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
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
An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the...An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.展开更多
Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as...Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.展开更多
In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving ...In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving these two goals,high-availability clusters and load-balancing clusters have significant differences in their design concepts and application scenarios,while also maintaining close connections.This paper aims to conduct an in-depth analysis of the core objectives,working principles,technical advantages and disadvantages,and typical application cases of high-availability clusters and load-balancing clusters.By introducing an analogical model of a“restaurant kitchen,”the differences between the two are intuitively explained,and their technical characteristics are compared in detail.Additionally,a detailed practical case is included to specifically demonstrate the collaborative work of high-availability and load-balancing technologies through the construction process of Keepalived and HAProxy.Finally,taking the architecture of a typical e-commerce website as an example,this paper demonstrates the best practice of organically combining the two cluster technologies in a production environment to build a robust and high-performance distributed system.Research shows that understanding the differences between the two and implementing collaborative deployment is the cornerstone of designing modern IT infrastructure.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
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
Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc...Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.展开更多
Objective This study aimed to investigate the prevalence of HIV pretreatment drug resistance(PDR)and the transmission clusters associated with PDR-related mutations in newly diagnosed,treatmentnaive patients between 2...Objective This study aimed to investigate the prevalence of HIV pretreatment drug resistance(PDR)and the transmission clusters associated with PDR-related mutations in newly diagnosed,treatmentnaive patients between 2020 and 2023 in Dehong prefecture,Yunnan province,China.Methods Demographic information and plasma samples were collected from study participants.PDR was assessed using the Stanford HIV Drug Resistance Database.The Tamura-Nei 93 model within HIVTRACE was employed to compute pairwise matches with a genetic distance of 0.015 substitutions per site.Results Among 948 treatment-naive individuals with eligible sequences,36 HIV subtypes were identified,with unique recombinant forms(URFs)being the most prevalent(18.8%,178/948).The overall prevalence of PDR was 12.4%(118/948),and resistance to non-nucleotide reverse transcriptase inhibitors(NNRTIs),nucleotide reverse transcriptase inhibitors(NRTIs),and protease inhibitors(PIs)was10.7%,1.3%,and 1.6%,respectively.A total of 91 clusters were identified,among which eight showed evidence of PDR strain transmission.The largest PDR-associated cluster consisted of six CRF01_AE drugresistant strains carrying K103N and V179T mutations;five of these individuals had initial CD4^(+)cell counts<200 cells/μL.Conclusion The distribution of HIV subtypes in Dehong is diverse and complex.PDR was moderately prevalent(12.4%)between 2020 and 2023.Evidence of transmission of CRF01_AE strains carrying K103N and V179T mutations was found.Routine surveillance of PDR and the strengthening of control measures are essential to limit the spread of drug-resistance HIV strains.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
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
Objective:This study aims to investigate the patterns of symptom occurrence in patients experiencing acute exacerbations of chronic obstructive pulmonary disease(AECOPD).It will explore the composition of symptom clus...Objective:This study aims to investigate the patterns of symptom occurrence in patients experiencing acute exacerbations of chronic obstructive pulmonary disease(AECOPD).It will explore the composition of symptom clusters and analyze the correlation between these clusters and health-related quality of life(HRQoL).Methods:A total of 207 patients with AE-COPD were surveyed from a tertiary grade A hospital.Data collection was conducted using three validated instruments:the Basic Information Questionnaire(BIQ),Disease Symptom Survey Questionnaire(MSAS),and Quality of Life Questionnaire(CAT).Statistical software SPSS 22.0 was used to analyze the correlation between symptom clusters and quality of life.Results:Exploratory factor analysis showed that five major symptom clusters existed in the patients,including the psycho-emotional symptom cluster,the sleep-related symptom cluster,the other side effects symptom cluster,the energy deficiency symptom cluster and the cough-loss of appetite symptom cluster,and the severity of the symptom clusters showed a significant negative correlation with the quality of life of the patients(P<0.05).Conclusion:Strengthening the comprehensive management of symptom clusters in patients with AE-COPD can help to effectively reduce the symptom burden of patients,and then significantly improve their quality of life.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
We investigated the ionization and dissociation processes of ammonia clusters ranging from dimer to pentamer induced by 800-nm femtosecond laser fields.Time-of-flight(TOF)mass spectra of the ammonia clusters were reco...We investigated the ionization and dissociation processes of ammonia clusters ranging from dimer to pentamer induced by 800-nm femtosecond laser fields.Time-of-flight(TOF)mass spectra of the ammonia clusters were recorded over a range of laser intensities from 2.1×10^(12)W/cm^(2) to 5.6×10^(12)W/cm^(2).The protonated ion signals dominate the spectra,which is consistent with the stability of the geometric structures.The ionization and dissociation channels of ammonia clusters are discussed.The competition and switching among observed dissociation channels are revealed by analyzing the variations in the relative ionic yields of specific protonated and unprotonated clusters under different laser intensities.These results indicate that the ionization of the neutral multiple-ammonia units,produced through the dissociation of cluster ions,may start to contribute,as well as the additional processes to consume protonated ions and/or produce unprotonated ions induced by the femtosecond laser fields when the laser intensity is above^4×10^(12)W/cm^(2).These findings provide deeper insights into the ionization and dissociation dynamics in multi-photon ionization experiments involving ammonia clusters.展开更多
To fulfill the training requirements for the daily operations of multirotor unmanned aerial vehicles(UAVs)clusters,a UAV cluster collaborative task integrated simulation platform(UAV-TISP)was developed.The platform in...To fulfill the training requirements for the daily operations of multirotor unmanned aerial vehicles(UAVs)clusters,a UAV cluster collaborative task integrated simulation platform(UAV-TISP)was developed.The platform integrates a suite of hardware and software to simulate a range of collaborative UAV cluster operation scenarios.It features modules for collaborative task planning,UAV cluster simulations,and tactical monitoring.The platform significantly reduces training costs by eliminating physical drone dependencies while offering a flexible environment for testing swarm algorithms.UAV-TISP supports both individual UAV and swarm operations,incorporating high-fidelity flight dynamics,real-time communication via user datagram protocol(UDP),and collision avoidance strategies.Utilizing the OSGEarth engine,it enables dynamic 3D environment visualization and scenario customization.Three key task scenarios-route flight,formation reconstruction,and formation transformation-were tested to validate the platform’s efficacy.Results demonstrated robust formation maintenance,adaptive collision avoidance,and seamless task execution.Comparative analysis with Gazebo Sim revealed lower trajectory deviations in UAV-TISP,highlighting its superior accuracy in simulating real-world flight dynamics.Future work will focus on enhancing scalability for diverse UAV models,optimizing swarm networking under communication constraints,and expanding mission scenarios.UAV-TISP serves as a versatile tool for both operational training and advanced algorithm development in UAV cluster applications.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
Taking advantage of the relatively automatic and easy operation procedure,continuous-flow catalysis has become a promising wastewater treatment technique for organic dye removal.However,developing suitable packing cat...Taking advantage of the relatively automatic and easy operation procedure,continuous-flow catalysis has become a promising wastewater treatment technique for organic dye removal.However,developing suitable packing catalysts with favorable activity and low flow resistance remains a challenging task for the construction of continuous-flow catalytic systems.In this paper,we report the preparation of a catalytic module,in which palladium clusters(PdC)are incorporated on defect-rich nitrogen-doped holey graphene(NHG)co-assembled withaluminum silicate fibers(ASFs)(PdC/NHG-ASFs).The resultant PdC/NHG-ASFs composite catalyst exhibits an assembly morphology and can be facilely integrated into a glass reactor to construct an efficient fixed-bed system for continuous-flow catalysis.The corresponding catalytic system demonstrates high processing capacity and excellent durability for the reduction of six N-containing organic dyes owing to the robust hierarchical structure and dualactive components(i.e.,NHG and PdC)of the PdC/NHGASFs composite.The processing rate of the fixed-bed system constructed with the PdC/NHG-ASFs catalyst for the reduction of a representative dye(i.e.,4-nitrophenol)was 1.45×10^(-3)mmol·mg^(-1)·min^(-1),surpassing those previously reported for systems based on metal catalysts.Theoretical calculations show that the activity enhancement in nitroarene reduction reaction originate from the synergistic effect of the two active components.The integration of heterogeneous catalysis and flow-chemistry techniques provides a rational design concept for environmental catalysis,offering a more efficient,scalable,and sustainable approach.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
Strong Coulombic repulsion in small doubly charged molecular ions usually leads to fragmentation.Some of these ions,such as CO_(2)^(++),could survive and be detected if they are stable or metastable in energetics,but ...Strong Coulombic repulsion in small doubly charged molecular ions usually leads to fragmentation.Some of these ions,such as CO_(2)^(++),could survive and be detected if they are stable or metastable in energetics,but how to produce these observable doubly charged ions is a puzzling issue.Here we investigate CO_(2)^(++)production by electron-impact ionization with a supersonic molecular beam of CO_(2)under different nozzle pressures,using time-of-flight mass spectrometry measurements and ab initio calculations.The mass spectral profile of CO_(2)^(++)varies slightly with the nozzle pressure,implying different mechanisms of the ion production.The calculations indicate that the ground state of CO_(2)^(++)is 3Aʺwith a nonlinear conformation,while the linear conformer is in the first excited state 1Δ_(g).We further suggest that,besides CO_(2)^(++)(1Δ_(g))produced from CO_(2),CO_(2)^(++)(3Aʺ)could be produced by the dissociation of doubly charged dimer(C2O4^(++))in a repulsive triplet state.展开更多
Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfull...Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster(Cu11),which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule.Notably,this Cu11cluster exhibited excellent photocatalytic hydrogen evolution activity(8.13 mmol g-1h-1)even in the absence of a mediator and noble metal co-catalyst.Furthermore,when Cu11clusters were loaded onto the surface of TiO_(2)nanosheets,the resultant Cu11@TiO_(2)nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency,which is 60 times higher than that of pure TiO_(2)nanosheets.The incorporation of Cu11clusters within the Cu11@TiO_(2)effectively inhibits the recombination of photogenerated electrons and holes,thereby accelerating the charge separation and migration in the composite material.This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.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An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.
文摘Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
文摘In modern distributed systems and cloud computing architectures,high availability and high scalability are core requirements to ensure the continuous and stable operation of services.As key technologies for achieving these two goals,high-availability clusters and load-balancing clusters have significant differences in their design concepts and application scenarios,while also maintaining close connections.This paper aims to conduct an in-depth analysis of the core objectives,working principles,technical advantages and disadvantages,and typical application cases of high-availability clusters and load-balancing clusters.By introducing an analogical model of a“restaurant kitchen,”the differences between the two are intuitively explained,and their technical characteristics are compared in detail.Additionally,a detailed practical case is included to specifically demonstrate the collaborative work of high-availability and load-balancing technologies through the construction process of Keepalived and HAProxy.Finally,taking the architecture of a typical e-commerce website as an example,this paper demonstrates the best practice of organically combining the two cluster technologies in a production environment to build a robust and high-performance distributed system.Research shows that understanding the differences between the two and implementing collaborative deployment is the cornerstone of designing modern IT infrastructure.
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 by the National Key R&D Program of China(No.2023YFB3712504)the National Natural Science Foundation of China(Nos.22273038,22073043,and 22033004)。
文摘Accurate description of noncova-lent interactions in large systems is challenging due to the require-ment of high-level electron corre-lation methods.The generalized energy-based fragmentation(GEBF)approach,in conjunc-tion with the domain-based local pair natural orbital(DLPNO)method,has been applied to assess the average binding energies(ABEs)of large benzene clus-ters,specifically(C6H6)13,at the coupled cluster singles and doubles with perturbative triples correction[CCSD(T)]level and the complete basis set(CBS)limit.Utilizing GEBF-DLPNO-CCSD(T)/CBS ABEs as benchmarks,various DFT functionals were evaluated.It was found that several functionals with empirical dispersion correction,including M06-2X-D3,B3LYP-D3(BJ),and PBE-D3(BJ),provide accurate descriptions of the ABEs for(C6H6)13 clusters.Additionally,the M06-2X-D3 functional was used to calculate the ABEs and relative stabili-ties of(C6H6)n clusters for n=11,12,13,14,and 15 revealing that the(C6H6)13 cluster ex-hibits the highest relative stability.These findings align with experimental evidence suggest-ing that n=13 is one of the magic numbers for benzene clusters(C6H6)n,with n≤30.
基金supported by the National Key Research and Development Program of China(2022YFC2305201)National Natural Science Foundation of China(71874168)。
文摘Objective This study aimed to investigate the prevalence of HIV pretreatment drug resistance(PDR)and the transmission clusters associated with PDR-related mutations in newly diagnosed,treatmentnaive patients between 2020 and 2023 in Dehong prefecture,Yunnan province,China.Methods Demographic information and plasma samples were collected from study participants.PDR was assessed using the Stanford HIV Drug Resistance Database.The Tamura-Nei 93 model within HIVTRACE was employed to compute pairwise matches with a genetic distance of 0.015 substitutions per site.Results Among 948 treatment-naive individuals with eligible sequences,36 HIV subtypes were identified,with unique recombinant forms(URFs)being the most prevalent(18.8%,178/948).The overall prevalence of PDR was 12.4%(118/948),and resistance to non-nucleotide reverse transcriptase inhibitors(NNRTIs),nucleotide reverse transcriptase inhibitors(NRTIs),and protease inhibitors(PIs)was10.7%,1.3%,and 1.6%,respectively.A total of 91 clusters were identified,among which eight showed evidence of PDR strain transmission.The largest PDR-associated cluster consisted of six CRF01_AE drugresistant strains carrying K103N and V179T mutations;five of these individuals had initial CD4^(+)cell counts<200 cells/μL.Conclusion The distribution of HIV subtypes in Dehong is diverse and complex.PDR was moderately prevalent(12.4%)between 2020 and 2023.Evidence of transmission of CRF01_AE strains carrying K103N and V179T mutations was found.Routine surveillance of PDR and the strengthening of control measures are essential to limit the spread of drug-resistance HIV strains.
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 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.
文摘Objective:This study aims to investigate the patterns of symptom occurrence in patients experiencing acute exacerbations of chronic obstructive pulmonary disease(AECOPD).It will explore the composition of symptom clusters and analyze the correlation between these clusters and health-related quality of life(HRQoL).Methods:A total of 207 patients with AE-COPD were surveyed from a tertiary grade A hospital.Data collection was conducted using three validated instruments:the Basic Information Questionnaire(BIQ),Disease Symptom Survey Questionnaire(MSAS),and Quality of Life Questionnaire(CAT).Statistical software SPSS 22.0 was used to analyze the correlation between symptom clusters and quality of life.Results:Exploratory factor analysis showed that five major symptom clusters existed in the patients,including the psycho-emotional symptom cluster,the sleep-related symptom cluster,the other side effects symptom cluster,the energy deficiency symptom cluster and the cough-loss of appetite symptom cluster,and the severity of the symptom clusters showed a significant negative correlation with the quality of life of the patients(P<0.05).Conclusion:Strengthening the comprehensive management of symptom clusters in patients with AE-COPD can help to effectively reduce the symptom burden of patients,and then significantly improve their quality of life.
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.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.92261201,12134005,12334011)。
文摘We investigated the ionization and dissociation processes of ammonia clusters ranging from dimer to pentamer induced by 800-nm femtosecond laser fields.Time-of-flight(TOF)mass spectra of the ammonia clusters were recorded over a range of laser intensities from 2.1×10^(12)W/cm^(2) to 5.6×10^(12)W/cm^(2).The protonated ion signals dominate the spectra,which is consistent with the stability of the geometric structures.The ionization and dissociation channels of ammonia clusters are discussed.The competition and switching among observed dissociation channels are revealed by analyzing the variations in the relative ionic yields of specific protonated and unprotonated clusters under different laser intensities.These results indicate that the ionization of the neutral multiple-ammonia units,produced through the dissociation of cluster ions,may start to contribute,as well as the additional processes to consume protonated ions and/or produce unprotonated ions induced by the femtosecond laser fields when the laser intensity is above^4×10^(12)W/cm^(2).These findings provide deeper insights into the ionization and dissociation dynamics in multi-photon ionization experiments involving ammonia clusters.
文摘To fulfill the training requirements for the daily operations of multirotor unmanned aerial vehicles(UAVs)clusters,a UAV cluster collaborative task integrated simulation platform(UAV-TISP)was developed.The platform integrates a suite of hardware and software to simulate a range of collaborative UAV cluster operation scenarios.It features modules for collaborative task planning,UAV cluster simulations,and tactical monitoring.The platform significantly reduces training costs by eliminating physical drone dependencies while offering a flexible environment for testing swarm algorithms.UAV-TISP supports both individual UAV and swarm operations,incorporating high-fidelity flight dynamics,real-time communication via user datagram protocol(UDP),and collision avoidance strategies.Utilizing the OSGEarth engine,it enables dynamic 3D environment visualization and scenario customization.Three key task scenarios-route flight,formation reconstruction,and formation transformation-were tested to validate the platform’s efficacy.Results demonstrated robust formation maintenance,adaptive collision avoidance,and seamless task execution.Comparative analysis with Gazebo Sim revealed lower trajectory deviations in UAV-TISP,highlighting its superior accuracy in simulating real-world flight dynamics.Future work will focus on enhancing scalability for diverse UAV models,optimizing swarm networking under communication constraints,and expanding mission scenarios.UAV-TISP serves as a versatile tool for both operational training and advanced algorithm development in UAV cluster applications.
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.
基金financially supported by the Key Research and Development Program of Hubei Province(No.2022BAA026)the Open Project of Hubei Key Laboratory of Novel Reactor and Green Chemical Technology(No.NRGC202203)+3 种基金the Open/Innovation Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202203)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(No.GCX2022005)the Open/Innovation Project of Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry(No.2022BEEA06)the Innovation and Entrepreneurship Training Program Funded by Wuhan Institute of Technology(No.202310490007)
文摘Taking advantage of the relatively automatic and easy operation procedure,continuous-flow catalysis has become a promising wastewater treatment technique for organic dye removal.However,developing suitable packing catalysts with favorable activity and low flow resistance remains a challenging task for the construction of continuous-flow catalytic systems.In this paper,we report the preparation of a catalytic module,in which palladium clusters(PdC)are incorporated on defect-rich nitrogen-doped holey graphene(NHG)co-assembled withaluminum silicate fibers(ASFs)(PdC/NHG-ASFs).The resultant PdC/NHG-ASFs composite catalyst exhibits an assembly morphology and can be facilely integrated into a glass reactor to construct an efficient fixed-bed system for continuous-flow catalysis.The corresponding catalytic system demonstrates high processing capacity and excellent durability for the reduction of six N-containing organic dyes owing to the robust hierarchical structure and dualactive components(i.e.,NHG and PdC)of the PdC/NHGASFs composite.The processing rate of the fixed-bed system constructed with the PdC/NHG-ASFs catalyst for the reduction of a representative dye(i.e.,4-nitrophenol)was 1.45×10^(-3)mmol·mg^(-1)·min^(-1),surpassing those previously reported for systems based on metal catalysts.Theoretical calculations show that the activity enhancement in nitroarene reduction reaction originate from the synergistic effect of the two active components.The integration of heterogeneous catalysis and flow-chemistry techniques provides a rational design concept for environmental catalysis,offering a more efficient,scalable,and sustainable approach.
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.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences(XDB0450202)。
文摘Strong Coulombic repulsion in small doubly charged molecular ions usually leads to fragmentation.Some of these ions,such as CO_(2)^(++),could survive and be detected if they are stable or metastable in energetics,but how to produce these observable doubly charged ions is a puzzling issue.Here we investigate CO_(2)^(++)production by electron-impact ionization with a supersonic molecular beam of CO_(2)under different nozzle pressures,using time-of-flight mass spectrometry measurements and ab initio calculations.The mass spectral profile of CO_(2)^(++)varies slightly with the nozzle pressure,implying different mechanisms of the ion production.The calculations indicate that the ground state of CO_(2)^(++)is 3Aʺwith a nonlinear conformation,while the linear conformer is in the first excited state 1Δ_(g).We further suggest that,besides CO_(2)^(++)(1Δ_(g))produced from CO_(2),CO_(2)^(++)(3Aʺ)could be produced by the dissociation of doubly charged dimer(C2O4^(++))in a repulsive triplet state.
基金supported by the National Natural Science Foundation of China(Nos.22371263 and U2004193)Natural Science Foundation of Henan Province(No.232300421225)。
文摘Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster(Cu11),which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule.Notably,this Cu11cluster exhibited excellent photocatalytic hydrogen evolution activity(8.13 mmol g-1h-1)even in the absence of a mediator and noble metal co-catalyst.Furthermore,when Cu11clusters were loaded onto the surface of TiO_(2)nanosheets,the resultant Cu11@TiO_(2)nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency,which is 60 times higher than that of pure TiO_(2)nanosheets.The incorporation of Cu11clusters within the Cu11@TiO_(2)effectively inhibits the recombination of photogenerated electrons and holes,thereby accelerating the charge separation and migration in the composite material.This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.
