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
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
Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is sti...Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.展开更多
The selective semi-hydrogenation of phenylacetylene(PA)to styrene(ST)represents a critical industrial reaction,essential for producing polymer-grade styrene.Yet,achieving high selectivity at high conversions remains f...The selective semi-hydrogenation of phenylacetylene(PA)to styrene(ST)represents a critical industrial reaction,essential for producing polymer-grade styrene.Yet,achieving high selectivity at high conversions remains fundamentally challenging due to competing overhydrogenation.Here we report an atomic-scale approach for encapsulating ultrafine PtCu(Platinum,Copper)bimetallic nanoclusters(NCs)within the microporous TS-1 zeolite matrix through a ligand-as sis ted hydrothermal strategy.Remarkably,the as-synthesized PtCu@TS-1 catalyst exhibited an unprecedented turnover frequency(TOF)of 2006.7 h^(-1)and a superior styrene yield of 87.7%,significantly surpassing conventional Pt-based catalysts.Advanced characterization and in situ spectroscopy revealed that electron-rich Pt sites,induced by electron transfer from Cu in confined PtCu ensembles,substantially lower the activation barrier for hydrogen dissociation,accelerating selective hydrogenation.Moreover,the atomic confinement effect within the zeolite structure effectively modulates intermediate adsorption and accelerates product desorption,thus overcoming the selectivity-activity tradeoff.This study introduces a generalizable atomic-level catalyst design principle,highlighting the immense potential of quantum-sized bimetallic clusters within porous materials for precisely tuning reaction selectivity and activity.展开更多
Noble metal nanoclusters have attracted great scientific interests due to their tempting properties and applications.Significant strides have been made in recent years to synthesis atomically precise nanoclusters by u...Noble metal nanoclusters have attracted great scientific interests due to their tempting properties and applications.Significant strides have been made in recent years to synthesis atomically precise nanoclusters by utilizing polyoxometalates as protecting ligands.Remarkably,the group of Professor Suzuki from the University of Tokyo has made a great contribution in this field.Here we spotlight on four related papers in this area and present a brief highlight of these publications.展开更多
It remains highly challenging to achieve the high-order nonlinear optical(NLO)properties of atomically precise metal nanoclusters via template-maintained manipulation.Here,based on the M_(1)Ag_(24)(SR)_(18)(M=Ag/Au/Pt...It remains highly challenging to achieve the high-order nonlinear optical(NLO)properties of atomically precise metal nanoclusters via template-maintained manipulation.Here,based on the M_(1)Ag_(24)(SR)_(18)(M=Ag/Au/Pt/Pd;SR=2,4-dimethylthiophenol)cluster template,we demonstrated that the innermost kernel alloying rendered these nanoclusters highly controllable towards the nonlinear optics.The Pd-alloyed Pd_(1)Ag_(24)(SR)_(18) only dis-played single-photon-excited fluorescence,while the homo-silver Ag_(25)(SR)_(18) nanocluster generated the two-photonexcited fluorescence characterization.The Au-and Pt-doped M_(1)Ag_(24)(SR)_(18) nanoclusters showed high-order three-and four-photon-excited fluorescence,respectively,demonstrating that the order-by-order control over the nonlinear optics of nanoclusters has been accomplished.Moreover,Pd_(1)Ag_(24)(SR)_(18) with high-order NLO characterization exhibited the best optical limiting performance under 1000 nm excitation,in agreement with its most prominent NLO property.Overall,this work presents an intriguing cluster template that enables successive order control over the nonlinear optics of atomically precise metal nanoclusters,hopefully paving the way for developing cluster-based nanomaterials with customized optical characterizations.展开更多
Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,ligh...Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,light-harvesting capability and multitude of active sites.Nonetheless,wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan,uncontrollable charge transport pathway,and light-induced poor stability,impeding the construction of robust and stable metal NC-based photosystems.Herein,we report the fabrication of stable alloy(Au_(1-x)Pt_(x))NCs photosystem,for which tailor-made negatively charged l-glutathione(GSH)-capped Au_(1-x)Pt_(x)NCs as the building blocks are controllably deposited on the Bi VO_(4)(BVO)by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes(Au_(1-x)Pt_(x)/BVO).The self-assembled Au_(1-x)Pt_(x)/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Au_(x)/BVO photoanodes,which is caused by the Pt atom doping into the Au_(x)NCs for elevating photosensitivity and boosting the stability.The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation,improving the photostability and accelerating the surface charge transfer kinetics.Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.展开更多
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.
基金supported by Guangdong Natural Science Funds(No.2023A0505050107)Hong Kong Research Grant Council General Research Fund(Nos.16201820 and 16201622)+1 种基金Green Tech Fund(No.GTF202020131)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(No.HZQB-KCZYB-2020083).
文摘Cu-based nanomaterials have demonstrated great potential as efficient and economic catalysts for oxygen evolution reaction(OER),yet an ideal model catalyst with definitive composition and well-defined structure is still lacking for understanding the structure-performance relationship at atomical level.Herein,we report the synthesis,structure analysis,and OER catalytic properties of a novel atomically precise Cu nanocluster of[Cu_(6)(C≡CR)4(dppe)3](R=Fe(C_(5)H_(5))_(2),abbreviated as Cu_(6)NC).Cu_(6)NC possesses a unique metal core configuration and metal-ligand binding motifs.Interestingly,Cu_(6)NC has superior OER performance to pure phosphine ligand-protected Cu18 nanocluster(Cu18NC in short,same Cu amount)and Cu nanoparticle(CuNP)with larger size,manifested by the lower overpotential at 10 mA·cm^(−2),smaller Tafel slope,and reduced charge transfer resistance.Cu_(6)NC also demonstrated excellent long-term stability for prolonged operation.Density functional theory(DFT)calculations further confirm that the alkynyl ligand plays a critical role in promoting the catalytic performance,and Cu_(6)NC has a lower energy barrier in the rate-determining step of the OER process.This study not only highlights the unique advantages of employing ultrasmall Cu nanoclusters for OER,but also can shed light on designing ligand-functionalized metal nanoclusters for electrochemical energy conversion and beyond.
基金financially supported by the Taishan Scholar Program of Shandong Province(No.tsqn202408211)China Postdoctoral Science Foundation(No.2024M761141)+3 种基金Postdoctoral Fellowship Program of CPSF(No.GZC20250785)Postdoctoral Innovation Program of Shandong Province(No.SDCX-ZG-202503085)Shandong Excellent YoungScientists Fund Program(No.2022HWYQ-082)National Natural Science Foundation of China(Nos.22278174,21808079,and 22378159)
文摘The selective semi-hydrogenation of phenylacetylene(PA)to styrene(ST)represents a critical industrial reaction,essential for producing polymer-grade styrene.Yet,achieving high selectivity at high conversions remains fundamentally challenging due to competing overhydrogenation.Here we report an atomic-scale approach for encapsulating ultrafine PtCu(Platinum,Copper)bimetallic nanoclusters(NCs)within the microporous TS-1 zeolite matrix through a ligand-as sis ted hydrothermal strategy.Remarkably,the as-synthesized PtCu@TS-1 catalyst exhibited an unprecedented turnover frequency(TOF)of 2006.7 h^(-1)and a superior styrene yield of 87.7%,significantly surpassing conventional Pt-based catalysts.Advanced characterization and in situ spectroscopy revealed that electron-rich Pt sites,induced by electron transfer from Cu in confined PtCu ensembles,substantially lower the activation barrier for hydrogen dissociation,accelerating selective hydrogenation.Moreover,the atomic confinement effect within the zeolite structure effectively modulates intermediate adsorption and accelerates product desorption,thus overcoming the selectivity-activity tradeoff.This study introduces a generalizable atomic-level catalyst design principle,highlighting the immense potential of quantum-sized bimetallic clusters within porous materials for precisely tuning reaction selectivity and activity.
基金financially supported by the Foundation of Jilin Educational Committee(JJKH20231298KJ)Natural Scientific Foundation of Jilin Province Science and Technology Department(20230101032JC)
文摘Noble metal nanoclusters have attracted great scientific interests due to their tempting properties and applications.Significant strides have been made in recent years to synthesis atomically precise nanoclusters by utilizing polyoxometalates as protecting ligands.Remarkably,the group of Professor Suzuki from the University of Tokyo has made a great contribution in this field.Here we spotlight on four related papers in this area and present a brief highlight of these publications.
基金the NSFC(U24A20480,22371003,22471001,22475002)the Ministry of Education,Natural Science Foundation of Anhui Province(2408085Y006)the Scientific Research Program of Universities in Anhui Province(2022AH030009).
文摘It remains highly challenging to achieve the high-order nonlinear optical(NLO)properties of atomically precise metal nanoclusters via template-maintained manipulation.Here,based on the M_(1)Ag_(24)(SR)_(18)(M=Ag/Au/Pt/Pd;SR=2,4-dimethylthiophenol)cluster template,we demonstrated that the innermost kernel alloying rendered these nanoclusters highly controllable towards the nonlinear optics.The Pd-alloyed Pd_(1)Ag_(24)(SR)_(18) only dis-played single-photon-excited fluorescence,while the homo-silver Ag_(25)(SR)_(18) nanocluster generated the two-photonexcited fluorescence characterization.The Au-and Pt-doped M_(1)Ag_(24)(SR)_(18) nanoclusters showed high-order three-and four-photon-excited fluorescence,respectively,demonstrating that the order-by-order control over the nonlinear optics of nanoclusters has been accomplished.Moreover,Pd_(1)Ag_(24)(SR)_(18) with high-order NLO characterization exhibited the best optical limiting performance under 1000 nm excitation,in agreement with its most prominent NLO property.Overall,this work presents an intriguing cluster template that enables successive order control over the nonlinear optics of atomically precise metal nanoclusters,hopefully paving the way for developing cluster-based nanomaterials with customized optical characterizations.
基金The support by the award Program for Minjiang scholar professorship is greatly acknowledgedfinancially supported by the National Natural Science Foundation of China(Nos.21703038,22072025)The financial support from State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Science is acknowledged(No.20240018)。
文摘Atomically precise metal nanoclusters(NCs)have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner,quantum confinement effects,light-harvesting capability and multitude of active sites.Nonetheless,wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan,uncontrollable charge transport pathway,and light-induced poor stability,impeding the construction of robust and stable metal NC-based photosystems.Herein,we report the fabrication of stable alloy(Au_(1-x)Pt_(x))NCs photosystem,for which tailor-made negatively charged l-glutathione(GSH)-capped Au_(1-x)Pt_(x)NCs as the building blocks are controllably deposited on the Bi VO_(4)(BVO)by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes(Au_(1-x)Pt_(x)/BVO).The self-assembled Au_(1-x)Pt_(x)/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Au_(x)/BVO photoanodes,which is caused by the Pt atom doping into the Au_(x)NCs for elevating photosensitivity and boosting the stability.The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation,improving the photostability and accelerating the surface charge transfer kinetics.Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
