Carbon nanotube(CNT),particularly single-walled CNT,possesses exceptional properties,and can be utilized in many high-end applications including high-performance electronics.However,the atomic arrangement of a CNT det...Carbon nanotube(CNT),particularly single-walled CNT,possesses exceptional properties,and can be utilized in many high-end applications including high-performance electronics.However,the atomic arrangement of a CNT determines its band structure,making the atomic-precision fabrication one of most important topics for the development of this material.In this perspective,the author gives a personal summary on the history,current status of the atomic-precision fabrication of CNT and outlines the remaining challenges as well as the possible paths that may lead the production of atomically precise CNTs from‘fabrication’to‘manufacturing’.展开更多
Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clus...Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.展开更多
Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfull...Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster(Cu11),which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule.Notably,this Cu11cluster exhibited excellent photocatalytic hydrogen evolution activity(8.13 mmol g-1h-1)even in the absence of a mediator and noble metal co-catalyst.Furthermore,when Cu11clusters were loaded onto the surface of TiO_(2)nanosheets,the resultant Cu11@TiO_(2)nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency,which is 60 times higher than that of pure TiO_(2)nanosheets.The incorporation of Cu11clusters within the Cu11@TiO_(2)effectively inhibits the recombination of photogenerated electrons and holes,thereby accelerating the charge separation and migration in the composite material.This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.展开更多
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
Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can...Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.展开更多
To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO...To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO_(2) RR) is involved with multiple electrons and multiple products,plus the complexity of the surface chemical environment of the catalyst,it is extremely challenging to establish the structure/function relationship.Atomically precise metal nanoclusters(NCs),with crystallographically resolved structure,molecule-like characters and strong quantum confinement effects,have been emerging as a new type of catalyst for CO_(2) RR,and more importantly,they can provide an ideal platform to unravel the comprehensive mechanistic insights and establish the structure/function relationship eventually.In this review,the recent advances regarding employing molecular metal NCs with well-defined structure including Au NCs,Au-based alloy NCs,Ag NCs,Cu NCs for CO_(2) RR and relevant mechanistic studies are discussed,and the opportunities and challenges are proposed at the end for paving the development of CO_(2) RR by using atomically precise metal NCs.展开更多
The potential application of gold nanoparticles(GNPs)in biomedicine has been extensively reported.However,there is still too much puzzle about their real face and potential health risks in comparison with the commerci...The potential application of gold nanoparticles(GNPs)in biomedicine has been extensively reported.However,there is still too much puzzle about their real face and potential health risks in comparison with the commercial drug molecules.The emergence of atomically precise gold nanoclusters(APGNCs)provides the opportunity to address the puzzle due to their ultrasmall size,defined molecular formula,editable surface engineering,available structures and unique physicochemical properties including excellent biocompatibility,strong luminescence,enzyme-like activity and efficient renal clearance,et al.Recently,these advantages of APGNCs also endow them promising performances in healthcare such as bioimaging,drug delivery,antibacterial and cancer therapy.Especially,their clear composition and structures like the commercial drug molecules facilitate the study of their functions and the structure-activity relationship in healthcare,which is essential for the guided design of APGNC nanomedicine.Therefore,this review will focus the advantages and recent progress of APGNCs in health care and envision their prospects for the future.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
The photocatalytic reduction of CO_(2)presents a promising avenue for carbon fuel conversion.However,the efficiency of charge utilization remains a critical barrier to industrial applications.In this study,we introduc...The photocatalytic reduction of CO_(2)presents a promising avenue for carbon fuel conversion.However,the efficiency of charge utilization remains a critical barrier to industrial applications.In this study,we introduce a tandem design of Bi_(2)WO_(6)-BiOCl with an atomically matched interface,achieving highly efficient photoreduction of CO_(2)to CO.By incorporating WO_(4)^(2-)ions and tuning coordination environment,the(110)facet of BiOCl was in-situ grown on the(200)facet of Bi_(2)WO_(6).Compared to single phases and ball-milling samples,Bi_(2)WO_(6)-BiOCl exhibits a remarkable CO yield of 68.03μmol g^(-1)h^(-1)with a selectivity of 98%.Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport.Density functional theory(DFT)calculations and in-situ Fourier transform infrared(FTIR)spectroscopy provide insights into the intrinsic active sites and reaction mechanisms.The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.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
Supported atomically dispersed metal catalysts(ADMCs)have received enormous attention due to their high atom utilization efficiency,mass activity and excellent selectivity.Single-atom site catalysts(SACs)with monometa...Supported atomically dispersed metal catalysts(ADMCs)have received enormous attention due to their high atom utilization efficiency,mass activity and excellent selectivity.Single-atom site catalysts(SACs)with monometal-center as the quintessential ADMCs have been extensively studied in the catalysis-related fields.Beyond SACs,novel atomically dispersed metal catalysts(NADMCs)with flexible active sites featuring two or more catalytically centers including dual-atom and triple-atom catalysts have drawn ever-increasing attention recently.Owing to the presence of multiple neighboring active sites,NADMCs could exhibit much higher activity and selectivity compared with SACs,especially in those complicated reactions with multi-step intermediates.This review comprehensively outlines the recent exciting advances on the NADMCs with emphasis on the deeper understanding of the synergistic interactions among multiple metal atoms and underlying structure-performance relationships.It starts with the systematical introduction of principal synthetic approaches for NADMCs highlighting the key issues of each fabrication method including the atomically precise control in the design of metal nuclearity,and then the state-of-the-art characterizations for identifying and monitoring the atomic structure of NADMCs are explored.Thereafter,the recent development of NADMCs in energy-related applications is systematically discussed.Finally,we provide some new insights into the remaining challenges and opportunities for the development of NADMCs.展开更多
Materials and chemical scientists have tirelessly pursued the vision of creating atomically tailored materials.The promise of atomic precision in material synthesis lies in the potential to precisely control every asp...Materials and chemical scientists have tirelessly pursued the vision of creating atomically tailored materials.The promise of atomic precision in material synthesis lies in the potential to precisely control every aspect of a material's structure,thereby opening up opportunities for discovering and tuning novel physical properties[1].However,achieving atomically precise assemblies in practice remains a formidable challenge,largely due to the difficulty of controlling nucleation and growth processes at the most fundamental scale.展开更多
Numerous atomically precise coinage metal nanoclusters have been synthesized,exhibiting diverse structures and promising properties for catalytic and other functional applications.However,silver nanoclusters featuring...Numerous atomically precise coinage metal nanoclusters have been synthesized,exhibiting diverse structures and promising properties for catalytic and other functional applications.However,silver nanoclusters featuring layered core structures remain largely unexplored,limiting investigations into the effects of atomic arrangements on catalytic functions.Herein,we report the synthesis and atomic level structure of a novel thiolate-phosphine co-stabilized silver nanocluster,Ag_(26)(SR)_(16)(DPPE)_(4)Cl_(2)(denoted as Ag_(26)),where SR is 3,5-bis(trifluoromethyl)benzenethiolate and DPPE is 1,2-bis(diphenylphosphino)ethane.Single-crystal X-ray diffraction analysis reveals that Ag26 comprises a three-layered Ag_(18)core,with each layer consisting of six silver atoms arranged in a distorted parallelogram configuration.This Ag18 core is stabilized by four Ag_(2)(SR)_(4)(DPPE)metal-ligand motifs and two chlorides.Notably,TiO_(2)-supported Ag_(26)nanoclusters(Ag_(26)/TiO_(2))demonstrated promising photocatalytic performance for solar-driven hydrogen production,achieving a hydrogen evolution rate of 2006μmol·g^(-1)·h^(-1),representing 16.2-and 6.5-fold enhancements compared to bare TiO_(2)support and similarly sized Ag_(25)/TiO_(2)nanoclusters,respectively.The layered atomic arrangement in the Ag_(26)core favorably regulates the energy level alignment with TiO_(2),leading to efficient photogenerated charge separation and enhanced catalytic activity.This work highlights the potential of structurally tailored silver nanoclusters and offers valuable insights for the design of advanced materials for energy conversion applications.展开更多
The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being c...The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being challenging.In this work,we developed an acid-induction method and synthesized a Au_(52)(TBBT)_(30)(TBBTH=4-tert-butylbenzenelthiol)nanocluster with the kernel composed of two parts:the amorphous Au_(22)part and the fcc Au_(21)part,which represents the first construction of fcc-amorphous homometal heterojunction with∼1 nm size.Density function theory(DFT)revealed that the HOMO−LUMO majorly distributed in the amorphous part and the HOMO−LUMO gap was dominated by the amorphous part,indicating the redox activity of the amorphous Au_(22)part in contrast to the fcc Au_(21)part,which was experimentally confirmed by differential pulse voltammetry,antioxidation test and anti-Galvanic reaction.But for electro-catalyzing reduction of CO_(2)to CO,the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO_(2)to CO,and the most active sites were assigned to the cosurface sites of amorphous Au_(22)and fcc Au_(21),which is also responsible for the high performance of Au_(52)(TBBT)_(30)relative to the pure fcc-structured Au_(52)(TBBT)_(32)(the highest CO FE:96.7%at−0.67 V vs 73.3%at−0.57 V;CO partial current density at the corresponding potential:−7.3 vs−2.7 mA cm^(−2)).展开更多
Coherent vibrational dynamics can be observed in atomically precise gold nanoclusters using femtosecond time-resolved pump-probe spectroscopy.It can not only reveal the coupling between electrons and vibrations,but al...Coherent vibrational dynamics can be observed in atomically precise gold nanoclusters using femtosecond time-resolved pump-probe spectroscopy.It can not only reveal the coupling between electrons and vibrations,but also reflect the mechanical and electronic properties of metal nanoclusters,which holds potential applications in biological sensing and mass detection.Here,we investigated the coherent vibrational dynamics of[Au_(25)(SR)_(18)]^(-)nanoclusters by ultrafast spectroscopy and revealed the origins of thesecoherent vibrations by analyzing their frequency,phase and probe wavelength distributions.Strong coherent oscillations with frequency of 40 cm^(-1) and 80 cm^(-1) can be reproduced in the excited state dynamics of[Au_(25)(SR)_(18)]^(-),which should originate from acoustic vibrations of the Au13 metal core.Phase analysis on the oscillations indicates that the 80 cm^(-1) mode should arise from the frequency modulation of the electronic states while the 40 cm^(-1) mode should originate from the amplitude modulation of the dynamic spectrum.Moreover,it is found that the vibration frequencies of[Au_(25)(SR)_(18)]^(-)obtained in pump-probe measurements are independent of the surface ligands so that they are intrinsic properties of the metal core.These results are of great value to understand the electron-vibration coupling of metal nanoclusters.展开更多
Inspired by the Mn_(4)CaO_(5)cluster at the catalytic water oxidation center of natural enzymes,artificial multinuclear metal clusters have attracted significant attention as water oxidation catalysts due to their syn...Inspired by the Mn_(4)CaO_(5)cluster at the catalytic water oxidation center of natural enzymes,artificial multinuclear metal clusters have attracted significant attention as water oxidation catalysts due to their synergistic interactions among multiple metal atoms[1-8].Atomically precise metal cluster catalysts serve as model systems for uncovering the synergistic mechanisms of the oxygen evolution reaction(OER)[9-14].展开更多
Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property...Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property relationship at the atomic level remains a challenge due to the inherent polydispersity of catalysts,which hinders a comprehensive understanding of the defect catalysts.Atomically precise metal nanoclusters can serve as model catalysts because of their perfect monodispersity and well-defined structure.While,the understanding about defects in atomically precise metal nanoclusters is insufficient.This review encompasses various types of defects(such as heteroatom incorporation,vacancies,ligand deficiencies,etc.)in atomically precise coingage metal clusters,characterization methods,and their applications within the realm of catalysis.At the conclusion of this review,we propose several prospects,including the controllable construction of defects,further enhancement of the performance of clusters with defects,and monitoring the in-situ evolution of defects in clusters during catalysis.The purpose of this review is to deepen the understanding of defects in atomically precise clusters,establish the relationship between defect structure and catalytic performance,and offer valuable insights for the designing and developing of efficient defect-rich cluster catalysts.展开更多
Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear s...Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.展开更多
Achieving atomically precise spatial control over surface domains in nanoparticles represents a grand challenge in nanoscience,and holds the key for advancing targeted drug delivery,adaptive catalysis,and programmable...Achieving atomically precise spatial control over surface domains in nanoparticles represents a grand challenge in nanoscience,and holds the key for advancing targeted drug delivery,adaptive catalysis,and programmable self-assembly.The ability to control exactly where and how chemical functionalities reside on a nanoparticle determines not only its local reactivity,but also the directional forces that govern its collective behavior.Yet despite decades of progress in colloidal synthesis and ligand engineering,truly deterministic patterning of nanoscale surfaces remains elusive.展开更多
Copper hydride clusters have become especially fascinating in the field of functional cluster-based materials due to the various compositions and architectures as well as intriguing properties especially hydride-relat...Copper hydride clusters have become especially fascinating in the field of functional cluster-based materials due to the various compositions and architectures as well as intriguing properties especially hydride-related applications.A comprehensive understanding of the synthesis,structure determination,the relationship between structure and properties of copper hydride clusters hold great significance for development of the functional characteristics.In this review,advances in the methodology for the preparation and understanding of atomically precise copper hydride clusters are comprehensively summarized.The functional properties of copper hydride clusters including luminescence behaviors,especially for the tailoring emission features,chirality and catalysis were mainly highlighted.Furthermore,the importance of balancing the stability of copper hydride clusters and the effective development of their functional properties is emphasized.The review discusses the potential of hydride atoms in modulating functionality of copper hydride clusters,which is expected to bring about significant advancements in catalysis and chiral applications.Finally,we provide insights into the prospects for future development on the copper hydride clusters.展开更多
基金supported by JSPS KAKENHI(Grant Nos.JP18H05329,JP19H02543,JP20H00220,and JP20KK0114)by JST,CREST Grant No.JPMJCR20B5,Japansupported by the‘Nanotechnology Platform’of the MEXT,Japan,Grant Nos.JPMXP09A20UT0063 and JPMXP09A21UT0050.
文摘Carbon nanotube(CNT),particularly single-walled CNT,possesses exceptional properties,and can be utilized in many high-end applications including high-performance electronics.However,the atomic arrangement of a CNT determines its band structure,making the atomic-precision fabrication one of most important topics for the development of this material.In this perspective,the author gives a personal summary on the history,current status of the atomic-precision fabrication of CNT and outlines the remaining challenges as well as the possible paths that may lead the production of atomically precise CNTs from‘fabrication’to‘manufacturing’.
基金supported by the Start-Up Research Funding of Fujian Normal University(No.Y0720326K13)the National Natural Science Foundation of China(Nos.22103035 and 22033005)+2 种基金the National Key R&D Program of China(No.2022YFA1503900)Shenzhen Science and Technology Program(No.RCYX20231211090357078)Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002).
文摘Atomically precise palladium(Pd)clusters are emerging as versatile nanomaterials with applications in catalysis and biomedicine.This study explores the synthesis,structure evolution,and catalytic properties of Pd clusters stabilized by cyclohexanethiol(HSC_(6)H_(11))ligands.Using electrospray ionization mass spectrometry(ESI-MS)and single-crystal X-ray diffraction(SXRD),structures of the Pd clusters ranging from Pd4(SC_(6)H_(11))8 to Pd18(SC_(6)H_(11))36 were determined.This analysis revealed a structure evolution from polygonal to elliptical geometries of the PdnS2n frameworks as the cluster size increased.UV-Vis-NIR spectroscopy,combined with quantum chemical calculations,elucidated changes in the electronic structure of the clusters.Catalytic studies on the Sonogashira cross-coupling reactions demonstrated a size-dependent decline in activity attributed to variations in structural arrangements and electronic properties.Mechanistic insights proposed a distinctive Pd(Ⅱ)-Pd(Ⅳ)catalytic cycle.This research underscores how ligands and cluster size influence the structures and properties of Pd clusters,offering valuable insights for the future design and application of Pd clusters in advanced catalysis and beyond.
基金supported by the National Natural Science Foundation of China(Nos.22371263 and U2004193)Natural Science Foundation of Henan Province(No.232300421225)。
文摘Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features.Herein,we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster(Cu11),which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule.Notably,this Cu11cluster exhibited excellent photocatalytic hydrogen evolution activity(8.13 mmol g-1h-1)even in the absence of a mediator and noble metal co-catalyst.Furthermore,when Cu11clusters were loaded onto the surface of TiO_(2)nanosheets,the resultant Cu11@TiO_(2)nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency,which is 60 times higher than that of pure TiO_(2)nanosheets.The incorporation of Cu11clusters within the Cu11@TiO_(2)effectively inhibits the recombination of photogenerated electrons and holes,thereby accelerating the charge separation and migration in the composite material.This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.
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financial support from National Natural Science Foundation of China(22125202,21932004,22101128)Natural Science Foundation of Jiangsu Province(BK20220033)。
文摘Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.
基金the grant from the National Natural Science Foundation of China(No.21805170)financial support from Guangdong Natural Science Funds for Distinguished Young Scholars(No.2015A030306006)+1 种基金Guangzhou Science and Technology Plan Projects(No.201804010323)the fundamental funds for central universities(SCUT No.2018ZD022)。
文摘To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO_(2) RR) is involved with multiple electrons and multiple products,plus the complexity of the surface chemical environment of the catalyst,it is extremely challenging to establish the structure/function relationship.Atomically precise metal nanoclusters(NCs),with crystallographically resolved structure,molecule-like characters and strong quantum confinement effects,have been emerging as a new type of catalyst for CO_(2) RR,and more importantly,they can provide an ideal platform to unravel the comprehensive mechanistic insights and establish the structure/function relationship eventually.In this review,the recent advances regarding employing molecular metal NCs with well-defined structure including Au NCs,Au-based alloy NCs,Ag NCs,Cu NCs for CO_(2) RR and relevant mechanistic studies are discussed,and the opportunities and challenges are proposed at the end for paving the development of CO_(2) RR by using atomically precise metal NCs.
基金supported by the National Natural Science Foundation of China(21971246,22371108,22075122)Taishan Scholar Foundation of Shandong Province(tsqn202211242)the Chunhui Program of the Ministry of Education of China(HZKY20220463).
文摘The potential application of gold nanoparticles(GNPs)in biomedicine has been extensively reported.However,there is still too much puzzle about their real face and potential health risks in comparison with the commercial drug molecules.The emergence of atomically precise gold nanoclusters(APGNCs)provides the opportunity to address the puzzle due to their ultrasmall size,defined molecular formula,editable surface engineering,available structures and unique physicochemical properties including excellent biocompatibility,strong luminescence,enzyme-like activity and efficient renal clearance,et al.Recently,these advantages of APGNCs also endow them promising performances in healthcare such as bioimaging,drug delivery,antibacterial and cancer therapy.Especially,their clear composition and structures like the commercial drug molecules facilitate the study of their functions and the structure-activity relationship in healthcare,which is essential for the guided design of APGNC nanomedicine.Therefore,this review will focus the advantages and recent progress of APGNCs in health care and envision their prospects for the future.
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supported by the National Key R&D Program of China(No.2021YFA1200201)the Beijing Outstanding Young Scientists Projects(No.BJJWZYJH01201910005018)+1 种基金The Basic Science Center Program for Multiphase Evolution in Hypergravity of the National Natural Science Foundation of China(No.51988101)the National Natural Science Foundation of China(Nos.52071003 and 91860202)。
文摘The photocatalytic reduction of CO_(2)presents a promising avenue for carbon fuel conversion.However,the efficiency of charge utilization remains a critical barrier to industrial applications.In this study,we introduce a tandem design of Bi_(2)WO_(6)-BiOCl with an atomically matched interface,achieving highly efficient photoreduction of CO_(2)to CO.By incorporating WO_(4)^(2-)ions and tuning coordination environment,the(110)facet of BiOCl was in-situ grown on the(200)facet of Bi_(2)WO_(6).Compared to single phases and ball-milling samples,Bi_(2)WO_(6)-BiOCl exhibits a remarkable CO yield of 68.03μmol g^(-1)h^(-1)with a selectivity of 98%.Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport.Density functional theory(DFT)calculations and in-situ Fourier transform infrared(FTIR)spectroscopy provide insights into the intrinsic active sites and reaction mechanisms.The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.
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the Beijing Natural Science Foundation(No.2224096)the National Key R&D Program of China(No.2018YFA0702003)+3 种基金the Science and Technology Key Project of Guangdong Province,China(No.2020B010188002)the China Postdoctoral Science Foundation(Nos.2021M690086 and 2021TQ0170)X.B.Z.acknowledges funding support from the Office of China Postdoctoral Council(No.YJ20200277)the“Shuimu Tsinghua Scholar Program"(No.2020SM109)of Tsinghua University,China.
文摘Supported atomically dispersed metal catalysts(ADMCs)have received enormous attention due to their high atom utilization efficiency,mass activity and excellent selectivity.Single-atom site catalysts(SACs)with monometal-center as the quintessential ADMCs have been extensively studied in the catalysis-related fields.Beyond SACs,novel atomically dispersed metal catalysts(NADMCs)with flexible active sites featuring two or more catalytically centers including dual-atom and triple-atom catalysts have drawn ever-increasing attention recently.Owing to the presence of multiple neighboring active sites,NADMCs could exhibit much higher activity and selectivity compared with SACs,especially in those complicated reactions with multi-step intermediates.This review comprehensively outlines the recent exciting advances on the NADMCs with emphasis on the deeper understanding of the synergistic interactions among multiple metal atoms and underlying structure-performance relationships.It starts with the systematical introduction of principal synthetic approaches for NADMCs highlighting the key issues of each fabrication method including the atomically precise control in the design of metal nuclearity,and then the state-of-the-art characterizations for identifying and monitoring the atomic structure of NADMCs are explored.Thereafter,the recent development of NADMCs in energy-related applications is systematically discussed.Finally,we provide some new insights into the remaining challenges and opportunities for the development of NADMCs.
文摘Materials and chemical scientists have tirelessly pursued the vision of creating atomically tailored materials.The promise of atomic precision in material synthesis lies in the potential to precisely control every aspect of a material's structure,thereby opening up opportunities for discovering and tuning novel physical properties[1].However,achieving atomically precise assemblies in practice remains a formidable challenge,largely due to the difficulty of controlling nucleation and growth processes at the most fundamental scale.
基金the financial support by the Research Center Program of the IBS(IBS-R006-D1)in Republic of Korea.
文摘Numerous atomically precise coinage metal nanoclusters have been synthesized,exhibiting diverse structures and promising properties for catalytic and other functional applications.However,silver nanoclusters featuring layered core structures remain largely unexplored,limiting investigations into the effects of atomic arrangements on catalytic functions.Herein,we report the synthesis and atomic level structure of a novel thiolate-phosphine co-stabilized silver nanocluster,Ag_(26)(SR)_(16)(DPPE)_(4)Cl_(2)(denoted as Ag_(26)),where SR is 3,5-bis(trifluoromethyl)benzenethiolate and DPPE is 1,2-bis(diphenylphosphino)ethane.Single-crystal X-ray diffraction analysis reveals that Ag26 comprises a three-layered Ag_(18)core,with each layer consisting of six silver atoms arranged in a distorted parallelogram configuration.This Ag18 core is stabilized by four Ag_(2)(SR)_(4)(DPPE)metal-ligand motifs and two chlorides.Notably,TiO_(2)-supported Ag_(26)nanoclusters(Ag_(26)/TiO_(2))demonstrated promising photocatalytic performance for solar-driven hydrogen production,achieving a hydrogen evolution rate of 2006μmol·g^(-1)·h^(-1),representing 16.2-and 6.5-fold enhancements compared to bare TiO_(2)support and similarly sized Ag_(25)/TiO_(2)nanoclusters,respectively.The layered atomic arrangement in the Ag_(26)core favorably regulates the energy level alignment with TiO_(2),leading to efficient photogenerated charge separation and enhanced catalytic activity.This work highlights the potential of structurally tailored silver nanoclusters and offers valuable insights for the design of advanced materials for energy conversion applications.
基金National Natural Science Foundation of China(Nos.22373082,22471275,21905284,21829501,21925303,22075290,22075291,92475105,U24A20480,22272179,21771186,21528303,21222301,21171170,22403096)Science and Technology Innovation Program of Hunan Province(2023RC1055)+4 种基金Hefei Institute of Physical Science,Chinese Academy of Sciences(BR-E44BGGBR12B)CASHIPS Director’s Fund(BJPY2019A02)Key Program of 13th five-year plan,CASHIPS(KP-2017-16)Collaborative Innovation Program of Hefei Center for Physical Science and Technology(2020HSC-CIP005,2022HSC-CIP018)the State Key Laboratory of Mesoscience and Engineering,Institute of Process Engineering,Chinese Academy of Sciences(MESO-24-A01)for financial support.
文摘The emerging of ultrasmall gold nanoparticles(nanoclusters)with atomic precision provides opportunities for precisely studying crystalline−amorphous heterostructures,despite the construction of such structures being challenging.In this work,we developed an acid-induction method and synthesized a Au_(52)(TBBT)_(30)(TBBTH=4-tert-butylbenzenelthiol)nanocluster with the kernel composed of two parts:the amorphous Au_(22)part and the fcc Au_(21)part,which represents the first construction of fcc-amorphous homometal heterojunction with∼1 nm size.Density function theory(DFT)revealed that the HOMO−LUMO majorly distributed in the amorphous part and the HOMO−LUMO gap was dominated by the amorphous part,indicating the redox activity of the amorphous Au_(22)part in contrast to the fcc Au_(21)part,which was experimentally confirmed by differential pulse voltammetry,antioxidation test and anti-Galvanic reaction.But for electro-catalyzing reduction of CO_(2)to CO,the crystalline surface sites were revealed to be more catalytically active than the amorphous surface sites in catalyzing the reduction of CO_(2)to CO,and the most active sites were assigned to the cosurface sites of amorphous Au_(22)and fcc Au_(21),which is also responsible for the high performance of Au_(52)(TBBT)_(30)relative to the pure fcc-structured Au_(52)(TBBT)_(32)(the highest CO FE:96.7%at−0.67 V vs 73.3%at−0.57 V;CO partial current density at the corresponding potential:−7.3 vs−2.7 mA cm^(−2)).
基金supported by the startup funding from University of Science and Technology of China(KY2340000137)the startup funding from Chinese Academy of Sciences
文摘Coherent vibrational dynamics can be observed in atomically precise gold nanoclusters using femtosecond time-resolved pump-probe spectroscopy.It can not only reveal the coupling between electrons and vibrations,but also reflect the mechanical and electronic properties of metal nanoclusters,which holds potential applications in biological sensing and mass detection.Here,we investigated the coherent vibrational dynamics of[Au_(25)(SR)_(18)]^(-)nanoclusters by ultrafast spectroscopy and revealed the origins of thesecoherent vibrations by analyzing their frequency,phase and probe wavelength distributions.Strong coherent oscillations with frequency of 40 cm^(-1) and 80 cm^(-1) can be reproduced in the excited state dynamics of[Au_(25)(SR)_(18)]^(-),which should originate from acoustic vibrations of the Au13 metal core.Phase analysis on the oscillations indicates that the 80 cm^(-1) mode should arise from the frequency modulation of the electronic states while the 40 cm^(-1) mode should originate from the amplitude modulation of the dynamic spectrum.Moreover,it is found that the vibration frequencies of[Au_(25)(SR)_(18)]^(-)obtained in pump-probe measurements are independent of the surface ligands so that they are intrinsic properties of the metal core.These results are of great value to understand the electron-vibration coupling of metal nanoclusters.
基金supported by the National Natural Science Foundation of China(92461035,92161104,92161203,92361301)Fujian Province(2024J01313)。
文摘Inspired by the Mn_(4)CaO_(5)cluster at the catalytic water oxidation center of natural enzymes,artificial multinuclear metal clusters have attracted significant attention as water oxidation catalysts due to their synergistic interactions among multiple metal atoms[1-8].Atomically precise metal cluster catalysts serve as model systems for uncovering the synergistic mechanisms of the oxygen evolution reaction(OER)[9-14].
基金This work was supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Recent advancements in defect engineering have significantly improved catalysis by modulating the electronic structure and enhancing the intrinsic abilities of catalysts.However,establishing a clear structure-property relationship at the atomic level remains a challenge due to the inherent polydispersity of catalysts,which hinders a comprehensive understanding of the defect catalysts.Atomically precise metal nanoclusters can serve as model catalysts because of their perfect monodispersity and well-defined structure.While,the understanding about defects in atomically precise metal nanoclusters is insufficient.This review encompasses various types of defects(such as heteroatom incorporation,vacancies,ligand deficiencies,etc.)in atomically precise coingage metal clusters,characterization methods,and their applications within the realm of catalysis.At the conclusion of this review,we propose several prospects,including the controllable construction of defects,further enhancement of the performance of clusters with defects,and monitoring the in-situ evolution of defects in clusters during catalysis.The purpose of this review is to deepen the understanding of defects in atomically precise clusters,establish the relationship between defect structure and catalytic performance,and offer valuable insights for the designing and developing of efficient defect-rich cluster catalysts.
基金supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.
文摘Achieving atomically precise spatial control over surface domains in nanoparticles represents a grand challenge in nanoscience,and holds the key for advancing targeted drug delivery,adaptive catalysis,and programmable self-assembly.The ability to control exactly where and how chemical functionalities reside on a nanoparticle determines not only its local reactivity,but also the directional forces that govern its collective behavior.Yet despite decades of progress in colloidal synthesis and ligand engineering,truly deterministic patterning of nanoscale surfaces remains elusive.
基金supported by the Excellent Youth Foundation of Henan Scientific Committee(No.252300421188)the Henan Provincial Science and Technology Research and Development Joint Fund(242301420062)+5 种基金the National Natural Science Foundation of China(Nos.22575077,92461304,92356304,22201261,22305067,2011YFA1200301)the Doctoral Fund of Henan University of Technology(2023BS105)Henan Province Postdoctoral Launched Research Projects(HN2025009)the Youngbackbone Teacher Foundation of Colleges and Universities of Henan Province(2023GGJS062)Cultivation Project of Tuoxin Team in Henan University of Technology,China(Nos.2024TXTD11,2024TXTD10)Zhengzhou University.
文摘Copper hydride clusters have become especially fascinating in the field of functional cluster-based materials due to the various compositions and architectures as well as intriguing properties especially hydride-related applications.A comprehensive understanding of the synthesis,structure determination,the relationship between structure and properties of copper hydride clusters hold great significance for development of the functional characteristics.In this review,advances in the methodology for the preparation and understanding of atomically precise copper hydride clusters are comprehensively summarized.The functional properties of copper hydride clusters including luminescence behaviors,especially for the tailoring emission features,chirality and catalysis were mainly highlighted.Furthermore,the importance of balancing the stability of copper hydride clusters and the effective development of their functional properties is emphasized.The review discusses the potential of hydride atoms in modulating functionality of copper hydride clusters,which is expected to bring about significant advancements in catalysis and chiral applications.Finally,we provide insights into the prospects for future development on the copper hydride clusters.
