When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for N...When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for Na-salt sulfonated polystyrene ionomer,the electron-diffraction lattice fringes of the nanoclusters,which proved their internal crystalline ordering driven by electrostatic attractions overcoming steric hindrance.Kinetically,the nanoclusters'enhanced melting endotherm upon aging indicate their quasi-,slow-ordering character.Extended tight binding molecular dynamics simulations provide an insight into the mechanism underlying the ionic-group aggregation during nanoclustering.We hence proposed an uncommon state of order,polymer-bound ceramic quasicrystal,supplementary to the order phenomena in crystalline ceramics.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
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
As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attra...As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.展开更多
Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching a...Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole(ONZ)on BSA-Gly CuNCs,a simple and sensitive detection method for ONZ was successfully developed.The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs,and thus enhance its fluorescence intensity and stability.The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60μmol·L^(-1)and a detection limit of 0.069μmol·L^(-1).Compared with the single-ligand-modified CuNCs,dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity,stability,and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.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
The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;d...The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.展开更多
AuCu bimetallic nanoclusters exhibit enhanced emission relative to structurally analogous Au nanoclusters,though their excited-state dynamics remains incompletely characterized.Here,we chose AuCu_(14)as a system to pr...AuCu bimetallic nanoclusters exhibit enhanced emission relative to structurally analogous Au nanoclusters,though their excited-state dynamics remains incompletely characterized.Here,we chose AuCu_(14)as a system to probe the excited-state behaviors and triplet energy transfer dynamics of bimetallic nanoclusters.The O_(2)sensitivity of both photoluminescence quantum yield and excited-state lifetime confirms triplet-origin emission,while the minimal spectral changes at low temperature suggest weak electron-vibration coupling.Notably,although O_(2)induces significant photoluminescence quenching,the addition of triplet-state acceptors(perylene and anthracene)shows no quenching effect due to steric hindrance from surface ligands.These results advance the mechanistic understanding of triplet-state dynamics in AuCu bimetallic nanoclusters.展开更多
Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations i...Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.展开更多
Developing efficient and stable catalysts for the hydrogen evolution reaction(HER)is essential for advancing anion-exchange membrane water electrolyzer(AEMWE)technology.In this study,we present a facile microwave redu...Developing efficient and stable catalysts for the hydrogen evolution reaction(HER)is essential for advancing anion-exchange membrane water electrolyzer(AEMWE)technology.In this study,we present a facile microwave reduction and low-temperature phosphorization strategy to synthesize a highly efficient HER catalyst,comprising P,N-codoped carbon-supported RuP_(2)nanocluster(RuP_(2)@PNC).RuP_(2)@PNC demonstrates outstanding HER performance,achieving overpotentials of 18 and 44 mV at a current density of 10 mA cm^(-2)in alkaline and acidic media,respectively.Furthermore,an AEMWE device utilizing RuP_(2)@PNC as the cathode catalyst delivers a current density of 0.5 A cm^(-2)at a cell voltage of 1.84 V and exhibits remarkable stability over 150 h of operation.Experimental analyses and density functional theory(DFT)calculations reveal that the synergistic effects of P,N-codoped and the unique structure of RuP_(2)enhance electron transfer between Ru and the support,optimize the electronic structure,and regulate the d–band center of Ru.These features improve water adsorption,weaken the Ru–H binding strength,and facilitate efficient H_(2)desorption,collectively driving the superior HER activity of RuP_(2)@PNC.This work offers an effective design strategy for high-performance HER catalysts and provides valuable insights for accelerating the development of AEMWE technology.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
A 12-metal Zn(Ⅱ)-Nd(Ⅲ) cluster 1(sizes:1.8 nm×2.0 nm×2.0 nm) was synthesized from a long-chain type Schiff base ligand.It displays ratiometric fluorescence response to neopterin(Neo) with high selectivity ...A 12-metal Zn(Ⅱ)-Nd(Ⅲ) cluster 1(sizes:1.8 nm×2.0 nm×2.0 nm) was synthesized from a long-chain type Schiff base ligand.It displays ratiometric fluorescence response to neopterin(Neo) with high selectivity and sensitivity,which can be expressed by the equation I_(545)_(nm)/I_(1060)_(nm)=A·[Neo]^(2)+B·[Neo]+C.1 is used to quantitatively test Neo concentrations in fetal calf serum(FCS) and urine,and the recovery ranges are 98.57%-103.82% and 99.25%-103.50%,respectively,while the relative standard deviations(RSDs) are 7.89%-9.46% and 1.85%-4.16%,respectively.The limits of detection of 1 to Neo in FCS and urine are 0.034 and 0.021 μmol/L,respectively.展开更多
基金Funded by the Hubei Province Key Research Foundation for Water Resources,China(No.HBSLKY2023035)as well as by the Technology Foundation for Selected Overseas Scholars,Ministry of Human Resources and Social Security,China(No.[2013]277)+2 种基金the Natural Science Foundation of the Hubei Province of China(No.2014CFA094)the Overseas High-level Talents Scientific-research Starting Fund of Hubei University of Technology,China(HBUTscience-[2005]2)the National Natural Science Foundation of China(No.51703053)。
文摘When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate,is the ordered structure maintained within the sterically hindered nanocluster?We observed,for Na-salt sulfonated polystyrene ionomer,the electron-diffraction lattice fringes of the nanoclusters,which proved their internal crystalline ordering driven by electrostatic attractions overcoming steric hindrance.Kinetically,the nanoclusters'enhanced melting endotherm upon aging indicate their quasi-,slow-ordering character.Extended tight binding molecular dynamics simulations provide an insight into the mechanism underlying the ionic-group aggregation during nanoclustering.We hence proposed an uncommon state of order,polymer-bound ceramic quasicrystal,supplementary to the order phenomena in crystalline ceramics.
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.
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.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(NSFC,Nos.22102018 and 52171201)+4 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale(No.KF2021005)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)。
文摘As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.
文摘Bovine serum albumin(BSA)and glycine(Gly)dual-ligand-modified copper nanoclusters(BSA-Gly CuNCs)with high fluorescence intensity were synthesized by a one-pot strategy.Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole(ONZ)on BSA-Gly CuNCs,a simple and sensitive detection method for ONZ was successfully developed.The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs,and thus enhance its fluorescence intensity and stability.The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60μmol·L^(-1)and a detection limit of 0.069μmol·L^(-1).Compared with the single-ligand-modified CuNCs,dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity,stability,and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.
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.
文摘The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.
基金supported by the National Natural Science Foundation of China(No.22273095).
文摘AuCu bimetallic nanoclusters exhibit enhanced emission relative to structurally analogous Au nanoclusters,though their excited-state dynamics remains incompletely characterized.Here,we chose AuCu_(14)as a system to probe the excited-state behaviors and triplet energy transfer dynamics of bimetallic nanoclusters.The O_(2)sensitivity of both photoluminescence quantum yield and excited-state lifetime confirms triplet-origin emission,while the minimal spectral changes at low temperature suggest weak electron-vibration coupling.Notably,although O_(2)induces significant photoluminescence quenching,the addition of triplet-state acceptors(perylene and anthracene)shows no quenching effect due to steric hindrance from surface ligands.These results advance the mechanistic understanding of triplet-state dynamics in AuCu bimetallic nanoclusters.
基金financially supported by the National Natural Science Foundation of China(Nos.22301155,22171156,21803001)Taishan Scholar Foundation of Shandong Province(China)+2 种基金the Natural Science Foundation of Shandong Province(No.ZR2023QB122)Shandong Province Excellent Youth Innovation TeamStartup Funds from Qingdao University of Science and Technology
文摘Understanding the synergistic effect between ligands at the atomic level to control the catalytic selectivity of catalysts remains a significant challenge due to the complexity of ligand interactions and limitations in current analytical techniques.Herein,using precisely structured metal nanoclusters as models,we discovered that altering the electronegativity of substituents on donor thiolate ligands can modulate the bond dissociation energy of coordinated phosphine ligands on the clusters.This change leads to the selective dissociation of ligands during the catalytic process,thereby enabling control over catalytic selectivity with an abrupt increase in formate production from~0%to 23%.This work provides crucial insights into understanding ligand interactions on metal nanoparticle surfaces at the atomic level and lays the foundation for designing highly selective catalysts in the future.
基金supported by the National Natural Science Foundation of China(Nos.52371222 and 52271211)the Natural Science Foundation of Hunan Province in China(Nos.2025JJ60350,2024JJ4022,and 2023JJ30277)+1 种基金the Key Research and Development Program of Hunan Province(No.2023GK2035)HORIZON–Marie Sk?odowska–Curie Actions–2021–PF(No.101065098),European Union
文摘Developing efficient and stable catalysts for the hydrogen evolution reaction(HER)is essential for advancing anion-exchange membrane water electrolyzer(AEMWE)technology.In this study,we present a facile microwave reduction and low-temperature phosphorization strategy to synthesize a highly efficient HER catalyst,comprising P,N-codoped carbon-supported RuP_(2)nanocluster(RuP_(2)@PNC).RuP_(2)@PNC demonstrates outstanding HER performance,achieving overpotentials of 18 and 44 mV at a current density of 10 mA cm^(-2)in alkaline and acidic media,respectively.Furthermore,an AEMWE device utilizing RuP_(2)@PNC as the cathode catalyst delivers a current density of 0.5 A cm^(-2)at a cell voltage of 1.84 V and exhibits remarkable stability over 150 h of operation.Experimental analyses and density functional theory(DFT)calculations reveal that the synergistic effects of P,N-codoped and the unique structure of RuP_(2)enhance electron transfer between Ru and the support,optimize the electronic structure,and regulate the d–band center of Ru.These features improve water adsorption,weaken the Ru–H binding strength,and facilitate efficient H_(2)desorption,collectively driving the superior HER activity of RuP_(2)@PNC.This work offers an effective design strategy for high-performance HER catalysts and provides valuable insights for accelerating the development of AEMWE technology.
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.
基金Project supported by the National Natural Science Foundation of China (21771141)。
文摘A 12-metal Zn(Ⅱ)-Nd(Ⅲ) cluster 1(sizes:1.8 nm×2.0 nm×2.0 nm) was synthesized from a long-chain type Schiff base ligand.It displays ratiometric fluorescence response to neopterin(Neo) with high selectivity and sensitivity,which can be expressed by the equation I_(545)_(nm)/I_(1060)_(nm)=A·[Neo]^(2)+B·[Neo]+C.1 is used to quantitatively test Neo concentrations in fetal calf serum(FCS) and urine,and the recovery ranges are 98.57%-103.82% and 99.25%-103.50%,respectively,while the relative standard deviations(RSDs) are 7.89%-9.46% and 1.85%-4.16%,respectively.The limits of detection of 1 to Neo in FCS and urine are 0.034 and 0.021 μmol/L,respectively.
