Effective control of gas-phase pollutants(volatile organic compounds(VOCs)and CO)is critical to human health and the ecological environment.Catalytic oxidation is one of the most promising technologies for achieving e...Effective control of gas-phase pollutants(volatile organic compounds(VOCs)and CO)is critical to human health and the ecological environment.Catalytic oxidation is one of the most promising technologies for achieving efficient volatile organic compounds and CO emission control.The subnano cluster catalyst can not only provide catalytic sites with multiple metal atoms,but also maintain full utilization efficiency.Almost all metal atoms in highly dispersed clusters can be used for adsorption and conversion of reactants.Recently,various types of sub-nano clusters,including subnano cluster oxides,have been developed and demonstrated excellent performance in low-temperature gas-phase pollutants combustion.In this mini review,we systematically summarize the structure,physicochemical properties,characterization,and applications of sub-nano cluster catalysts in catalytic oxidation of CO,methane,propane,propylene,toluene and its derivatives,formaldehyde and chlorinated volatile organic compounds.Finally,we have analyzed and discussed the problems and challenges faced by sub-nano cluster catalysts in both basic research and practical applications,providing a scientific basis for the design,synthesis,and application of efficient heterogeneous catalysts for CO and VOCs oxidation.展开更多
Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL ...Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.展开更多
Previous X-ray and optical studies of the galaxy cluster pair A222/223 suggested the possible presence of a=lamentary structure connecting the two clusters,a result that appears to be supported by subsequent weak-lens...Previous X-ray and optical studies of the galaxy cluster pair A222/223 suggested the possible presence of a=lamentary structure connecting the two clusters,a result that appears to be supported by subsequent weak-lensing analyses.This=lament has been reported to host a primordial warm-hot intergalactic medium,which existed prior to being heated by the interactions of the clusters.In this study,we made an attempt to examine the reported emission feature with data from an archival Suzaku observation,taking advantage of its low detector background.Because the emission is expected to be very weak,we=rst carefully examined all potential sources of“contamination,”and then modeled the residual emission.Due to large uncertainties,unfortunately,our results can neither con=rm the presence of the reported emission feature nor rule it out.We discuss the sources of uncertainties.展开更多
Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to p...Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to participate in this online questionnaire survey.The survey tools included a general information questionnaire and a self-made NMOSD symptoms scale,which included the prevalence,severity,and distress of 29 symptoms.Cluster analysis was used to identify symptom clusters,and network analysis was used to analyze the symptom network and node characteristics and central indicators including strength centrality(r_(s)),closeness centrality(r_(c))and betweeness centrality(r_(b))were used to identify core symptoms and symptom clusters.Results The most common symptom was pain(65.7%),followed by paraesthesia(65.0%),fatigue(65.0%),easy awakening(63.6%).Regarding the burden level of symptoms,pain was the most burdensome symptom,followed by paraesthesia,easy awakening,fatigue,and difficulty falling asleep.Six clusters were identified:somatosensory,motor,visual,and memory symptom clusters,bladder and rectum symptom clusters,sleep symptoms clusters,and neuropsychological symptom clusters.Fatigue(r_(s)=12.39,r_(b)=68.00,r_(c)=0.02)was the most central and prominent bridge symptom,and motor symptom cluster(r_(s)=2.68,r_(c)=0.10)was the most central symptom cluster among the six clusters.Conclusions Our study demonstrated the necessity of symptom management targeting fatigue,pain,and motor symptom cluster in patients with NMOSD.展开更多
Clusters greatly influence thermophysical properties of near critical gases. The cluster structures of supercritical fluids in general and Carbon Dioxide especially are important for the advanced supercritical fluid t...Clusters greatly influence thermophysical properties of near critical gases. The cluster structures of supercritical fluids in general and Carbon Dioxide especially are important for the advanced supercritical fluid technologies and analytics development. The paper extends to near critical densities the developed earlier methods to extract the clusters’ properties from Online Electronic Database of NIST on thermophysical properties of fluids. This Database contains a hidden knowledge of cluster fractions’ properties in real gases. The discovered earlier linear chain clusters dominate at intermediate densities. Their properties can be extrapolated to high density gases, thus opening the way to study large 3D clusters in near critical zone. The potential energy density of a gas, cleared from the chain clusters’ contribution, reflects only the 3D clusters’ characteristics. A series expansion of this value by the Monomer Fraction density discovers properties of n-particle 3D clusters. The paper demonstrates a discrete row of 3D clusters’ particle numbers and gives estimations for bond energies of these clusters.展开更多
The 11th data release of the LAMOST survey provides fundamental stellar parameters but lacks detailed abundance measurements forα-elements,which are crucial for understanding stellar populations and Galactic chemical...The 11th data release of the LAMOST survey provides fundamental stellar parameters but lacks detailed abundance measurements forα-elements,which are crucial for understanding stellar populations and Galactic chemical evolution.In this study,we derive the abundances of oxygen(O),magnesium(Mg),silicon(Si),calcium(Ca),and titanium(Ti)for over 6.8 million stars using LAMOST DR11 low-resolution spectra.To ensure reliable measurements,we select 760 open clusters spanning a broad range of ages and apply Monte Carlo sampling for accurate abundance estimates.Additionally,we utilize over 30,000 stars from the GALAH DR4 catalog to train an XGBoost model for extractingα-element abundances from LAMOST DR11 spectra.Bayesian linear regression is employed to analyze the compositional distribution across the Galactic disk and infer chemical gradients as a function of Galactocentric distance.Our results indicate a general increase in chemical abundances with Galactocentric distance,with oxygen showing the steepest gradient.Our results confirm the overall increase ofα-element abundances with Galactocentric distance,consistent with previous studies,while minor discrepancies in Mg,Ca,and Ti gradients likely arise from differences in sample selection,observational sensitivity,or Galactic enrichment processes.展开更多
Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integr...Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integrating both structural and attribute-based information.However,these models often emphasize node proximities without adequately balancing the efficiency of clustering based on both structural and attribute data.Furthermore,they tend to neglect the critical fuzzy information inherent in attributed graph clusters.To address these issues,we introduce a new framework,Markov lumpability optimization,for efficient clustering of large-scale attributed graphs.Specifically,we define a lumped Markov chain on an attribute-augmented graph and introduce a new metric,Markov lumpability,to quantify the differences between the original and lumped Markov transition probability matrices.To minimize this measure,we propose a conjugate gradient projectionbased approach that ensures the partitioning closely aligns with the intrinsic structure of fuzzy clusters through conditional optimization.Extensive experiments on both synthetic and real-world datasets demonstrate the superior performance of the proposed framework compared to existing clustering algorithms.This framework has many potential applications,including dynamic community analysis of social networks,user profiling in recommendation systems,functional module identification in biological molecular networks,and financial risk control,offering a new paradigm for mining complex patterns in high-dimensional attributed graph data.展开更多
LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully ...LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully revealed.Herein,we systematically studied the evolution of solvation structures with increasing LiNO_(3) concentration in both carbonate and ether electrolytes.The results from molecular dynamics simulations unveil that the Li^(+)solvation structure is less affected in carbonate electrolytes,while in ether electrolytes,there is a significant decrease of solvent molecules in Li^(+)coordination,and a larger average size of Li^(+)solvation structure emerges as LiNO_(3) concentration increases.Notably,the formation of large ion aggregates with size of several nanometers(nano-clusters),is observed in ether-based electrolytes at conventional Li^(+)concentration(1 M)with higher NO_(3)^(-) ratio,which is further proved by infrared spectroscopy and small-angle X-ray scattering experiments.The nano-clusters with abundant anions are endowed with a narrow energy gap of molecular orbitals,contributing to the formation of an inorganic rich electrode/electrolyte interphase that enhances the reversibility of lithium stripping/plating with Coulombic efficiency up to 99.71%.The discovery of nano-clusters elucidates the underlying mechanism linking ions/solvent aggregation states of electrolytes to interfacial stability in advanced battery systems.展开更多
Two-dimensional(2D)materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features.However,the usually-complicated synthesis proce...Two-dimensional(2D)materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features.However,the usually-complicated synthesis procedures impede in-depth clarification of their catalytic mechanisms.To this end,herein we developed an efficient one-step dimension-reduction carbonization strategy,with which we successfully architected a highly-efficient catalyst for oxygen reduction reaction(ORR),featured with symbiotic cobalt single atoms and clusters decorated in two-dimensional(2D)ultra-thin(3.5 nm thickness)nitrogen-carbon nanosheets.The synergistic effects of the two components afford excellent oxygen reduction activity in alkaline media(E_(1/2)=0.823 V vs.RHE)and thereof a high power density(146.61 mW cm^(-2))in an assembled Zn-air battery.As revealed by theoretical calculations,the cobalt clusters can regulate electrons surrounding those individual atoms and affect the adsorption of intermediate species.As a consequence,the derived active sites of single cobalt atoms lead to a significant improvement of the ORR performance.Thus,our work may fuel interests to delicate architectu re of single atoms and clusters coexisting 2D support toward optimal electrocatalytic performance.展开更多
Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited ...Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited by the use of different metal precursor salts corresponding to different ligands.An alternative approach,the ion exchange(IE)method,can overcome this limitation to some extent.Nevertheless,there is still an urgent need to address the stabilization of metals(especially precious metals)by using IE method.Here,we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction(reduced Pt/Zn-3-IE).The catalyst can achieve an initial propane conversion of 26%in a pure propane atmosphere at 550℃and shows little deactivation even after 7.5 d of operation.Moreover,the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.展开更多
The first three months after lung transplantation are the clinical“vulnerable period”.Complications during this period often appear in the form of symptom clusters.The core includes primary graft dysfunction(PGD),in...The first three months after lung transplantation are the clinical“vulnerable period”.Complications during this period often appear in the form of symptom clusters.The core includes primary graft dysfunction(PGD),infection,inflammatory response and multiple organ dysfunction,and are interconnected to form a complex network.The symptom cluster shows a clear dynamic trajectory:the risk of PGD peaks at 24 hours after surgery,and its evolution trajectory(recovery,delay,deterioration)directly affects long-term graft function;infections show a“double peak distribution”,with bacteria/fungi dominant in the early stage(<1 month)and viruses/opportunistic infections dominant in the middle stage(1-6 months),and promote each other with PGD.Influencing factors include four dimensions:donor(smoking history,infection),recipient(weakness,immune status),perioperative period(surgical method,support strategy)and postoperative management(balance of immunosuppression).In the future,dynamic prediction models and individualized management paths need to be built to improve patient outcomes.展开更多
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates ...The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.展开更多
Metal-based antimicrobial materials have been extensively studied and applied over decades.While these materials are notably characterized by their superior antibacterial performance and low propensity to induce drug ...Metal-based antimicrobial materials have been extensively studied and applied over decades.While these materials are notably characterized by their superior antibacterial performance and low propensity to induce drug resistance,critical limitations such as inherent cytotoxicity,poor solubility,and instability in aqueous solution remain significant challenges requiring systematic optimization.In this study,we synthesized water-soluble molecular iron-oxo clusters(MIC)with excellent biosafety and stability of aqueous solution.Our findings demonstrate that MIC exhibits marked therapeutic efficacy in cecal ligation and puncture induced sepsis models,a critical validation given sepsis'etiology as a life-threatening infection mediated systemic inflammatory syndrome.MIC combats bacteria by enhancing humoral immune responsiveness.MIC significantly improved the survival rate,reduced bacterial burden,stabilized body temperature,and modulated cytokine profiles in mice with sepsis.Further investigations revealed that MIC promotes B cells proliferation and oxidative phosphorylation,and mitigates mitochondrial damage and apoptosis in B cells,suggesting its role in modulating cellular metabolism.RNA sequencing analysis demonstrated that MIC exerts its effects by influencing key pathways involved in humoral immunity,inflammatory responses,and metabolic adaptation.These findings establish MIC as a novel therapeutic agent for regulating immune responses in sepsis,providing innovative strategies to improve recovery from this life-threatening condition.展开更多
Surface-supported clusters forming by aggregation of excessive adatoms could be the main defects of 2D materials after chemical vapor deposition.They will significantly impact the electronic/magnetic properties.Moreov...Surface-supported clusters forming by aggregation of excessive adatoms could be the main defects of 2D materials after chemical vapor deposition.They will significantly impact the electronic/magnetic properties.Moreover,surface supported atoms are also widely explored for high active and selecting catalysts.Severe deformation,even dipping into the surface,of these clusters can be expected because of the very active edge of clusters and strong interaction between supported clusters and surfaces.However,most models of these clusters are supposed to simply float on the top of the surface because ab initio simulations cannot afford the complex reconstructions.Here,we develop an accurate graph neural network machine learning potential(MLP)from ab initio data by active learning architecture through fine-tuning pre-trained models,and then employ the MLP into Monte Carlo to explore the structural evolutions of Mo and S clusters(1-8 atoms)on perfect and various defective MoS2 monolayers.Interestingly,Mo clusters can always sink and embed themselves into MoS2 layers.In contrast,S clusters float on perfect surfaces.On the defective surface,a few S atoms will fill the vacancy and rest S clusters float on the top.Such significant structural reconstructions should be carefully taken into account.展开更多
Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01815-z In the original publication,Fig.5 was published with few mistakes.The correct version of Fig.5 is given in this correction.
Correction to:Nano-Micro Letters(2025)17:123 https://doi.org/10.1007/s40820-025-01654-y Following publication of the original article[1],the authors reported that Dr.Mohamed Bououdina’s affiliation needed to be corre...Correction to:Nano-Micro Letters(2025)17:123 https://doi.org/10.1007/s40820-025-01654-y Following publication of the original article[1],the authors reported that Dr.Mohamed Bououdina’s affiliation needed to be corrected from 1 to 2.The correct author affiliation has been provided in this Correction and the original article[1]has been corrected.展开更多
The magneto-volume effect in Fe-based clusters,as a microscopic manifestation of the Invar effect in Fe-Ni alloys,has recently attracted increasing attention.However,a deeper understanding of the physical mechanism un...The magneto-volume effect in Fe-based clusters,as a microscopic manifestation of the Invar effect in Fe-Ni alloys,has recently attracted increasing attention.However,a deeper understanding of the physical mechanism underlying the magneto-volume effect remains lacking.Here we employed first-principles calculations to investigate the ground-state properties and thermal expansion behaviors of icosahedral Fe_(12)X(X=Ti,Fe,Co,Ni)clusters.The spin arrangement of Fe_(12)X clusters is determined by the magnetic exchange interaction between atomic pairs.During thermal expansion,Fe_(12)X clusters exhibit different volume and magnetic moment behaviors.The magnetic moment attenuation induced by thermal excitation is a prerequisite for the emergence of the magneto-volume effect in Fe_(12)X clusters,consistent with the Invar anomaly observed in Fe-Ni alloys.The bonding characteristic analysis reveals that there are two competing bonding transitions in the process of the moment attenuation.The strengthening of the bonding state of the surface Fe-Fe bonds significantly exceeds the weakening of the bonding state of the Fe-X bonds,resulting in a contraction of the cluster volume,which is considered to be the explanation of the magneto-volume effect at the electronic structure level.Understanding the origin of the magneto-volume effect in magnetic metal clusters not only deepens the insight into the Invar effect but also provides theoretical guidance for its practical application.展开更多
The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model clust...The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model cluster has been extensively investigated in various fields,including structural modulation,catalysis,and self-assembly under laboratory conditions,with the aim of gaining an in-depth understanding of their roles in biological functions.Herein,we revisited three well-known[Fe_(4)S_(4)(SR)_(4)]^(2–)molecules,namely[Me_(4)N]_(2)[Fe_(4)S_(4)(SR)_(4)](R=o-MBT,m-MBT,p-MBT),and successfully established their single crystal structures that remain unknown prior to this work.Interestingly,it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the[4Fe–4S]core,which further influences their overall packing patterns in single crystals.In addition,this work unveils two new structure transformation behaviors for the[Fe_(4)S_(4)(SR)_(4)]^(2–)system:i)the monomeric[Fe(SR)_(4)]^(2–)and tetrameric[Fe_(4)S_(4)(SR)_(4)]^(2–)can be interconverted,and ii)[Fe_(4)S_(4)(SR)_(4)]^(2–)can be transferred into an intriguing iron-oxide complex Na_(2)Fe_(6)O(OMe)_(18)·6MeOH in a well-controlled oxidizing environment.展开更多
Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clus...Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.展开更多
CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–deri...CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.展开更多
基金supported by the National Natural Science Foundation of China(No.22506042)the Natural Science Foundation of Henan Province(Nos.252300421710 and 252300421552)the High level Talent Research Launch Fund of Henan University of Technology(No.2024BS061).
文摘Effective control of gas-phase pollutants(volatile organic compounds(VOCs)and CO)is critical to human health and the ecological environment.Catalytic oxidation is one of the most promising technologies for achieving efficient volatile organic compounds and CO emission control.The subnano cluster catalyst can not only provide catalytic sites with multiple metal atoms,but also maintain full utilization efficiency.Almost all metal atoms in highly dispersed clusters can be used for adsorption and conversion of reactants.Recently,various types of sub-nano clusters,including subnano cluster oxides,have been developed and demonstrated excellent performance in low-temperature gas-phase pollutants combustion.In this mini review,we systematically summarize the structure,physicochemical properties,characterization,and applications of sub-nano cluster catalysts in catalytic oxidation of CO,methane,propane,propylene,toluene and its derivatives,formaldehyde and chlorinated volatile organic compounds.Finally,we have analyzed and discussed the problems and challenges faced by sub-nano cluster catalysts in both basic research and practical applications,providing a scientific basis for the design,synthesis,and application of efficient heterogeneous catalysts for CO and VOCs oxidation.
基金financially supported by the National Natural Science Foundation of China(22471268)the National Key Research and Development Project(2022YFA1503900)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1170000)the Natural Science Foundation of Fujian Province(2022J05090,2024T3003)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH03,CXZX-2024-JQ08).
文摘Chiral metal-organic clusters(MOCs)integrating lanthanide ions(Ln^(3+))and organic luminophores present a promising platform for modulating circularly polarized luminescence(CPL).However,achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge.Herein,two enantiomeric pairs of heterometallic EuSn oxo clusters,designated as Sn_(2)EuL_(2)-R/S and Sn_(2)EuL_(4)-R/S,were strategically synthesized using axially chiral binaphthol-phosphonate ligands.These hybrid clusters exhibit dual emission,characterized by a broad ligand-derived fluorescence band superimposed with sharp,characteristic Eu^(3+)f-f transitions,which enables excitation-dependent luminescence color tuning.Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn^(4+)centers.Notably,Sn_(2)EuL_(2)-R/S demonstrates CPL activity in both near-UV(|g_(lum)|=1.7×10^(-3))and visible(|g_(lum)|=3.1×10^(-2))regions.This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.
基金supported in part by the National Natural Science Foundation of China through Grant 11821303by the Ministry of Science and Technology of China through Grant 2018YFA0404502+1 种基金support from the China Scholarship Councilthe nancial support of the GA?R EXPRO grant No.21-13491X.
文摘Previous X-ray and optical studies of the galaxy cluster pair A222/223 suggested the possible presence of a=lamentary structure connecting the two clusters,a result that appears to be supported by subsequent weak-lensing analyses.This=lament has been reported to host a primordial warm-hot intergalactic medium,which existed prior to being heated by the interactions of the clusters.In this study,we made an attempt to examine the reported emission feature with data from an archival Suzaku observation,taking advantage of its low detector background.Because the emission is expected to be very weak,we=rst carefully examined all potential sources of“contamination,”and then modeled the residual emission.Due to large uncertainties,unfortunately,our results can neither con=rm the presence of the reported emission feature nor rule it out.We discuss the sources of uncertainties.
基金supported by the Specific Research Fund for Top-notch Talents of Guangdong Provincial Hospital of Chinese Medicine(No.2022KT1188).
文摘Objectives To identify core symptoms and symptom clusters in patients with neuromyelitis optica spectrum disorder(NMOSD)by network analysis.Methods From October 10 to 30,2023,140 patients with NMOSD were selected to participate in this online questionnaire survey.The survey tools included a general information questionnaire and a self-made NMOSD symptoms scale,which included the prevalence,severity,and distress of 29 symptoms.Cluster analysis was used to identify symptom clusters,and network analysis was used to analyze the symptom network and node characteristics and central indicators including strength centrality(r_(s)),closeness centrality(r_(c))and betweeness centrality(r_(b))were used to identify core symptoms and symptom clusters.Results The most common symptom was pain(65.7%),followed by paraesthesia(65.0%),fatigue(65.0%),easy awakening(63.6%).Regarding the burden level of symptoms,pain was the most burdensome symptom,followed by paraesthesia,easy awakening,fatigue,and difficulty falling asleep.Six clusters were identified:somatosensory,motor,visual,and memory symptom clusters,bladder and rectum symptom clusters,sleep symptoms clusters,and neuropsychological symptom clusters.Fatigue(r_(s)=12.39,r_(b)=68.00,r_(c)=0.02)was the most central and prominent bridge symptom,and motor symptom cluster(r_(s)=2.68,r_(c)=0.10)was the most central symptom cluster among the six clusters.Conclusions Our study demonstrated the necessity of symptom management targeting fatigue,pain,and motor symptom cluster in patients with NMOSD.
文摘Clusters greatly influence thermophysical properties of near critical gases. The cluster structures of supercritical fluids in general and Carbon Dioxide especially are important for the advanced supercritical fluid technologies and analytics development. The paper extends to near critical densities the developed earlier methods to extract the clusters’ properties from Online Electronic Database of NIST on thermophysical properties of fluids. This Database contains a hidden knowledge of cluster fractions’ properties in real gases. The discovered earlier linear chain clusters dominate at intermediate densities. Their properties can be extrapolated to high density gases, thus opening the way to study large 3D clusters in near critical zone. The potential energy density of a gas, cleared from the chain clusters’ contribution, reflects only the 3D clusters’ characteristics. A series expansion of this value by the Monomer Fraction density discovers properties of n-particle 3D clusters. The paper demonstrates a discrete row of 3D clusters’ particle numbers and gives estimations for bond energies of these clusters.
基金supported by the National Natural Science Foundation of China under program Nos.12090040,12090043,12473031,and 12003025as well as the Basic Research Program of Yunnan Province(No.202401AT070142)+2 种基金the International Center of Supernovae,Yunnan Key Laboratory(No.202302AN360001)the Natural Science Foundation of Yunnan Province(No.202201BC070003)the support of the Postdoctoral Fellowship Program of CPSF under grant Nos.GZC20240124 and 2024M760242.
文摘The 11th data release of the LAMOST survey provides fundamental stellar parameters but lacks detailed abundance measurements forα-elements,which are crucial for understanding stellar populations and Galactic chemical evolution.In this study,we derive the abundances of oxygen(O),magnesium(Mg),silicon(Si),calcium(Ca),and titanium(Ti)for over 6.8 million stars using LAMOST DR11 low-resolution spectra.To ensure reliable measurements,we select 760 open clusters spanning a broad range of ages and apply Monte Carlo sampling for accurate abundance estimates.Additionally,we utilize over 30,000 stars from the GALAH DR4 catalog to train an XGBoost model for extractingα-element abundances from LAMOST DR11 spectra.Bayesian linear regression is employed to analyze the compositional distribution across the Galactic disk and infer chemical gradients as a function of Galactocentric distance.Our results indicate a general increase in chemical abundances with Galactocentric distance,with oxygen showing the steepest gradient.Our results confirm the overall increase ofα-element abundances with Galactocentric distance,consistent with previous studies,while minor discrepancies in Mg,Ca,and Ti gradients likely arise from differences in sample selection,observational sensitivity,or Galactic enrichment processes.
基金supported by the National Natural Science Foundation of China(Grant No.72571150)Beijing Natural Science Foundation(Grant No.9182015)。
文摘Attributed graph clustering plays a vital role in uncovering hidden network structures,but it presents significant challenges.In recent years,various models have been proposed to identify meaningful clusters by integrating both structural and attribute-based information.However,these models often emphasize node proximities without adequately balancing the efficiency of clustering based on both structural and attribute data.Furthermore,they tend to neglect the critical fuzzy information inherent in attributed graph clusters.To address these issues,we introduce a new framework,Markov lumpability optimization,for efficient clustering of large-scale attributed graphs.Specifically,we define a lumped Markov chain on an attribute-augmented graph and introduce a new metric,Markov lumpability,to quantify the differences between the original and lumped Markov transition probability matrices.To minimize this measure,we propose a conjugate gradient projectionbased approach that ensures the partitioning closely aligns with the intrinsic structure of fuzzy clusters through conditional optimization.Extensive experiments on both synthetic and real-world datasets demonstrate the superior performance of the proposed framework compared to existing clustering algorithms.This framework has many potential applications,including dynamic community analysis of social networks,user profiling in recommendation systems,functional module identification in biological molecular networks,and financial risk control,offering a new paradigm for mining complex patterns in high-dimensional attributed graph data.
基金supported by the National Natural Science Foundation of China(No.22372083,52201259)the National Key R&D Program of China(2021YFB2500300)+2 种基金the Fundamental Research Funds for the Central Universities:Nankai University(63241607)the Natural Science Foundation of Tianjin(No.22JCZDJC00380)the Young Elite Scientist Sponsorship Program by CAST.
文摘LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully revealed.Herein,we systematically studied the evolution of solvation structures with increasing LiNO_(3) concentration in both carbonate and ether electrolytes.The results from molecular dynamics simulations unveil that the Li^(+)solvation structure is less affected in carbonate electrolytes,while in ether electrolytes,there is a significant decrease of solvent molecules in Li^(+)coordination,and a larger average size of Li^(+)solvation structure emerges as LiNO_(3) concentration increases.Notably,the formation of large ion aggregates with size of several nanometers(nano-clusters),is observed in ether-based electrolytes at conventional Li^(+)concentration(1 M)with higher NO_(3)^(-) ratio,which is further proved by infrared spectroscopy and small-angle X-ray scattering experiments.The nano-clusters with abundant anions are endowed with a narrow energy gap of molecular orbitals,contributing to the formation of an inorganic rich electrode/electrolyte interphase that enhances the reversibility of lithium stripping/plating with Coulombic efficiency up to 99.71%.The discovery of nano-clusters elucidates the underlying mechanism linking ions/solvent aggregation states of electrolytes to interfacial stability in advanced battery systems.
基金supported by the National Natural Science Foundation of China(51872115 and 12234018)Beijing Synchrotron Radiation Facility(BSRF)4B9A.
文摘Two-dimensional(2D)materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features.However,the usually-complicated synthesis procedures impede in-depth clarification of their catalytic mechanisms.To this end,herein we developed an efficient one-step dimension-reduction carbonization strategy,with which we successfully architected a highly-efficient catalyst for oxygen reduction reaction(ORR),featured with symbiotic cobalt single atoms and clusters decorated in two-dimensional(2D)ultra-thin(3.5 nm thickness)nitrogen-carbon nanosheets.The synergistic effects of the two components afford excellent oxygen reduction activity in alkaline media(E_(1/2)=0.823 V vs.RHE)and thereof a high power density(146.61 mW cm^(-2))in an assembled Zn-air battery.As revealed by theoretical calculations,the cobalt clusters can regulate electrons surrounding those individual atoms and affect the adsorption of intermediate species.As a consequence,the derived active sites of single cobalt atoms lead to a significant improvement of the ORR performance.Thus,our work may fuel interests to delicate architectu re of single atoms and clusters coexisting 2D support toward optimal electrocatalytic performance.
文摘Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods,which exhibit unique properties such as suppressing structure-sensitive side reactions.However,this method is limited by the use of different metal precursor salts corresponding to different ligands.An alternative approach,the ion exchange(IE)method,can overcome this limitation to some extent.Nevertheless,there is still an urgent need to address the stabilization of metals(especially precious metals)by using IE method.Here,we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction(reduced Pt/Zn-3-IE).The catalyst can achieve an initial propane conversion of 26%in a pure propane atmosphere at 550℃and shows little deactivation even after 7.5 d of operation.Moreover,the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.
文摘The first three months after lung transplantation are the clinical“vulnerable period”.Complications during this period often appear in the form of symptom clusters.The core includes primary graft dysfunction(PGD),infection,inflammatory response and multiple organ dysfunction,and are interconnected to form a complex network.The symptom cluster shows a clear dynamic trajectory:the risk of PGD peaks at 24 hours after surgery,and its evolution trajectory(recovery,delay,deterioration)directly affects long-term graft function;infections show a“double peak distribution”,with bacteria/fungi dominant in the early stage(<1 month)and viruses/opportunistic infections dominant in the middle stage(1-6 months),and promote each other with PGD.Influencing factors include four dimensions:donor(smoking history,infection),recipient(weakness,immune status),perioperative period(surgical method,support strategy)and postoperative management(balance of immunosuppression).In the future,dynamic prediction models and individualized management paths need to be built to improve patient outcomes.
基金supported by the Natural Science Foundation of Hunan Province(No.2023JJ30650)the Central South University Innovation-Driven Research Programme(No.2023CXQD061)。
文摘The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO_(2)conversion.This study demonstrates how controlled exposure of metal sites governs CO_(2)electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures.The Bi_(8)-DMF cluster,constructed using tert–butylthiacalix[4]arene(TC4A)as the sole ligand,features two surface-exposed Bi active sites,while the dual-ligand Bi_(8)-Fc(with TC4A/ferrocene carboxylate)forms a fully encapsulated structure.Electrocatalytic tests reveal Bi_(8)-DMF achieves exceptional formate selectivity(>90%Faradaic efficiency)across a broad potential window(-0.9 V to-1.6 V vs.RHE)with 20 h stability,outperforming Bi_(8)-Fc(60%efficiency at-1.5 V).Theoretical calculations attribute Bi_(8)-DMF's superiority to exposed Bi sites that stabilize the critical*OCHO intermediate via optimized orbital interactions.This work provides crucial guidance for polynuclear catalyst design:moderate exposure of metal active sites significantly enhances CO_(2)reduction performance.
基金the generous supported by the National Key R&D Program of China(No.2023YFC2413100)the National Natural Science Foundation of China(Nos.22322102,21871042 and 21471028)+1 种基金the Fundamental Research Funds for the Central Universities-Excellent Youth Team Program(No.2412023YQ001)the Natural Science Foundation of Jilin Province(Nos.YDZJ202401550ZYTS,20200201083JC)。
文摘Metal-based antimicrobial materials have been extensively studied and applied over decades.While these materials are notably characterized by their superior antibacterial performance and low propensity to induce drug resistance,critical limitations such as inherent cytotoxicity,poor solubility,and instability in aqueous solution remain significant challenges requiring systematic optimization.In this study,we synthesized water-soluble molecular iron-oxo clusters(MIC)with excellent biosafety and stability of aqueous solution.Our findings demonstrate that MIC exhibits marked therapeutic efficacy in cecal ligation and puncture induced sepsis models,a critical validation given sepsis'etiology as a life-threatening infection mediated systemic inflammatory syndrome.MIC combats bacteria by enhancing humoral immune responsiveness.MIC significantly improved the survival rate,reduced bacterial burden,stabilized body temperature,and modulated cytokine profiles in mice with sepsis.Further investigations revealed that MIC promotes B cells proliferation and oxidative phosphorylation,and mitigates mitochondrial damage and apoptosis in B cells,suggesting its role in modulating cellular metabolism.RNA sequencing analysis demonstrated that MIC exerts its effects by influencing key pathways involved in humoral immunity,inflammatory responses,and metabolic adaptation.These findings establish MIC as a novel therapeutic agent for regulating immune responses in sepsis,providing innovative strategies to improve recovery from this life-threatening condition.
基金supported by the National Natural Science Foundation of China(Grant No.12374253,12074053,12004064)J.G.thanks the Foreign talents project(G2022127004L),The authors also acknowledge computer support from the Shanghai Supercomputer Center,the DUT Supercomputing Center,and the Tianhe supercomputer of Tianjin Center.
文摘Surface-supported clusters forming by aggregation of excessive adatoms could be the main defects of 2D materials after chemical vapor deposition.They will significantly impact the electronic/magnetic properties.Moreover,surface supported atoms are also widely explored for high active and selecting catalysts.Severe deformation,even dipping into the surface,of these clusters can be expected because of the very active edge of clusters and strong interaction between supported clusters and surfaces.However,most models of these clusters are supposed to simply float on the top of the surface because ab initio simulations cannot afford the complex reconstructions.Here,we develop an accurate graph neural network machine learning potential(MLP)from ab initio data by active learning architecture through fine-tuning pre-trained models,and then employ the MLP into Monte Carlo to explore the structural evolutions of Mo and S clusters(1-8 atoms)on perfect and various defective MoS2 monolayers.Interestingly,Mo clusters can always sink and embed themselves into MoS2 layers.In contrast,S clusters float on perfect surfaces.On the defective surface,a few S atoms will fill the vacancy and rest S clusters float on the top.Such significant structural reconstructions should be carefully taken into account.
文摘Correction to:Rare Met.https://doi.org/10.1007/s12598-021-01815-z In the original publication,Fig.5 was published with few mistakes.The correct version of Fig.5 is given in this correction.
文摘Correction to:Nano-Micro Letters(2025)17:123 https://doi.org/10.1007/s40820-025-01654-y Following publication of the original article[1],the authors reported that Dr.Mohamed Bououdina’s affiliation needed to be corrected from 1 to 2.The correct author affiliation has been provided in this Correction and the original article[1]has been corrected.
基金financially supported by the National Natural Science Foundation of China(No.52171038)the Key Technology Research and Development Program of Shandong Province(Nos.2021SFGC1001 and 2023CXGC010403)+2 种基金the program of Jinan Science and Technology Bureau(No.2020GXRC019)key projects for serving Shandong Province(No.31370004012207)the National Key Research and Development Program of China(No.2023YFB3712600).
文摘The magneto-volume effect in Fe-based clusters,as a microscopic manifestation of the Invar effect in Fe-Ni alloys,has recently attracted increasing attention.However,a deeper understanding of the physical mechanism underlying the magneto-volume effect remains lacking.Here we employed first-principles calculations to investigate the ground-state properties and thermal expansion behaviors of icosahedral Fe_(12)X(X=Ti,Fe,Co,Ni)clusters.The spin arrangement of Fe_(12)X clusters is determined by the magnetic exchange interaction between atomic pairs.During thermal expansion,Fe_(12)X clusters exhibit different volume and magnetic moment behaviors.The magnetic moment attenuation induced by thermal excitation is a prerequisite for the emergence of the magneto-volume effect in Fe_(12)X clusters,consistent with the Invar anomaly observed in Fe-Ni alloys.The bonding characteristic analysis reveals that there are two competing bonding transitions in the process of the moment attenuation.The strengthening of the bonding state of the surface Fe-Fe bonds significantly exceeds the weakening of the bonding state of the Fe-X bonds,resulting in a contraction of the cluster volume,which is considered to be the explanation of the magneto-volume effect at the electronic structure level.Understanding the origin of the magneto-volume effect in magnetic metal clusters not only deepens the insight into the Invar effect but also provides theoretical guidance for its practical application.
基金supported by the Fundamental Research Funds for the Central Universities(22120240204 and 22120240039)the National Natural Science Foundation of China(22301219,Z.Z.,22101205,H.H.)。
文摘The synthesized molecular clusters featuring the cubic[4Fe–4S]core have been studied for several decades,as they serve as true analogs of the active components in ferritin within biological systems.Such a model cluster has been extensively investigated in various fields,including structural modulation,catalysis,and self-assembly under laboratory conditions,with the aim of gaining an in-depth understanding of their roles in biological functions.Herein,we revisited three well-known[Fe_(4)S_(4)(SR)_(4)]^(2–)molecules,namely[Me_(4)N]_(2)[Fe_(4)S_(4)(SR)_(4)](R=o-MBT,m-MBT,p-MBT),and successfully established their single crystal structures that remain unknown prior to this work.Interestingly,it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the[4Fe–4S]core,which further influences their overall packing patterns in single crystals.In addition,this work unveils two new structure transformation behaviors for the[Fe_(4)S_(4)(SR)_(4)]^(2–)system:i)the monomeric[Fe(SR)_(4)]^(2–)and tetrameric[Fe_(4)S_(4)(SR)_(4)]^(2–)can be interconverted,and ii)[Fe_(4)S_(4)(SR)_(4)]^(2–)can be transferred into an intriguing iron-oxide complex Na_(2)Fe_(6)O(OMe)_(18)·6MeOH in a well-controlled oxidizing environment.
基金supported by the Start-Up Research Funding of Fujian Normal University(No.Y0720326K13)the National Natural Science Foundation of China(Nos.22103035 and 22033005)+2 种基金the National Key R&D Program of China(No.2022YFA1503900)Shenzhen Science and Technology Program(No.RCYX20231211090357078)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.
基金support from National Natural Science Foundation of China(32101474 and 42377249)National Key Research and Development Program of China(2023YFD2201605).
文摘CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.
