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
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
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
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
Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies...Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies on the synthesis of water-soluble selenolate-protected AuNCs,and the impact of selenolate ligands on the optical properties of AuNCs is still unclear.In this study,we synthesized selenolatecostabilized water-soluble,near-infrared fluorescent AuNCs with four different amounts of benzeneselenol(PhSeH),and systematically investigated the role of PhSeH on their optical properties.It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect.Moreover,AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands,owing to the introduction of Au-Se bond on their surfaces.Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property.These results provide important knowledges for further development of new,robust selenolate-stabilized metal NCs for biological application.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
Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunct...Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.展开更多
Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalit...Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.展开更多
Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually le...Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually leads to hypertrichosis.This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority,anxiety and irritability.Current therapies are limited and often unsatisfactory,such as pharmacological and physical therapies,which have adverse effects and cause the irreversible destruction of hair follicles.Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment(OSM),which could be a safe and effective drug for ROS-induced skin injury.In our study,we demonstrated that zero valence fluorescent gold nanoclusters(FGNCs)were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors(+3),while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B(NFκB)-mediated inflammatory response signaling pathway(NFκB/tumor necrosis factor-α(TNF-α)axis).This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.展开更多
Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthes...Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthesize a kind of dynamic luminescent NCs through Schiff base crosslinking between triethylenetetramine(TETA)and tannic acid at room temperature.The proposed NCs have an excitation-independent blue emission,and the maximum emission is available at about 458 nm with two excitation centers.Furthermore,the crosslinking degree of the NCs can be effectively adjusted by TETA and their formation is a kineticcontrol process.Most importantly,the proposed NCs show a property of pHcontrolled reversible depolymerization and polymerization,accompanied by a cyclic“on-off-on”photoswitching,which is directly attributed to pH-stimulated reversible C=N bond cleavage and re-formation.Because of the reversible structure change properties,the dynamic NCs have been well used in reversible information encryption.This new finding provides not only us with a powerful strategy to study the structure–properties relationship of luminescent NCs but also a design idea for constructing smart optical nanomaterials.展开更多
Atomically precise copper-based nanoclusters stand out as one of the highly promising catalysts in the realm of electrochemical nitrate reduction reaction(NITRR)aimed at ammonia(NH_(3))synthesis.However,the controllab...Atomically precise copper-based nanoclusters stand out as one of the highly promising catalysts in the realm of electrochemical nitrate reduction reaction(NITRR)aimed at ammonia(NH_(3))synthesis.However,the controllable synthesis of stable Cu-based nanoclusters featuring fully inorganic anionic ligands for electrochemical NITRR remains a challenge.Herein,we present a simple and gentle chelated co-precipitation method for the uniform growth of ultrafine amorphous Cu(OH)Cl(a-Cu(OH)Cl)nanoclusters,featuring a diameter of approximately 9 nm,onto carbon nanotubes(a-Cu(OH)Cl/CNTs),aimed at enhancing electrocatalytic NITRR performance.Intriguingly,trisodium citrate dihydrate(TCD)could effectively change the crystalline form of Cu-based nanoclusters to obtain a-Cu(OH)Cl nanoclusters instead of high-crystallinity Cu_(2)(OH)_(3)Cl(c-Cu_(2)(OH)_(3)Cl)nanoclusters.In comparison to c-Cu_(2)(OH)_(3)Cl nanoclusters,a-Cu(OH)Cl nanoclusters,featuring a smaller particle size and containing more lowcoordination Cu atoms,provide more efficient catalytic sites,thereby enhancing the reaction rate and energy efficiency for NH_(3)production.The proposed chelated co-precipitation method provides a promising crystalline modulation engineering strategy to boost the electrocatalytic performances of metal nanoclusters.展开更多
CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface en...CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface engineering of charge-asymmetry nanocluster catalyst(CuZnSCN),in which zinc and copper atoms together form a metal cluster loaded on sulfur and nitrogen co-etched carbon matrix.The synergistic promotion mechanism of CO_(2)RR by Cu–Zn atom interactions and sulfur–nitrogen atom doping was investigated.A CO partial current density of 74.1 mA cm^(-2)was achieved in an alkaline electrolyte,as well as a considerable CO Faraday efficiency of 97.7%.In situ XAS(X-ray absorption spectroscopy)showed that the stabilization of Cu^(+)and Zn^(2+)species in the nanoclusters and doped sulfur atoms during the CO_(2)RR process contributes to the sustained adsorption of protons and the generation and conversion of the CO.This work verifies the possibility of metal-support and intermetallic interactions to synergistically enhance electrochemical catalytic performance and provides ideas for further bimetallic cluster catalyst development.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
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
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
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.
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.
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support from the National Natural Science Foundation of China(No.22274131)Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHQ071)。
文摘Selenolate ligands are expected to endow fluorescent gold nanoclusters(AuNCs)with better stability and more bioactivity than thiolate ligands,making them promising in the biological field.However,there are few studies on the synthesis of water-soluble selenolate-protected AuNCs,and the impact of selenolate ligands on the optical properties of AuNCs is still unclear.In this study,we synthesized selenolatecostabilized water-soluble,near-infrared fluorescent AuNCs with four different amounts of benzeneselenol(PhSeH),and systematically investigated the role of PhSeH on their optical properties.It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect.Moreover,AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands,owing to the introduction of Au-Se bond on their surfaces.Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property.These results provide important knowledges for further development of new,robust selenolate-stabilized metal NCs for biological application.
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supported by the National Natural Science Foundation of China(Nos.52371222 and 52271211)the Natural Science Foundation of Hunan Province in China(Nos.2024JJ4022,2023JJ30277 and 2023JJ50043)+1 种基金the Science and Technology Innovation Program of Hunan Province(No.2023RC3185),ChinaHORIZON-Marie Skłodowska-Curie Actions-2021-PF(No.101065098),European Union.
文摘Hydrazine-assisted water electrolysis presents a promising and efficient hydrogen production technology.However,developing high-performance hydrazine oxidation reaction(HzOR)and hydrogen evolution reaction(HER)bifunctional catalysts remains challenging.Here,we report a bifunctional electrocatalyst of Ru NCs@NPC,embedding the ultrafine Ru nanoclusters into N-doped porous carbon via microwave reduction.Due to the ultrafine Ru nanoclusters and N doping,the composite exhibits exceptional activity for both HER and HzOR,requiring−55 and−67 mV to reach 10 mA·cm^(−2) in alkaline media.In the overall hydrazine splitting(OHzS)system,Ru NCs@NPC is used as both anode and cathode materials,achieving 10 mA·cm^(−2) only at 0.036 V.The zinc hydrazine(Zn-Hz)battery assembled with Ru NCs@NPC cathode and Zn foil anode can provide a stable voltage of 0.4 V and exhibit 98.5%energy efficiency.Therefore,integrating Zn-Hz battery with OHzS system enables self-powered H_(2) evolution.The density function theory calculations reveal that the Ru-N bond increases the metal-support interaction.
基金supported by the open funds of Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Chinathe funding from Guangdong Natural Science Funds (No. 2023A0505050107)。
文摘Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.
基金supported by the National Natural Science Foundation of China(Nos.82061148012,82027806,82372220,21974019)the National Key Research and Development Program of China(No.2017YFA0205300)the Primary Research&Development Plan of Jiangsu Province(No.BE2019716)。
文摘Skins expose to kinds of risk factors for damage,such as the hormone drugs,skin care products and ultraviolet radiation,which is accompanied by the production of excessive reactive oxygen species(ROS)and eventually leads to hypertrichosis.This skin disease is not aesthetically pleasing and even causes psychological and spiritual problems such as inferiority,anxiety and irritability.Current therapies are limited and often unsatisfactory,such as pharmacological and physical therapies,which have adverse effects and cause the irreversible destruction of hair follicles.Gold nanoclusters have good biocompatibility and their biosynthesis in vivo is responsive to oxidative stress microenvironment(OSM),which could be a safe and effective drug for ROS-induced skin injury.In our study,we demonstrated that zero valence fluorescent gold nanoclusters(FGNCs)were in situ biosynthesized in the plucking-induced damaged skin but not in the normal skin after the administration of gold precursors(+3),while FGNCs inhibited hair follicle regeneration by negatively regulating nuclear transcription factor kappa B(NFκB)-mediated inflammatory response signaling pathway(NFκB/tumor necrosis factor-α(TNF-α)axis).This OSM-responsive in situ biosynthesis method is facile and safe and holds great promise for curing hypertrichosis associated with skin dermatitis and injury.
基金supported by the National Natural Science Foundation of China(52273197 and 52333007)Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)+2 种基金the Science and Technology Plan of Shenzhen(JCYJ2021324134613038,JCYJ20220818103007014,KQTD20210811090142053,GJHZ20210705141810031)the Innovation and Technology Commission(ITC-CNERC14SC01)Tianjin Key Medical Discipline(Specialty)Construction Project.
文摘Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthesize a kind of dynamic luminescent NCs through Schiff base crosslinking between triethylenetetramine(TETA)and tannic acid at room temperature.The proposed NCs have an excitation-independent blue emission,and the maximum emission is available at about 458 nm with two excitation centers.Furthermore,the crosslinking degree of the NCs can be effectively adjusted by TETA and their formation is a kineticcontrol process.Most importantly,the proposed NCs show a property of pHcontrolled reversible depolymerization and polymerization,accompanied by a cyclic“on-off-on”photoswitching,which is directly attributed to pH-stimulated reversible C=N bond cleavage and re-formation.Because of the reversible structure change properties,the dynamic NCs have been well used in reversible information encryption.This new finding provides not only us with a powerful strategy to study the structure–properties relationship of luminescent NCs but also a design idea for constructing smart optical nanomaterials.
基金the financial support from the National Natural Science Foundation of China(22479074 and 22475096)the Natural Science Foundation of Sichuan Province(2023NSFSC1074 and 2025NSFTD0005)+9 种基金the Talent Introduction Plan of Xihua University(Z222051)the Equipment Pre-Research and MOE Joint Fund General Project(8091B02052407)the National Science Foundation of Jiangsu Province(BK20240400 and BK20241236)the Jiangsu Province Science and Technology Major Project(BG2024013)the Jiangsu Province Scientiflc and Technological Achievenments Transformation Special Fund(BA2023037)the Jiangsu Province Academic Degree and Postgraduate Education Reform Project(JGKT24_C001)the Suzhou City Key Core Technology Open Competition Project(SYG2024122)the Open Research Fund of Suzhou Laboratory(SZLAB-1308-2024TS005)the Suzhou City Gusu Leading Talent Program of Scientific and Technological Innovation and Entrepreneurship(ZXL2021273)the Chenzhou National Sustainable Development Agenda Innovation Demonstration Zone Provincial Special Project(2023sfq11)。
文摘Atomically precise copper-based nanoclusters stand out as one of the highly promising catalysts in the realm of electrochemical nitrate reduction reaction(NITRR)aimed at ammonia(NH_(3))synthesis.However,the controllable synthesis of stable Cu-based nanoclusters featuring fully inorganic anionic ligands for electrochemical NITRR remains a challenge.Herein,we present a simple and gentle chelated co-precipitation method for the uniform growth of ultrafine amorphous Cu(OH)Cl(a-Cu(OH)Cl)nanoclusters,featuring a diameter of approximately 9 nm,onto carbon nanotubes(a-Cu(OH)Cl/CNTs),aimed at enhancing electrocatalytic NITRR performance.Intriguingly,trisodium citrate dihydrate(TCD)could effectively change the crystalline form of Cu-based nanoclusters to obtain a-Cu(OH)Cl nanoclusters instead of high-crystallinity Cu_(2)(OH)_(3)Cl(c-Cu_(2)(OH)_(3)Cl)nanoclusters.In comparison to c-Cu_(2)(OH)_(3)Cl nanoclusters,a-Cu(OH)Cl nanoclusters,featuring a smaller particle size and containing more lowcoordination Cu atoms,provide more efficient catalytic sites,thereby enhancing the reaction rate and energy efficiency for NH_(3)production.The proposed chelated co-precipitation method provides a promising crystalline modulation engineering strategy to boost the electrocatalytic performances of metal nanoclusters.
基金financially supported by the National Natural Science Foundation of China(No.22375019)Beijing Institute of Technology Research Fund Program for Young Scholars(No.3090012221909)
文摘CO_(2)electroreduction(CO_(2)RR)represents a promising negative-carbon technology,which is in urgent need for efficient and high-selectivity catalysts.Here,a support control strategy is employed for precise surface engineering of charge-asymmetry nanocluster catalyst(CuZnSCN),in which zinc and copper atoms together form a metal cluster loaded on sulfur and nitrogen co-etched carbon matrix.The synergistic promotion mechanism of CO_(2)RR by Cu–Zn atom interactions and sulfur–nitrogen atom doping was investigated.A CO partial current density of 74.1 mA cm^(-2)was achieved in an alkaline electrolyte,as well as a considerable CO Faraday efficiency of 97.7%.In situ XAS(X-ray absorption spectroscopy)showed that the stabilization of Cu^(+)and Zn^(2+)species in the nanoclusters and doped sulfur atoms during the CO_(2)RR process contributes to the sustained adsorption of protons and the generation and conversion of the CO.This work verifies the possibility of metal-support and intermetallic interactions to synergistically enhance electrochemical catalytic performance and provides ideas for further bimetallic cluster catalyst development.
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.
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.
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.
