Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous st...Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous structures,including metalorganic frameworks(MOFs),covalent organic frameworks(COFs),hydrogen-bonded organic frameworks(HOFs),and supramolecular organic frameworks(SOFs),possess a variety of unique properties due to their high crystallinity,high porosity,large surface area,and adjustable structure.The integration of MNCs with RFs endows the resulting composites with desirable features(e.g.,enhanced and tunable optical properties,improved catalytic and photophysical activities,selective molecular recognition),which facilitates a broad spectrum of biomedical applications and advancing the development of integrated theranostic nanoplatforms.This review summarizes recent advances in the synthesis and biomedical applications of various MNCs/RFs composites.We systematically categorize and evaluate key strategies for incorporating MNCs into four types of RFs(MOFs,COFs,HOFs,and SOFs)while discussing the advantages and limitations of each approach.The biomedical applications of these composites are comprehensively reviewed,encompassing biosensing,bioimaging,antitumor therapy,and antibacterial treatments.Finally,the review addresses current challenges and outlines future research directions,with the aim of guiding the rational design of novel MNCs/RFs composites,enabling precise control over their structures and functions toward advanced biomedical applications.展开更多
Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminesce...Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.展开更多
The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver n...The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.展开更多
Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Here...Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.展开更多
We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average partic...We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average particle size of 2.62 nm.The catalyst shows excellent catalytic activity when applied to the hydrolysis of AB,which owns a high turnover frequency value of 531.56 mol_(H2)mol_(Ru)^(-1)min^(-1)and a low activation energy of 46.38 kJ·mol^(-1),it also exhibits good durability which maintains 61.13%initial activity after five cycles.The high catalytic performance of Ru_(1)Cu_(25)P_(7.5)/TiO_(2)may be attributed to the synergistic effects between Ru,Cu,and P elements,fine particle size,good dispersion,and the tight adhesion between nanoclusters and carrier.展开更多
Aflatoxin B_(1)(AFB_(1))in food is a threaten to food safety and human health.In this study,a colorimetric and fluorescent dual-mode aptamer sensor was constructed for rapid and accurate detection of AFB_(1)based on p...Aflatoxin B_(1)(AFB_(1))in food is a threaten to food safety and human health.In this study,a colorimetric and fluorescent dual-mode aptamer sensor was constructed for rapid and accurate detection of AFB_(1)based on polyvinylpyrrolidone-gold-copper bimetallic nanoclusters(PVP-Au/Cu NCs)and Mn_(3)O_(4)nanoparticles(Mn_(3)O_(4)NPs).In the presence of AFB_(1),the AFB_(1)aptamer on the surface of Mn_(3)O_(4)NPs specifically bound to AFB_(1).The oxidase-like activity of Mn_(3)O_(4)NPs was restored and 3,3',5,5'-0tetramethylbenzidine(TMB)was oxidized to oxidized TMB(ox TMB),which quenched the orange fluorescence of the PVP-Au/Cu NCs.With AFB_(1)concentrations increasing,the blue color of ox TMB deepened,the fluorescence quenching efficiency was enhanced.The working range was 0–56μg/Lwith a limit of detection(LOD)of 0.36μg/L(colorimetric),and2.86–40.00μg/L with a LOD of 0.29μg/L(fluorescent).In addition,the established sensor was successfully applied to determine AFB_(1)in milk,rice,oats,and corn,with a recovery rate of 91.1%–107.5%.This study provides an insight for fabricating a sensitive,efficient,and accurate analytical platform for rapid detection of AFB_(1)in food.展开更多
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies...Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies(Dp-Au NCs@Fe^(2+)) through the coordination of Fe^(2+) ions by a dopa-containing peptidomimetic ligand(Dp CDp).This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe^(2+)centers,bridged by Dp CDp to facilitate directional electron transfer.Comprehensive spectroscopic and kinetic analyses reveal that Dp CDp promotes efficient charge migration from the Au core to surface-bound Fe^(2+),significantly enhancing H_(2)O_(2)-mediated peroxidase-like activity.Compared to bare Dp-Au NCs,Dp-Au NCs@Fe^(2+) display a 4.3-fold improvement in detection sensitivity,a 6.7-fold increase in catalytic efficiency,and markedly stronger hydroxyl radical generation.Mechanistically,this activity stems from a synergistic triad:direct H_(2)O_(2) oxidation at gold surfaces,radical generation at Fe^(2+) sites,and Dp CDp-facilitated electron shuttling.This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering,offering valuable insights for the future design of bioinspired catalytic systems.展开更多
Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures ...Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures and properties.However,it is still challenging to get highly active and stable MNCs as surface ligands can hinder their activities,while a complete lack of surface ligand protection can lead to instability.To address this concern,here a series of Pd_(6)nanoclusters(NCs)with varying ligand amounts were synthesized by using Pd_(6)(SC_(6)(C_(2))H_(17))_(12)as precursor and single-walled carbon nanotube(s-CNT)as carrier through treating the composite at different temperatures and times.展开更多
Understanding the photoluminescence(PL)mechanism of metal nanoclusters from both molecular and supramolecular perspectives is crucial for developing highly emissive cluster-based nanomaterials.In this study,we synthes...Understanding the photoluminescence(PL)mechanism of metal nanoclusters from both molecular and supramolecular perspectives is crucial for developing highly emissive cluster-based nanomaterials.In this study,we synthesized two structurally similar Ag14 nanoclusters with different phosphine stabilizers,which demonstrated opposite PL behaviors in solution and crystalline states.The Ag14 nanocluster stabilized by P(Ph-OMe)_(3) ligands exhibited a higher PL intensity compared to the one stabilized by P(Ph-F)_(3) ligands,which was attributed to the stronger electron-donating ability of the P(Ph-OMe)_(3) ligand that improved ligand-to-metal charge transfer efficiency.In contrast,the P(Ph-F)_(3) stabilized Ag14 crystals displayed greater PL intensity than the Ag14 cluster crystal with a-OMe surface,which was due to stronger intermolecular interactions within the cluster lattice of the former that limited non-radiative energy loss and thus enhanced PL.Overall,this work aims to promote a comprehensive understanding of the fluorescence in cluster-based nanomaterials,which will be beneficial for their downstream applications.展开更多
Atomically precise silver nanoclusters(AgNCs)offer unique opportunities to correlate structure and photophysical properties,yet enhancing their photoluminescence emission remains challenging due to dominance of non-ra...Atomically precise silver nanoclusters(AgNCs)offer unique opportunities to correlate structure and photophysical properties,yet enhancing their photoluminescence emission remains challenging due to dominance of non-radiative decay pathways.Here,we report a ligand-engineering strategy to modulate the optical properties of high-nuclearity Ag_(56) NCs.The synthesized two NCs,Ag_(56)S_(12)(^(t)BuS)_(20)(CF_(3)CO_(2))_(12)(MeCN)_(3)(NC-I) and Ag_(56)S_(12)(^(t)BuS)_(20)(^(n)BuSO_(3))_(12)(NC-II),possess a similar hexagonal-close-packed Ag_(14) kernel,which is encapsulated by a similar icosahedral S_(12) middle-shell and an outer Ag_(42) shell,but differ in overall symmetry and outer Ag-ligand shell connectivity.Replacement of bidentate CF_(3) CO_(2)^(−)with tridentaten BuSO_(3)^(−) ligands increases overall Ag-X(X=O,S,and Ag)bonding interactions,resulting in not only a more rigid and compact outer Ag_(42) shell structure but also contraction of cationic Ag_(14) core and anionic icosahedral S_(12) middle-shell.These structural modifications enhance radiative decay and suppress non-radiative pathways,leading to a 17-fold increase in photoluminescence quantum yield and extended average emission lifetime.Computational analysis confirms that ligand-induced geometric stabilization and electronic delocalization govern the excited-state dynamics.This work demonstrates that rational ligand design can synergistically tune cluster geometry,rigidity,and electronic structure,providing a general strategy to improve the photophysical performance of high-nuclearity AgNCs.展开更多
Solar-driven H_(2) production coupled with selective organic transformation represents a promising strategy for co-generation of green hydrogen and high-value chemicals,yet its feasibility relies critically on effecti...Solar-driven H_(2) production coupled with selective organic transformation represents a promising strategy for co-generation of green hydrogen and high-value chemicals,yet its feasibility relies critically on effective bifunctional photocatalysts.Herein,we report the synthesis of ultrafine Cd_(x)Zn_(1-x)S nanocrystals derived from a zeolitic imidazolate framework(ZIF),featuring high surface area,shortened charge diffusion path,and enhanced H_(2) evolution activity.Anchoring amorphous Pt sub-nanoclusters onto these nanocrystals created a bifunctional catalyst(Pt-Cd_(x)Zn_(1-x)S)for efficient lactic acid photoreforming,enabling coproduction of H_(2) with switchable selectivity toward pyruvic acid(PA)or 2,3-dihydroxy-2,3-dimethylsuccinic acid(DTA).The optimized 0.5Pt-Cd_(0.3)Zn_(0.7)S catalyst achieved an exceptional H_(2) production rate of 270.6 mmol h^(-1) g^(-1),73.1%PA selectivity,and 62.8% apparent quantum efficiency at 400 nm.Mechanistic studies revealed that lactic acid undergoes C-H cleavage to form carbon-centered radicals.Pt sub-nanoclusters served as electron sinks to facilitate O-H dissociation and PA formation,whereas pristine Cd_(0.3)Zn_(0.6)7S promoted direct C-C coupling of radicals to predominantly yield DTA.This work offers critical insights for designing advanced bifunctional photocatalysts to integrate solar hydrogen and value-added chemical synthesis.展开更多
The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.R...The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.Recent advances in the precise synthesis of metal nanoclusters,coupled with state-of-the-art characterization techniques,have enabled atomic-level investigation of structure-activity relationships in nanocatalysts.Due to their well-defined atomic architectures,the active metal sites within these nanocatalysts can be accurately identified,facilitating systematic studies on how compositions(structures)modulate catalytic performance.This review begins by summarizing recent advances in the controlled synthesis of atomically precise metal nanoclusters,followed by an overview of progress in the electrochemical reduction of CO_(2) to CO using nanoclusters as catalysts.Subsequently,we systematically investigate the effects of metal kernel characteristics and staple properties on catalytic activity,selectivity,and stability.Furthermore,current challenges are outlined,and prospective research directions are proposed in this rapidly evolving field.It is anticipated that this review will inspire further innovation in the synthesis of atomically precise nanocluster catalysts,promote a deeper mechanistic understanding of metal nanocluster-mediated electrochemical CO_(2) reduction,and push forward the related industrial applications.展开更多
Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical p...Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.展开更多
Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attribu...Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attributes encompassing molecular magnetism[1],photoluminescence[2],and catalysis[3].Organic ligands play a crucial role in effectively shielding these NCs,serving two primary functions:firstly,vital in preventing NC aggregation,particularly for the formation of robust single-crystal structures;secondly,acting as either bridging or peripheral structural components of NCs[4].This characterization of organic-inorganic hybridization offers unique advantages for unraveling the intricate relationships between structure and properties[5].展开更多
To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration signific...To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration significance and systematic research re-quirements.By utilizing the low-cost and excellent magnetic and stable chemical characteristics of barium ferrite(BaFe_(12)O_(19))and using the high dielectric loss and excellent chemical inertia of nanocarbon clusters,a new type of nanocomposites with carbon nanoclusters en-capsulating BaFe_(12)O_(19)was designed and synthesized by combining an impregnation method and a high-temperature calcination strategy.Furthermore,Ce-Mn ions were introduced into the BaFe_(12)O_(19)lattice to improve the dielectric and magnetic properties of BaFe_(12)O_(19)cores significantly,and the energy band structure of the doped lattice and the orders of Ce replacing Fe sites were calculated.Benefiting from Ce-Mn ion doping and carbon nanocluster encapsulation,the composite material exhibited excellent dual functionality of corrosion resist-ance and EWA.When BaCe_(0.2)Mn_(0.3)Fe_(11.5)O_(19)-C(BCM-C)was calcined at 600°C,the minimum reflection loss of-20.1 dB was achieved at 14.43 GHz.The Ku band’s effective absorption bandwidth of 4.25 GHz was achieved at an absorber thickness of only 1.3 mm.The BCM-C/polydimethylsiloxane coating had excellent corrosion resistance in the simulated marine environment(3.5wt%NaCl solution).The|Z|0.01Hz value of BCM-C remained at 106Ω·cm^(2)after 12 soaking days.The successful preparation of the BaFe_(12)O_(19)composite en-capsulated with carbon nanoclusters provides new insights into the preparation of multifunctional absorbent materials and the fabrication of absorbent devices applied in humid marine environments in the future.展开更多
Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,an...Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,and precursor,respectively.Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs,including transmission electron microscopy(TEM),X-ray photoelectron spectrometer(XPS),Fourier transform infrared spectrometer(FTIR),X-ray diffractometer(XRD),fluorescence spectrometer,and ultraviolet visible absorption spectrometer.FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm.Moreover,the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm,respectively.Under the optimal detection conditions,FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200μmol·L^(-1).The detection limit was 0.084μmol·L^(-1).The fluorescence-quenching mechanism was ascribed to the static quenching.The detection system based on FA@AgNCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.展开更多
Copper nanoclusters(CuNCs)have gained prominence due to their remarkable color-tunable light emission and cost-effective,versatile solution-based synthesis.The use of various functional ligands in the synthesis of CuN...Copper nanoclusters(CuNCs)have gained prominence due to their remarkable color-tunable light emission and cost-effective,versatile solution-based synthesis.The use of various functional ligands in the synthesis of CuNCs enables the modulation of their emission wavelengths and enhances their environmental stability.These nanoclusters have found applications across diverse fields,including catalysis,sensing,bioimaging,and optoelectronics.This review offers a focused and up-to-date perspective by covering literature from the past decade(2015―2025)with an explicit emphasis on practical environmental matrices,including heavy metal ions,organic pollutants,pharmaceuticals,and other environmental contaminants.It systematically compares sensing mechanisms(e.g.,fluorescence quenching,turn-on responses,ratiometric and inner-filter effects)and provides tabulated limits of detection for key heavy metals,organic pollutants,and pharmaceuticals to facilitate direct benchmarking.Finally,the review highlights translational gaps for in-field deployment,such as matrix interferences,long-term stability of ligand-stabilized CuNCs,sample pre-treatment needs,and the absence of standardized validation protocols and proposes targeted research directions to bridge laboratory advances with real-world environmental monitoring.展开更多
Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quen...Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quently,composite fluorescent nanoparticles,chitosan-functionalized silica nanoparticles(CSNPs)-coated Cu NCs(Cu NCs/CSNPs),were synthesized via a reverse microemulsion method.Compared with Cu NCs,the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance.Based on the composite Cu NCs/CSNPs,a fluorescence method for the detection of cefixime fluorescence quenching was estab-lished.The technique was simple,sensitive,and selective for detecting cefixime.The fluorescence quenching effi-ciency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5µmol·L^(-1)(1.81-17.46 mg·L^(-1)),with a limit of detection of 0.0455µmol·L^(-1)(20.6µg·L^(-1)).展开更多
Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but rema...Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but remains a great challenge.Here,we report the efficient white emission from Au_(10) NCs by elaborately deploying the surface chemistry engi⁃neering strategy.Specifically,the bis-aldehyde ligands of 4-hydroxyisophthalaldehyde(HOA)are decorated on the surface of Au_(10)(SG)_(10) NCs(glutathione denoted as SG)through the cross-linking reaction of imine bonds(-CH==N-).The combination of 477 nm blue emission from HOA ligands and 620 nm orange-yellow emission from Au_(10)(SG)_(10) NCs generates white-light emission in HOA-Au_(10)(SG)_(10) NCs in the solvent mixture of ethanol and water.More importantly,dynamic color tuning from blue light to yellow light is achieved by controlling the volume fraction of ethanol in the solvent mixture.In addi⁃tion,the as-formed imine bonds significantly improve the structural rigidity of HOA-Au_(10)(SG)_(10) NCs,resulting in the 51.2%absolute photoluminescence quantum yield(PLQY)of white emission.The present study exemplifies the paradigm to control the emission color and improve the PLQY of metal NCs through rational surface chemistry engineering.展开更多
Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing suc...Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing such control remains challenging,even in well-optimized Ln^(3+) -doped nanocrystals.Here,by exploiting the atomically precise structure of metal nanoclusters,we demonstrate symmetry engineering in the Eu_(2)Ti_(4) nanoclusters through stepwise ligand substitution(BA/Phen→FBA/Phen→FBA/Bpy.BA:benzoicacid;Phen:1,10-phenanthroline;FBA:p-fluorobenzoicacid;Bpy:2,2'-bipyridine).The incorporation of FBA effectively suppresses nonradiative relaxation,while the flexible Bpy ligand induces symmetry reduction from D_(2d) to C_(2v) through coordination modulation,yielding a high photoluminescence quantum yield(PLQY)of 91.2%in the Ln^(3+) cluster systems.The transient-absorption,Judd-Ofelt theory,crystal-field analysis,and temperature-dependent photophysical studies elucidated the underlying modulation mechanisms.Furthermore,these clusters exhibit promising potential for optoelectronic applications,offering a new design strategy for high-performance luminescent materials.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U213010103,22274131).
文摘Metal nanoclusters(MNCs),comprising several to hundreds of metal atoms,have attracted significant research interest owing to their distinctive physicochemical properties.Reticular frameworks(RFs)with ordered porous structures,including metalorganic frameworks(MOFs),covalent organic frameworks(COFs),hydrogen-bonded organic frameworks(HOFs),and supramolecular organic frameworks(SOFs),possess a variety of unique properties due to their high crystallinity,high porosity,large surface area,and adjustable structure.The integration of MNCs with RFs endows the resulting composites with desirable features(e.g.,enhanced and tunable optical properties,improved catalytic and photophysical activities,selective molecular recognition),which facilitates a broad spectrum of biomedical applications and advancing the development of integrated theranostic nanoplatforms.This review summarizes recent advances in the synthesis and biomedical applications of various MNCs/RFs composites.We systematically categorize and evaluate key strategies for incorporating MNCs into four types of RFs(MOFs,COFs,HOFs,and SOFs)while discussing the advantages and limitations of each approach.The biomedical applications of these composites are comprehensively reviewed,encompassing biosensing,bioimaging,antitumor therapy,and antibacterial treatments.Finally,the review addresses current challenges and outlines future research directions,with the aim of guiding the rational design of novel MNCs/RFs composites,enabling precise control over their structures and functions toward advanced biomedical applications.
基金RGM is grateful to CNPq for the PDE fellowship(200437/2025-9),MTM acknowledges CNPq research scholarship(314470/2023-9)FAPESP fundings(2022/01825-22025/063196).
文摘Peptide-and drug-protected gold nanoclusters(Au NCs)with atomic precision have attracted research attention in the last few years owing to their ultrasmall size(<2 nm),well-defined structures,tunable photoluminescence from the visible to near-infrared range,water solubility,and good biocompatibility.These features,combined with low toxicity and efficient renal clearance,make such Au NCs promising candidates for biomedical use,including diagnosis,therapy,and theranostic.The incorporation of peptides or drugs into Au NCs enhances the stability,targeting specificity,cellular uptake,and prolonged circulation,enabling precise modulation of biological responses.Despite notable advances in achieving atomic precision employing complex ligands such as peptides or drugs,the synthetic methods of this new class of NCs remain a challenge.Careful control of molar ratio(Au:peptide/drug),reducing agent,temperature,and reaction time is required,because these factors directly influence the cluster size,optical properties,and in vivo performance.In this review,we highlight different synthetic approaches of atomically precise peptide-and drug-protected Au NCs,emphasizing the role of rational ligand design and reaction conditions,as well as the challenges associated with structural determination.We further discuss the optical and photoluminescence properties of peptide-protected Au NCs-the mostly explored features for biomedical applications.Finally,we conclude by outlining the current challenges,opportunities for scale-up synthesis,and future design perspectives for these emerging nanomaterials.
基金support from the Jiangsu Natural Science Foundation of China(BK20230329)the National Natural Science Foundation of China(22401147,22361132540,and 22178161)the Russian Science Foundation(23-73-30007).
文摘The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.
基金the Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)the Science and Technology Project of China Northern Rare Earth(BFXT-2023-D-0048 and BFXT-2022-D-0078)。
文摘Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.
基金Funded by the National Natural Science Foundation of China(No.21805217)the Fundamental Research Funds for the Central Universities(WUT:2019IVB014 and 2021IVA014)。
文摘We synthesized Ru_(1)Cu_(25)P_(7.5)/TiO_(2)catalyst using sodium borohydride(NaBH_(4))as reductant in a facile strategy.The highly dispersed RuCuP nanoclusters are anchored on the TiO_(2)surface with an average particle size of 2.62 nm.The catalyst shows excellent catalytic activity when applied to the hydrolysis of AB,which owns a high turnover frequency value of 531.56 mol_(H2)mol_(Ru)^(-1)min^(-1)and a low activation energy of 46.38 kJ·mol^(-1),it also exhibits good durability which maintains 61.13%initial activity after five cycles.The high catalytic performance of Ru_(1)Cu_(25)P_(7.5)/TiO_(2)may be attributed to the synergistic effects between Ru,Cu,and P elements,fine particle size,good dispersion,and the tight adhesion between nanoclusters and carrier.
基金supported by the Scientific Key Project of Hunan Provincial Department of Education(23A0204)Open Project Program of Ministry of Agriculture and Rural Affairs Key Laboratory of Testing and Evaluation for Agro-product Safety and Quality(NK202401)Dongting Laboratory Special Fund Project(2024-DTPY-008).
文摘Aflatoxin B_(1)(AFB_(1))in food is a threaten to food safety and human health.In this study,a colorimetric and fluorescent dual-mode aptamer sensor was constructed for rapid and accurate detection of AFB_(1)based on polyvinylpyrrolidone-gold-copper bimetallic nanoclusters(PVP-Au/Cu NCs)and Mn_(3)O_(4)nanoparticles(Mn_(3)O_(4)NPs).In the presence of AFB_(1),the AFB_(1)aptamer on the surface of Mn_(3)O_(4)NPs specifically bound to AFB_(1).The oxidase-like activity of Mn_(3)O_(4)NPs was restored and 3,3',5,5'-0tetramethylbenzidine(TMB)was oxidized to oxidized TMB(ox TMB),which quenched the orange fluorescence of the PVP-Au/Cu NCs.With AFB_(1)concentrations increasing,the blue color of ox TMB deepened,the fluorescence quenching efficiency was enhanced.The working range was 0–56μg/Lwith a limit of detection(LOD)of 0.36μg/L(colorimetric),and2.86–40.00μg/L with a LOD of 0.29μg/L(fluorescent).In addition,the established sensor was successfully applied to determine AFB_(1)in milk,rice,oats,and corn,with a recovery rate of 91.1%–107.5%.This study provides an insight for fabricating a sensitive,efficient,and accurate analytical platform for rapid detection of AFB_(1)in food.
基金supported by the National Natural Science Foundation of China (Nos.22177133,22278438)。
文摘Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes.Herein,we report the construction of ultrasmall gold nanoclusterbased nanoassemblies(Dp-Au NCs@Fe^(2+)) through the coordination of Fe^(2+) ions by a dopa-containing peptidomimetic ligand(Dp CDp).This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe^(2+)centers,bridged by Dp CDp to facilitate directional electron transfer.Comprehensive spectroscopic and kinetic analyses reveal that Dp CDp promotes efficient charge migration from the Au core to surface-bound Fe^(2+),significantly enhancing H_(2)O_(2)-mediated peroxidase-like activity.Compared to bare Dp-Au NCs,Dp-Au NCs@Fe^(2+) display a 4.3-fold improvement in detection sensitivity,a 6.7-fold increase in catalytic efficiency,and markedly stronger hydroxyl radical generation.Mechanistically,this activity stems from a synergistic triad:direct H_(2)O_(2) oxidation at gold surfaces,radical generation at Fe^(2+) sites,and Dp CDp-facilitated electron shuttling.This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering,offering valuable insights for the future design of bioinspired catalytic systems.
基金financially supported by the Natural Science Foundation of Guangxi,China(Nos.2019GXNSFGA245003 and 2021GXNSFBA220058)the National Natural Science Foundation of China(Nos.22272036 and 22362008)+2 种基金Guangxi Technology Base and Talent Subject,China(GUIKE AD23026272)Guangxi Normal University Research Grant,China(No.2022TD)Innovation Project of Guangxi Graduate Education(No.XYCSR2023018)。
文摘Metal nanoclusters(MNCs)possess distinct chemical properties due to their diverse electronic structures.As a class of promising model catalysts,it is of importance to explore the relationship between their structures and properties.However,it is still challenging to get highly active and stable MNCs as surface ligands can hinder their activities,while a complete lack of surface ligand protection can lead to instability.To address this concern,here a series of Pd_(6)nanoclusters(NCs)with varying ligand amounts were synthesized by using Pd_(6)(SC_(6)(C_(2))H_(17))_(12)as precursor and single-walled carbon nanotube(s-CNT)as carrier through treating the composite at different temperatures and times.
基金support of the National Natural Science Foundation of China(NSFC,Nos.22371003,22101001,and 22471001)the Ministry of Education,Natural Science Foundation of Anhui Province(No.2408085Y006)+1 种基金the University Synergy Innovation Program of Anhui Province(No.GXXT-2020-053)the Scientific Research Program of Universities in Anhui Province(No.2022AH030009).
文摘Understanding the photoluminescence(PL)mechanism of metal nanoclusters from both molecular and supramolecular perspectives is crucial for developing highly emissive cluster-based nanomaterials.In this study,we synthesized two structurally similar Ag14 nanoclusters with different phosphine stabilizers,which demonstrated opposite PL behaviors in solution and crystalline states.The Ag14 nanocluster stabilized by P(Ph-OMe)_(3) ligands exhibited a higher PL intensity compared to the one stabilized by P(Ph-F)_(3) ligands,which was attributed to the stronger electron-donating ability of the P(Ph-OMe)_(3) ligand that improved ligand-to-metal charge transfer efficiency.In contrast,the P(Ph-F)_(3) stabilized Ag14 crystals displayed greater PL intensity than the Ag14 cluster crystal with a-OMe surface,which was due to stronger intermolecular interactions within the cluster lattice of the former that limited non-radiative energy loss and thus enhanced PL.Overall,this work aims to promote a comprehensive understanding of the fluorescence in cluster-based nanomaterials,which will be beneficial for their downstream applications.
基金support of the JSPS KAKENHI(Grant Numbers 23H00289 and 22K19012)Scientific Research on Innovative Areas“Aquatic Functional Materials”(Grant Number 22H04562)+2 种基金the Yazaki Memorial Foundation for Science and Technology,and the Ogasawara Foundation for the Promotion of Science and Engineeringsupport from the JSPS grant(Transformative Research Areas[A],22H05133,22H05131)for M.E.,the JSPS grant(21J00210)for T.S.the JSPS grant(24K17663)for P.Z.The computations were partly performed at the Research Center for Computational Science,Okazaki,Japan(24-IMS-C194 and 25-IMS-C224).
文摘Atomically precise silver nanoclusters(AgNCs)offer unique opportunities to correlate structure and photophysical properties,yet enhancing their photoluminescence emission remains challenging due to dominance of non-radiative decay pathways.Here,we report a ligand-engineering strategy to modulate the optical properties of high-nuclearity Ag_(56) NCs.The synthesized two NCs,Ag_(56)S_(12)(^(t)BuS)_(20)(CF_(3)CO_(2))_(12)(MeCN)_(3)(NC-I) and Ag_(56)S_(12)(^(t)BuS)_(20)(^(n)BuSO_(3))_(12)(NC-II),possess a similar hexagonal-close-packed Ag_(14) kernel,which is encapsulated by a similar icosahedral S_(12) middle-shell and an outer Ag_(42) shell,but differ in overall symmetry and outer Ag-ligand shell connectivity.Replacement of bidentate CF_(3) CO_(2)^(−)with tridentaten BuSO_(3)^(−) ligands increases overall Ag-X(X=O,S,and Ag)bonding interactions,resulting in not only a more rigid and compact outer Ag_(42) shell structure but also contraction of cationic Ag_(14) core and anionic icosahedral S_(12) middle-shell.These structural modifications enhance radiative decay and suppress non-radiative pathways,leading to a 17-fold increase in photoluminescence quantum yield and extended average emission lifetime.Computational analysis confirms that ligand-induced geometric stabilization and electronic delocalization govern the excited-state dynamics.This work demonstrates that rational ligand design can synergistically tune cluster geometry,rigidity,and electronic structure,providing a general strategy to improve the photophysical performance of high-nuclearity AgNCs.
基金supported by the National Natural Science Foundation of China(Grant 52276212)the National Key Research and Development Program of China(Grant 2022YFB3803600)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant BK20231211)the China Fundamental Research Funds for the Central Universities.
文摘Solar-driven H_(2) production coupled with selective organic transformation represents a promising strategy for co-generation of green hydrogen and high-value chemicals,yet its feasibility relies critically on effective bifunctional photocatalysts.Herein,we report the synthesis of ultrafine Cd_(x)Zn_(1-x)S nanocrystals derived from a zeolitic imidazolate framework(ZIF),featuring high surface area,shortened charge diffusion path,and enhanced H_(2) evolution activity.Anchoring amorphous Pt sub-nanoclusters onto these nanocrystals created a bifunctional catalyst(Pt-Cd_(x)Zn_(1-x)S)for efficient lactic acid photoreforming,enabling coproduction of H_(2) with switchable selectivity toward pyruvic acid(PA)or 2,3-dihydroxy-2,3-dimethylsuccinic acid(DTA).The optimized 0.5Pt-Cd_(0.3)Zn_(0.7)S catalyst achieved an exceptional H_(2) production rate of 270.6 mmol h^(-1) g^(-1),73.1%PA selectivity,and 62.8% apparent quantum efficiency at 400 nm.Mechanistic studies revealed that lactic acid undergoes C-H cleavage to form carbon-centered radicals.Pt sub-nanoclusters served as electron sinks to facilitate O-H dissociation and PA formation,whereas pristine Cd_(0.3)Zn_(0.6)7S promoted direct C-C coupling of radicals to predominantly yield DTA.This work offers critical insights for designing advanced bifunctional photocatalysts to integrate solar hydrogen and value-added chemical synthesis.
基金supported financially by the following:Natural Science Foundation of China,Grant Numbers:21829501,21925303,22471275,21771186,22075291,21222301,21171170,21528303,U24A20480,92475105,22503108CASHIPS Director’s Fund(BJPY2019A02)+6 种基金the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2020HSC-CIP005)the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(2022HSC-CIP018)Presidential Foundation of HFIPS of Chinese Academy of Sciences(no.YZJJ2023QN28)the HFIPS Director’s Fund(no.YZJJ-GGZX-2022-01)the CAS/SAFEA International Partner-ship Program for Creative Research Teamsthe Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(Grant Number:GZC20241744)Hefei Institute of Physical Science,Chinese Academy of Sciences(BR-E44BGGBR12B).
文摘The electrochemical reduction of CO_(2),as a renewable energy-driven electrochemical system,has emerged as an environmentally benign approach for producing valuable chemicals and fuels under mild reaction conditions.Recent advances in the precise synthesis of metal nanoclusters,coupled with state-of-the-art characterization techniques,have enabled atomic-level investigation of structure-activity relationships in nanocatalysts.Due to their well-defined atomic architectures,the active metal sites within these nanocatalysts can be accurately identified,facilitating systematic studies on how compositions(structures)modulate catalytic performance.This review begins by summarizing recent advances in the controlled synthesis of atomically precise metal nanoclusters,followed by an overview of progress in the electrochemical reduction of CO_(2) to CO using nanoclusters as catalysts.Subsequently,we systematically investigate the effects of metal kernel characteristics and staple properties on catalytic activity,selectivity,and stability.Furthermore,current challenges are outlined,and prospective research directions are proposed in this rapidly evolving field.It is anticipated that this review will inspire further innovation in the synthesis of atomically precise nanocluster catalysts,promote a deeper mechanistic understanding of metal nanocluster-mediated electrochemical CO_(2) reduction,and push forward the related industrial applications.
文摘Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.
基金financial support from the National Natural Science Foundation of China(Nos.22171094,21925104,92261204,and 22431005)Hubei Provincial Science and Technology Innovation Team Project[2022]The National Key R&D Program of China(No.2022YFB3807700)。
文摘Atomically precise coordination nanoclusters(NCs)constitute a pivotal and rapidly advancing domain in the realms of materials science and chemistry owing to their distinctive crystal structures and exceptional attributes encompassing molecular magnetism[1],photoluminescence[2],and catalysis[3].Organic ligands play a crucial role in effectively shielding these NCs,serving two primary functions:firstly,vital in preventing NC aggregation,particularly for the formation of robust single-crystal structures;secondly,acting as either bridging or peripheral structural components of NCs[4].This characterization of organic-inorganic hybridization offers unique advantages for unraveling the intricate relationships between structure and properties[5].
基金supported by the National Key R&D Program of China(Nos.2022YFB3504804 and 2023YFF0718303)the National Natural Science Foundation of China(Nos.51871219,52071324,52031014,and 52401255)+1 种基金Science and Technology Project of Shenyang City(No.22-101-0-27)Liaoning Institute of Science and Technology Doctoral Initiation Fund Project(No.2307B19).
文摘To realize the application of electromagnetic wave absorption(EWA)devices in humid marine environments,bifunctional EWA materials with better EWA capacities and anticorrosion properties have great exploration significance and systematic research re-quirements.By utilizing the low-cost and excellent magnetic and stable chemical characteristics of barium ferrite(BaFe_(12)O_(19))and using the high dielectric loss and excellent chemical inertia of nanocarbon clusters,a new type of nanocomposites with carbon nanoclusters en-capsulating BaFe_(12)O_(19)was designed and synthesized by combining an impregnation method and a high-temperature calcination strategy.Furthermore,Ce-Mn ions were introduced into the BaFe_(12)O_(19)lattice to improve the dielectric and magnetic properties of BaFe_(12)O_(19)cores significantly,and the energy band structure of the doped lattice and the orders of Ce replacing Fe sites were calculated.Benefiting from Ce-Mn ion doping and carbon nanocluster encapsulation,the composite material exhibited excellent dual functionality of corrosion resist-ance and EWA.When BaCe_(0.2)Mn_(0.3)Fe_(11.5)O_(19)-C(BCM-C)was calcined at 600°C,the minimum reflection loss of-20.1 dB was achieved at 14.43 GHz.The Ku band’s effective absorption bandwidth of 4.25 GHz was achieved at an absorber thickness of only 1.3 mm.The BCM-C/polydimethylsiloxane coating had excellent corrosion resistance in the simulated marine environment(3.5wt%NaCl solution).The|Z|0.01Hz value of BCM-C remained at 106Ω·cm^(2)after 12 soaking days.The successful preparation of the BaFe_(12)O_(19)composite en-capsulated with carbon nanoclusters provides new insights into the preparation of multifunctional absorbent materials and the fabrication of absorbent devices applied in humid marine environments in the future.
文摘Herein,a one-pot chemical reduction method was reported to prepare folic acid(FA)-stabilized silver nanoclusters(FA@Ag NCs),in which FA,hydrazine hydrate,and silver nitrate were used as capping agent,reducing agent,and precursor,respectively.Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs,including transmission electron microscopy(TEM),X-ray photoelectron spectrometer(XPS),Fourier transform infrared spectrometer(FTIR),X-ray diffractometer(XRD),fluorescence spectrometer,and ultraviolet visible absorption spectrometer.FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm.Moreover,the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm,respectively.Under the optimal detection conditions,FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200μmol·L^(-1).The detection limit was 0.084μmol·L^(-1).The fluorescence-quenching mechanism was ascribed to the static quenching.The detection system based on FA@AgNCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.
文摘Copper nanoclusters(CuNCs)have gained prominence due to their remarkable color-tunable light emission and cost-effective,versatile solution-based synthesis.The use of various functional ligands in the synthesis of CuNCs enables the modulation of their emission wavelengths and enhances their environmental stability.These nanoclusters have found applications across diverse fields,including catalysis,sensing,bioimaging,and optoelectronics.This review offers a focused and up-to-date perspective by covering literature from the past decade(2015―2025)with an explicit emphasis on practical environmental matrices,including heavy metal ions,organic pollutants,pharmaceuticals,and other environmental contaminants.It systematically compares sensing mechanisms(e.g.,fluorescence quenching,turn-on responses,ratiometric and inner-filter effects)and provides tabulated limits of detection for key heavy metals,organic pollutants,and pharmaceuticals to facilitate direct benchmarking.Finally,the review highlights translational gaps for in-field deployment,such as matrix interferences,long-term stability of ligand-stabilized CuNCs,sample pre-treatment needs,and the absence of standardized validation protocols and proposes targeted research directions to bridge laboratory advances with real-world environmental monitoring.
文摘Herein,copper nanoclusters(Cu NCs)were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand,with Cu(NO_(3))_(2)as copper source.Subse-quently,composite fluorescent nanoparticles,chitosan-functionalized silica nanoparticles(CSNPs)-coated Cu NCs(Cu NCs/CSNPs),were synthesized via a reverse microemulsion method.Compared with Cu NCs,the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance.Based on the composite Cu NCs/CSNPs,a fluorescence method for the detection of cefixime fluorescence quenching was estab-lished.The technique was simple,sensitive,and selective for detecting cefixime.The fluorescence quenching effi-ciency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5µmol·L^(-1)(1.81-17.46 mg·L^(-1)),with a limit of detection of 0.0455µmol·L^(-1)(20.6µg·L^(-1)).
文摘Photoluminescence(PL)is one of the most important properties of metal nanoclusters(NCs).Achieving effi⁃cient white light emission in metal NCs with a precise structures is important for practical applications but remains a great challenge.Here,we report the efficient white emission from Au_(10) NCs by elaborately deploying the surface chemistry engi⁃neering strategy.Specifically,the bis-aldehyde ligands of 4-hydroxyisophthalaldehyde(HOA)are decorated on the surface of Au_(10)(SG)_(10) NCs(glutathione denoted as SG)through the cross-linking reaction of imine bonds(-CH==N-).The combination of 477 nm blue emission from HOA ligands and 620 nm orange-yellow emission from Au_(10)(SG)_(10) NCs generates white-light emission in HOA-Au_(10)(SG)_(10) NCs in the solvent mixture of ethanol and water.More importantly,dynamic color tuning from blue light to yellow light is achieved by controlling the volume fraction of ethanol in the solvent mixture.In addi⁃tion,the as-formed imine bonds significantly improve the structural rigidity of HOA-Au_(10)(SG)_(10) NCs,resulting in the 51.2%absolute photoluminescence quantum yield(PLQY)of white emission.The present study exemplifies the paradigm to control the emission color and improve the PLQY of metal NCs through rational surface chemistry engineering.
基金Project supported by the National Key Research and Development Program of China(2024YFE0206100)the National Natural Science Foundation of China(T2325015,U21A2068,12174151)。
文摘Achieving high-efficiency photoluminescence in trivalent lanthanides(Ln^(3+))requires precise crystalfield perturbation to overcome parity-forbidden 4f-transitions and suppress nonradiative decay.However,realizing such control remains challenging,even in well-optimized Ln^(3+) -doped nanocrystals.Here,by exploiting the atomically precise structure of metal nanoclusters,we demonstrate symmetry engineering in the Eu_(2)Ti_(4) nanoclusters through stepwise ligand substitution(BA/Phen→FBA/Phen→FBA/Bpy.BA:benzoicacid;Phen:1,10-phenanthroline;FBA:p-fluorobenzoicacid;Bpy:2,2'-bipyridine).The incorporation of FBA effectively suppresses nonradiative relaxation,while the flexible Bpy ligand induces symmetry reduction from D_(2d) to C_(2v) through coordination modulation,yielding a high photoluminescence quantum yield(PLQY)of 91.2%in the Ln^(3+) cluster systems.The transient-absorption,Judd-Ofelt theory,crystal-field analysis,and temperature-dependent photophysical studies elucidated the underlying modulation mechanisms.Furthermore,these clusters exhibit promising potential for optoelectronic applications,offering a new design strategy for high-performance luminescent materials.
