pt site promotes K^(+)enrichment at the interface,which enhances H-OH bond polarization and accelerates water dissociation kinetics.The resulting D-TiO_(2)/Pt SACs exhibit superior HER activity across acidic,neutral,and alkaline conditions,achieving low overpotentials of 40,57,and 60 mV at 10 mA cm^(-2),respectively.Additionally,its mass activities at the overpotential of 100 mV are 10.3,33.9,and 20.9 times higher that of Pt/C,respectively.This study shows the key role of defectmediated electronic engineering in tailoring SACs'valence states and catalytic functions,advancing sustainable hydrogen production through rational catalyst design.展开更多
Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric fo...Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric for dynamic random access memory(DRAM)applications,offering a high dielectric constant with a remarkable leakage-lowering effect by Al acceptor doping.However,ATO fabrication via conventional supercycle-based ALD suffers from severe crystallinity loss during the growth of TiO_(2) upon Al doping owing to the dopant-induced lattice disorder.In addition,Al doping cannot reduce any inherent O vacancies(V_(O))of TiO_(2),although the original purpose of doping was to address the n-type nature caused by V_(O).To resolve these limitations,we propose a single-step,in-situ Ar/O_(2) post-doping plasma(PDP)process immediately after the Al dopant incorporation.Using the PDP process,simultaneous atomic-scale dopant migration-mediated crystallization and V_(O) annihilation were successfully initiated.Thus,the surface concentration of the dopant decreased,reducing the dopant-induced lattice distortion,while promoting the highly crystallized seed layer-like surface.Consequently,strong rutile-phase recovery was accompanied by enhanced lattice-matched growth.In addition,the PDP process significantly lowers the V_(O)-to-lattice oxygen ratio by facilitating the recombination between reactive O species and V_(O),increasing the corresponding 0.4 e V of conduction band offset(CBO).Despite the common trade-off between the dielectric constant and leakage,the Pt/PDP-ATO/Ru capacitor exhibited a simultaneous 30%increase in dielectric constant and up to a 1.6-order reduction in leakage current density.展开更多
基金supported by the Beijing Natural Science Foundation(Grant No.3252013)the Innovation Program for Quantum Science and Technology(Grant No.2021ZD0300402)+1 种基金the National Natural Science Foundation of China(Grant No.61673041)Key Area Research and Development Program of Guangdong Province(Grant No.2021B0101410005)。
文摘Atomic spin gyroscopes are promising candidates for next-generation inertial navigation due to extremely high theoretical precision,relatively small size among atomic gyroscopes,and promising potential for miniaturization.In particular,the spin-exchange relaxation-free(SERF)atomic gyroscope relies on optical pumping to polarize atoms,enabling rotation sensing through the Faraday optical rotation angle(FORA).However,fluctuations in atomic density introduce systematic errors in FORA measurements,limiting long-term stability.We present a data-driven decoupling method that isolates atomic density fluctuations from the FORA signal by modeling spatially resolved light absorption in the vapor cell.The model accounts for the spatial distribution of spin polarization in the pump-light interaction volume,density-dependent relaxation rates,wall-induced relaxation,and polarization diffusion,and is implemented within a finite-element framework.Compared to the conventional Lambert-Beer law,which assumes one-dimensional homogeneity,our approach captures the full threedimensional density and polarization distribution,significantly improving the accuracy of light absorption modeling.The resulting absorption-density maps are used to train a feedforward neural network,yielding a high-precision estimator for atomic density fluctuations.This estimator enables the construction of a decoupling equation that separates the density contribution from the FORA signal.Experimental validation shows that this method improves the bias instability atσ(100 s)of the gyroscope was improved by 73.1%compared to traditional platinum-resistance-based stabilization.The proposed framework is general and can be extended to other optical pumping-based sensors,such as optically pumped magnetometers.
基金supported by the National Key R&D Program of China (2021YFA1502802)the National Natural Science Foundation of China (U21B2092, 22202213, 22402210, 22502215, 22502214, 22572200, and 22579171)+3 种基金the International Partnership Program of Chinese Academy of Sciences (172GJHZ2022028MI)the Shenyang Bureau of Science and Technology (24-213-3-25)the Natural Science Foundation of Liaoning Province (2025BS0153)Zhongke Technology Achievement Transfer and Transformation Center of Henan Province 2025119
文摘Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.
基金supported by the National Natural Science Foundation of China[Grant No.21977083].
文摘The single-atom replacement strategy is a typical approach which just converts elements in lead compounds into their analogues with very small chemical changes.In this research,we implemented this strategy to modify the sulfonamide scaffold identified in our previous work,and resulting in the synthesis of 40 novel sulfonamide derivatives not previously reported in the literature.The insecticidal activities of these compounds against the Mythimna separata and Plutella xylostella were assessed.Our findings indicate that the pyridine sulfonamide structure significantly enhances insecticidal efficacy.Specifically,compound 7c exhibited LC 50 values of 0.157 and 0.256 mg/mL against the M.separata and P.xylostella,which significantly increased 97-and 41-fold compared to celangulin V,respectively.The experimental results revealed that pyridine sulfonamide analogues could serve as potential green insecticides.
基金supported by the National Natural Science Foundation of China(No.22208302)the Natural Science Foundation of Zhejiang Province of China(LQ21B020006).
文摘A new type of asymmetric hydrogen atom abstraction catalysts,originated from the cinchona alkaloid family of natural products,has been successfully developed to access enantioselective epimerizations of meso-diols.After undergoing single-electron oxidation,the catalyst fulfills desymmetrization of meso-diols by selectively traping a hydrogen atom from a carbon center,which subsequently recaptures a hydrogen atom via abstraction from a thiol.The publication of this work will have a significant influence in the field of asymmetric radical chemistry.
基金Princess Nourah bint Abdulrahman University Researchers Supporting Project number(PNURSP2025R8)。
文摘In this article,we introduce a new theoretical approach to improve the accuracy of twodimensional(2D)atomic localization within a tripod-type,four-level atomic system by analyzing its transmission spectrum.In this method,the atom interacts with two orthogonal standing-wave fields and a weak probe field.By examining how the weak probe field passes through the system,we can determine the atom position.Our analysis reveals the presence of both double and sharply defined single localized peaks in the transmission spectrum,which correspond to specific positions of the atom.Importantly,we achieve ultra-high-resolution atomic localization with accuracy confined to a region smaller thanλ/32×λ/32.This level of precision is a significant improvement compared to earlier methods,which had lower localization accuracy.The increased precision is due to the complex interaction between the atom and the carefully controlled standing-wave and probe fields,which allows for precise control over the atom's position.The implications of this work are significant,especially for applications like nano-lithography,where precise atomic placement is essential,and for laser cooling technologies,where better atomic localization could lead to more effective cooling processes and improved manipulation of atomic states.
基金supported by the National Natural Science Foundation of China(Nos.22406081,22276086,22306086)the Natural Science Foundation of Jiangxi Province(No.20232BAB213029),all of which are greatly acknowledged by the authors.
文摘Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C_(3)N_(4),as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe_(0.4)–C_(3)N_(4)/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe_(3)O_(4)/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe_(0.4)–C_(3)N_(4) still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe_(0.4)–C_(3)N_(4) exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O_(2))and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe_(0.4)–C_(3)N_(4)/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O_(2) and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe_(0.4)–C_(3)N_(4)/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.
基金supported by the National Natural Science Foundation of China(52402166)the Science and Technology Development Fund+2 种基金Macao SAR(0065/2023/AFJ,0116/2022/A3)the Australian Research Council(DE220100154)the Natural Science Foundation of Guangdong Province(2025A1515011120)。
文摘The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulate the electronic structure of MoS_(2),thereby obtaining a multifunctional catalyst that serves as an efficient sulfur host.The W/V dual single-atomdoped MoS_(2)grown on carbon nanofibers(CMWVS)demonstrates a strong adsorption ability for lithium polysulfides,suppressing the shuttle effects.Additionally,the doping process also results in the phase transition from 2H-MoS_(2)to 1T-MoS_(2)and generates sufficient edge sulfur atoms,promoting the charge/electron transfer and enriching the reaction sites.All these merits contribute to the superior conversion reaction kinetics,leading to the outstanding Li-S battery performance.When fabricated as cathodes by compositing with sulfur,the CMWVS/S cathode delivers a high capacity of 1481.7 mAh g^(-1)at 0.1 C(1 C=1672 mAh g^(-1))and maintains 816.3 m Ah g^(-1)after 1000 cycles at 1.0 C,indicating outstanding cycling stability.Even under a high sulfur loading of 7.9 mg cm^(-2)and lean electrolyte conditions(E/S ratio of 9.0μL mg^(-1)),the cathode achieves a high areal capacity of 8.2 m Ah cm^(-2),showing great promise for practical Li-S battery applications.This work broadens the scope of doping strategies in transition-metal dichalcogenides by tailoring their electronic structures,providing insightful direction for the rational development of high-efficiency electrocatalysts for advanced Li-S battery applications.
基金Project supported by the National Natural Science Foundation of China(Grant No.62471180)。
文摘We propose a novel cooling protocol within a triple-Laguerre-Gaussian cavity optomechanical system,which is designed to suppress the thermal vibrations of a rotating mirror to reach its quantum ground state.The system incorporates two auxiliary cavities and an atomic ensemble coupled to a Laguerre-Gaussian rotational cavity.By carefully selecting system parameters,the cooling process of the rotating mirror is significantly enhanced,while the heating process is effectively suppressed,enabling efficient ground-state cooling even in the unresolved sideband regime.Compared to previous works,our scheme reduces the stringent restrictions on auxiliary systems,making it more experimentally feasible under broader parameter conditions.These findings provide a robust approach for achieving ground-state cooling in mechanical resonators.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(No.20240101004JJ)the National Natural Science Foundation of China(No.22409165)+4 种基金the National Foreign Experts Program of the Ministry of Human Resources and Social Security(No.Y20240003)the Shaanxi Province Talent Programfinancially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Nos.XDB0600000,XDB0600100,XDB0600200,XDB0600300,XDB0600400)Liaoning Binhai Laboratory(No.LILBLB-2023-04)Dalian Revitalization Talents Program(No.2022RG01)。
文摘Exploring the influence of the coordination environment of single-atom catalysts(SACs)on the electrochemical CO_(2)reduction reaction is vital for assessing the reaction mechanism and structure-performance relationship.However,it is challenging to engineer the coordination configuration of isolated active metal atoms precisely.Herein,we strategically manipulate the coordination number of the Co-N_(x) configuration by simply changing the order of adding the metal precursor toward improved CO_(2)electrolysis performance.Compared with the symmetric Co-N_(4)coordination,the asymmetric Co-N_(3)coordination leads to reinforced Co-N interaction and downshifted 3d orbital energy toward the Fermi level of the active Co sites,promoting the activation of CO_(2)molecules and the formation of critical intermediate^(*)COOH.The as-designed Co-N_(3)SAC displays excellent Faradaic efficiency(FE)of 98.4%for CO_(2)-to-CO conversion at a low potential of-0.80 V,together with decent FE over a wide potential range(-0.50 V to-1.10 V)and high durability.This study presents an ideal platform to manipulate the coordination number of atomically dispersed metal catalysts and provides a fundamental understanding of coordination configurationperformance correlation for CO_(2)electroreduction.
基金supported by University-Industry Collaborative Education Program(Project No.220506627183928)。
文摘We developed a model of a quantum Otto engine using two coupled two-level atoms.Based on the platform,we show that frequency detuning and the coupling strength induced by dipoledipole interactions can lead to decoherence by disrupting coherent energy exchange.We focus on fundamental thermodynamic quantities,including heat absorption,release to heat baths,work done and efficiency.It is noteworthy that the interatomic coupling strength and frequency detuning do not merely affect the shape of the work and the efficiency but ultimately govern its quantitative magnitude.In the field of quantum thermodynamics,we have established an upper bound efficiency that is stricter than the Carnot limit.Moreover,our analysis confirms that quantum coherence enables the system to exceed the efficiency threshold of a classical Otto heat engine.The second law of thermodynamics holds all the while.Our results constitute a step forward in the design of conceptually new quantum thermodynamic devices which take advantage of uniquely quantum resources of quantum coherence.
基金supported by the National Natural Science Foundation of China(Grant Nos.12072182 and 12421002).
文摘Inorganic perovskites,a class of materials with the general formula ABX3,exhibit a wide range of electronic,dielectric,and structural properties,making them pivotal in energy,electronics,and catalysis applications.Accurate atomistic simulations of these materials require accurate interatomic potentials that capture both short-range and long-range interactions.While first-principles methods are of high accuracy,empirical and machine learning potentials remain essential for large-scale simulations.This survey categorizes and reviews the atomic potentials used in inorganic perovskite modeling based on how they treat electrostatic interactions:potentials without charges,potentials with constant charges,and potentials with variable charges.Given the ionic nature of perovskites,we emphasize the importance of charge treatment,and each class of potentials is discussed in detail with representative examples,functional forms,and application scenarios.For comparison,we perform molecular dynamics simulations to calculate the critical temperature for the phase transition of the perovskite CsPbI_(3) with available empirical potentials,highlighting their strengths and limitations in capturing structural evolution.Finally,we outline future directions for developing more accurate and transferable atomic potentials for inorganic perovskites.We hope that this review can serve as a guiding resource for researchers who are starting to perform simulations for inorganic perovskites.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62331024 and 62571549)the National Key Research and Development Program of China(Grant No.2022YFB2802804)。
文摘Rydberg-atom-based superheterodyne receivers integrate self-calibration,high sensitivity,a wide operational frequency range,and phase/frequency resolved detection capabilities,demonstrating broad application prospects as nextgeneration microwave receivers.Linear gain and linear dynamic range(LDR)are critical metrics for assessing receiver sensitivity and demodulation fidelity,respectively.We numerically solve the four-level master equation and then employ particle swarm optimization(PSO)algorithm to co-optimize linear gain and LDR in atomic superheterodyne receivers based on balanced homodyne detection.Further,we systematically account for dominant dephasing mechanisms in the simulation,encompassing spontaneous decay,transit dephasing,collision dephasing,laser linewidth dephasing,and Doppler averaging.Homodyne readout utilizes both the real and imaginary parts of polarizability for sensing.In the case of the photon shot noise limit,its signal-to-noise ratio(SNR)expression resembles that of direct optical-intensity readout.However,the inherent coherent subtraction operation in homodyne detection significantly suppresses common-mode noise,while appropriately increasing the reference beam power enhances the gain in practical experiments.Indeed,this co-optimization problem,characterized by a high-dimensional variable space,two objectives,and non-convexity,is well-suited for solution by PSO.In addition,probe and coupling detuning contribute equivalently to polarizability and compensate for each other owing to Doppler averaging,thereby reducing the optimization variable space by one.By adopting a product form of linear gain and LDR as the fitness function,the PSO achieves rapid convergence.Here,the effectiveness of the PSO results is verified via the total harmonic distortion(THD).The relative error-based LDR calculation method we proposed efficiently measures receiver response linearity with consuming fewer computational resources.This research is expected to offer valuable insights into enhancing the performance of Rydberg-atom-based superheterodyne receivers.
基金supported by the Program for Guangdong Province Introduced Innovative and Entrepreneurial Team Program(2023ZT10L061)the NSFC Projects(Grant No.22402232)the Project supported by the Natural Science Foundation of Guangdong Province,China(Grant No.2025A1515011742).
文摘The development of atomically dispersed multi-metallic catalysts is imperative for tailoring catalytic performance and elucidating structure-activity relationships.However,synthesizing such precisely engineered architectures while maintaining atomic dispersion of distinct metal centers remains a formidable challenge due to thermodynamic instability and synthetic complexity.We herein propose a topological confinement pre-anchoring strategy via pre-anchoring spatially resolved Zn/Fe dual-metal sources in a structurally engineered metal-organic framework precursor to synthesize atomically dispersed ZnFe bimetallic single-atom catalysts.Extended X-ray absorption fine structure measurements and X-ray absorption near-edge structure reveal that the atomically dispersed Zn/Fe metal sites and electronic redistribution in ZnFe bimetallic single-atom catalysts.The ultrahigh surface area,hierarchical pore,and synergistic effect between Zn/Fe can greatly favor the exposure of the active site,mass transport,and improvement of intrinsic activity.Consequently,the ZnFe bimetallic single-atom catalyst demonstrates superior oxygen reduction reaction performance,achieving a half-wave potential of 0.86 V and delivering a kinetic current density of 10.1 mA cm^(-2)at 0.85 V versus RHE in 0.1 m KOH electrolyte.These metrics not only surpass those of commercial Pt/C,but also rival the highest-performing catalysts reported to date.The Zn-air battery built with ZnFe bimetallic single-atom catalyst exhibits high power density(278.5 mW cm^(-2))and specific discharging capacities(657 mAh g^(-1)).This work provides a new design pathway for constructing atomically dispersed multi-metal electrocatalysts for high-performance energy-related applications.
基金financially supported by the Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(2025JJ20019)the National Key R&D Program of China(2025YFE0107600)。
文摘Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.
基金financially supported by the National Natural Science Foundation of China (No. 22579095)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project (B2024204027)+2 种基金the Youth Top-notch Talent Foundation of Hebei Provincial Universities (BJK2022023)the Natural Science Foundation of Hebei Province (B2023204006)the talent training project of Hebei province (No. B20231004)。
文摘The rate capability and cycling stability of sodium metal batteries taking FeS_(2) or sulfur as cathode are limited due to their low reaction kinetics and severe shuttle effect.Herein,we rationally design a novel single-atom-dispersed S_(2)-FeNC/FeS_(2) nanocluster heterojunction embedded in carbon spheres(SFNC/FeS_(2)) for the electrode material of sodium metal batteries.Interestingly,during the discharging process,the Na^(+) is inserted into FeS_(2) to generate Na_(2)S,as well as the unique electrochemical reaction between S_(2)-FeNC and Na^(+) to form Na_(2)S.Meanwhile,the FeNC can adsorb Na_(2)S and catalyze the conversion from Na_(2)S and Fe to FeS_(2) or from Na_(2)S and FeNC to S_(2)-FeNC for suppressing the shuttle effect and promoting the distinct hybrid reversible electrochemical behavior,which improves performance tremendously.Notably,the SFNC/FeS_(2) electrode delivers a specific capacity of 338.7 mAh g^(-1) after superlong 2000 cycles at a current density of 5.0 A g^(-1) and achieves a high energy density of 430.1 Wh Kg^(-1) at a current density of 0.05 A g^(-1).This work presents a novel approach to studying sodium metal batteries with hybrid behavior for excellent high energy density and cycling stability.
基金supported by the National Natural Science Foundation of China(Nos.22422806,22378136,and 22138003)the Guangdong Pearl River Talents Program(Nos.2021QN02C847and 2021ZT09Z109)+4 种基金the Natural Science Foundation of Guangdong Province(Nos.2024A1515011196 and 2023B1515040005)the Fundamental Research Funds for the Central Universities(Nos.2024ZYGXZR011,2025ZYGXZR025)the Science and Technology Program of Guangzhou(No.2025A04J5244)the State Key Laboratory of Pulp and Paper Engineering(No.2024ZD09)the TCL Young Talent Program。
文摘The breaking of the symmetric electronic distribution of single-atom catalysts is effective in improving the intrinsic activity.However,traditional modification strategies can only disrupt the electronic distribution in one dimension,resulting in limited regulation of electronic structure.Herein,we report a multidimensional coordination strategy to significantly break the symmetrical electron distribution of the metal single site to achieve highly efficient electrochemical CO_(2) reduction reaction(CO_(2) RR).Ni singleatom sites decorated with planar P and axial Cl atoms are successfully constructed on carbon support(Ni-NPCl-C).Ni-NPCl-C affords CO Faraday efficiency over 90%in a wide potential window range from-0.5 to-1.2 V and an ultrahigh turnover frequency of 1.17×10^(5)h^(-1),much superior to its counterparts with single-dimensional coordination.Ni-NPCl-C can be further applied as a bifunctional catalyst to construct a rechargeable Zn-CO_(2) battery.Spectroscopic characterizations and theoretical calculations demonstrate that the dual adjustments with axial Cl and planar P can synergistically disrupt the electron distribution in two dimensions to increase electrons around Ni sites with the upshift of the d-band center,thereby facilitating the formation of*COOH intermediates and improving the CO_(2) RR performance.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSITRS2024-00345635 and RS-2021-NR060090)the Research Grant Council of the Hong Kong SAR(PolyU15302824)。
文摘Iron-based single-atom(SA)catalysts offer a promising alternative to noble-metal catalysts for the oxygen reduction reaction(ORR),yet their limited intrinsic activity and durability hinder practical energy device applications.Herein,we introduce a novel TiN/TiC-supported Fe SA catalyst(TiNC/Fe-NC)with a hierarchical heterostructure that synergistically enhances Fe-N_(x) site activity and accessibility.The TiNC/Fe-NC catalyst achieves outstanding ORR performances,with half-wave potentials(E_(1/2))of 0.852 V in acidic media and 0.942 V in alkaline media.Theoretical simulations reveal that strong electronic interaction and efficient charge transfer between TiNC and Fe-N_(x) sites optimize the adsorption energetics of key ORR intermediates,driving the enhanced activity.Remarkably,TiNC effectively scavenges reactive oxygen radicals generated at the Fe centers,ensuring exceptional durability with a minimal 28 mV loss in E_(1/2) after 10,000 cycles at 80℃in acid media.In practical applications,TiNC/Fe-NC delivers peak power densities of 306 mW cm^(-2) in zinc-air battery and 732 mW cm^(-2) in proton exchange membrane fuel cells,with remarkable long-term stability.This work establishes TiNC/Fe-NC as a highperformance,durable catalyst for advanced energy storage and conversion technologies.
基金supported by National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(MSIT)(No.RS-2023-00260527,RS-2024-00407282,RS-2025-00557667)supported by Hanyang University Industry-University Cooperation Foundation(No.202400000003943)supported by Korea Planning&Evaluation Institute of Industrial Technology(KEIT)funded by South Korean Ministry of Trade,Industry and Energy(MOTIE)(No.RS-2025-25454815,RS-2025-02308064,20017382)。
文摘Oxide semiconductors(OSs),introduced by the Hosono group in the early 2000s,have evolved from display backplane materials to promising candidates for advanced memory and logic devices.The exceptionally low leakage current of OSs and compatibility with three-dimensional(3D)architectures have recently sparked renewed interest in their use in semiconductor applications.This review begins by exploring the unique material properties of OSs,which fundamentally originate from their distinct electronic band structure.Subsequently,we focus on atomic layer deposition(ALD),a core technique for growing excellent OS films,covering both basic and advanced processes compatible with 3D scaling.The basic surface reaction mechanisms—adsorption and reaction—and their roles in film growth are introduced.Furthermore,material design strategies,such as cation selection,crystallinity control,anion doping,and heterostructure engineering,are discussed.We also highlight challenges in memory applications,including contact resistance,hydrogen instability,and lack of p-type materials,and discuss the feasibility of ALD-grown OSs as potential solutions.Lastly,we provide an outlook on the role of ALD-grown OSs in memory technologies.This review bridges material fundamentals and device-level requirements,offering a comprehensive perspective on the potential of ALD-driven OSs for next-generation semiconductor memory devices.
基金financially supported by the National Oversea Postdoctoral Talent Attraction Programthe Pilot Group Program of the Research Fund for International Senior Scientists(52350710795)+2 种基金the Youth Fund of the National Natural Science Foundation of China(52402288)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(YESS20230183)the Yangfan Special Program of Shanghai Star Project(24YF2729700)。
文摘Defect engineering serves as a cornerstone in the design of high-effciency single-atom catalysts(SACs)for advanced electrocatalytic systems.This study demonstrates oxygen vacancy-induced near-zero-valent Pt SACs anchored on TiO2 for efficient hydrogen evolution reaction(HER).Synchrotron spectroscopy and density functional theory calculation reveal that oxygen vacancies create unconventional Pt-Ti coordination while strengthening electronic metal-support interactions.This facilitates substantial electron transfer from TiO2 to Pt,generating a near-zero-valent Pt state with elevated electron density.The modified electronic structure lowers the Pt d-band center,reducing hydrogen intermediate(*H)adsorption energy and optimizing HER kinetics.Moreover,ab initio molecular dynamics and in situ Raman spectra show that the negative charge accumulated at the Pt site promotes K^(+)enrichment at the interface,which enhances H-OH bond polarization and accelerates water dissociation kinetics.The resulting D-TiO_(2)/Pt SACs exhibit superior HER activity across acidic,neutral,and alkaline conditions,achieving low overpotentials of 40,57,and 60 mV at 10 mA cm^(-2),respectively.Additionally,its mass activities at the overpotential of 100 mV are 10.3,33.9,and 20.9 times higher that of Pt/C,respectively.This study shows the key role of defectmediated electronic engineering in tailoring SACs'valence states and catalytic functions,advancing sustainable hydrogen production through rational catalyst design.
基金supported by the Samsung Electronics Co.,Ltd.(ISO230414-05954-01)Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF2021R1A6A1A03039981)+2 种基金the Korea Institute for Advancement of Technology(KIAT)Grant,funded by the Korea Government(MOTIE)(P0023703,HRD Program for Industrial Innovation)The computations were performed at the Korea Institute of Science and Technology Information(KISTI)National Supercomputing Center(KSC-2024-CRE-0316)the UNIST Supercomputing Center。
文摘Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric for dynamic random access memory(DRAM)applications,offering a high dielectric constant with a remarkable leakage-lowering effect by Al acceptor doping.However,ATO fabrication via conventional supercycle-based ALD suffers from severe crystallinity loss during the growth of TiO_(2) upon Al doping owing to the dopant-induced lattice disorder.In addition,Al doping cannot reduce any inherent O vacancies(V_(O))of TiO_(2),although the original purpose of doping was to address the n-type nature caused by V_(O).To resolve these limitations,we propose a single-step,in-situ Ar/O_(2) post-doping plasma(PDP)process immediately after the Al dopant incorporation.Using the PDP process,simultaneous atomic-scale dopant migration-mediated crystallization and V_(O) annihilation were successfully initiated.Thus,the surface concentration of the dopant decreased,reducing the dopant-induced lattice distortion,while promoting the highly crystallized seed layer-like surface.Consequently,strong rutile-phase recovery was accompanied by enhanced lattice-matched growth.In addition,the PDP process significantly lowers the V_(O)-to-lattice oxygen ratio by facilitating the recombination between reactive O species and V_(O),increasing the corresponding 0.4 e V of conduction band offset(CBO).Despite the common trade-off between the dielectric constant and leakage,the Pt/PDP-ATO/Ru capacitor exhibited a simultaneous 30%increase in dielectric constant and up to a 1.6-order reduction in leakage current density.
