The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-ba...The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.展开更多
Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable stru...Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable structures.Here,we controllably prepared and structurally determined a valence-neutral Au_(24+x)Ag_(20-x)(SPhtBu)_(26)(0<x<4)nanocluster with comparable structure features to a well-known Au_(12)Ag_(32)(SPhF_(2))_(30) cluster.The Au_(24+x)Ag_(20-x)(SPhtBu)_(26) cluster contained a hollow Au_(12)@M_(20) metallic kernel(M=Au/Ag),12 Au_(1)(SR)_(2) staples,and two bridging SR molecules,and its average molecular formula was determined to be Au_(26.3)Ag_(17.7)(SPhtBu)_(26),as evidenced by X-ray crystallography and electrospray ionization mass spectrometry.Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage,the Au_(24+x)Ag_(20-x)(SPhtBu)_(26) nanocluster exhibited lower molecular symmetry relative to Au_(12)Ag_(32)(SPhF_(2))_(30) in terms of the dodecahedral kernel and motif shell structures.Besides,the strong π-π interaction in Au2_(4+x)Ag_(20-x)(SPhtBu)_(26) contributed to its enhanced photoluminescence intensity compared with Au_(12)Ag_(32)(SPhF_(2))_(30).The study,herein,extends the 44-metal-atom cluster family,thereby enabling us to better understand the correlations between their structures and properties at the atomic level.展开更多
Developing new templates to evaluate the ligand engineering effect in manipulating nanoclusters from both molecular and supramolecular aspects remains highly desired in cluster science because it allows for an in-dept...Developing new templates to evaluate the ligand engineering effect in manipulating nanoclusters from both molecular and supramolecular aspects remains highly desired in cluster science because it allows for an in-depth understanding of structure-property correlations.We herein presented the secondary ligand(i.e.,the phosphine ligand)engineering based on an Ag_(29) nanocluster template and its dual effects on intracluster structures and intercluster aggregates.The“dissociationcombination equilibrium”of phosphine ligands on the nanocluster surface was controlled by tailoring the C-H…πinteractions within the ligand shell,which led to the fabrication of a family of[Ag_(29)(BDT)_(12)(PR_(3))_(x)]^(3-)nanoclusters.On the molecular level,the dissociation of phosphine ligands contracted the nanocluster framework,while the overall configuration of[Ag_(29)(BDT)_(12)]^(3-)was retained.On the supramolecular level,the complete dissociation of phosphine ligands yielded a bare nanocluster,which followed a chiral crystallization mode,and its crystals displayed high optical activity,derived from circular dichroism and circularly polarized luminescence characterizations.Overall,this work presents the peripheral ligand effects in directionally controlling intracluster configurations and intercluster aggregations,which hopefully benefit future design and preparation of new nanoclusters or cluster-based nanomaterials with customized structures and performances.展开更多
Developing new approaches to fulfill the enantioseparation of nanocluster racemates and construct cluster-based nanomaterials with optical activity remains highly desired in cluster science,because it is an essential ...Developing new approaches to fulfill the enantioseparation of nanocluster racemates and construct cluster-based nanomaterials with optical activity remains highly desired in cluster science,because it is an essential prerequisite for fundamental research and extensive applications of these nanomaterials.We herein propose a strategy termed“active-site exposing and partly re-protecting”to trigger the symmetry breaking of highly symmetrical nanoclusters and to render cluster crystals optically active.The vertex PPh_(3)of the symmetrical Ag_(29)(SSR)_(12)(PPh_(3))_(4)(SSR=1,3-benzenedithiol)nanocluster was firstly dissociated in the presence of counterions with large steric hindrance,and then the exposed Ag active sites of the obtained Ag_(29)(SSR)_(12)nanocluster were partly re-protected by Ag^(+),yielding an Ag_(29)(SSR)_(12)-Ag_(2)nanocluster with a symmetry-breaking construction.Ag_(29)(SSR)_(12)-Ag_(2)followed a chiral crystallization mode,and its crystal displayed strong optical activity,derived from CD and CPL characterizations.Overall,this work presents a new approach(i.e.,active-site exposing and partly re-protecting)for the symmetry breaking of highly symmetrical nanoclusters,the enantioseparation of nanocluster racemates,and the achievement of highly optical activity.展开更多
基金the Natural Science research project of Universities in Anhui Province(No.KJ2021ZD0001)the Natural Science Foundation of Anhui Province(No.2208085MB20)the National Natural Science Foundation of China(No.22101001).
文摘The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.
基金the financial support of the NSFC(21631001,21871001,and 22101001)the Ministry of Education,and the University Synergy Innovation Program of Anhui Province(GXXT-2020-053).
文摘Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles,especially for those molecules with identical sizes but comparable structures.Here,we controllably prepared and structurally determined a valence-neutral Au_(24+x)Ag_(20-x)(SPhtBu)_(26)(0<x<4)nanocluster with comparable structure features to a well-known Au_(12)Ag_(32)(SPhF_(2))_(30) cluster.The Au_(24+x)Ag_(20-x)(SPhtBu)_(26) cluster contained a hollow Au_(12)@M_(20) metallic kernel(M=Au/Ag),12 Au_(1)(SR)_(2) staples,and two bridging SR molecules,and its average molecular formula was determined to be Au_(26.3)Ag_(17.7)(SPhtBu)_(26),as evidenced by X-ray crystallography and electrospray ionization mass spectrometry.Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage,the Au_(24+x)Ag_(20-x)(SPhtBu)_(26) nanocluster exhibited lower molecular symmetry relative to Au_(12)Ag_(32)(SPhF_(2))_(30) in terms of the dodecahedral kernel and motif shell structures.Besides,the strong π-π interaction in Au2_(4+x)Ag_(20-x)(SPhtBu)_(26) contributed to its enhanced photoluminescence intensity compared with Au_(12)Ag_(32)(SPhF_(2))_(30).The study,herein,extends the 44-metal-atom cluster family,thereby enabling us to better understand the correlations between their structures and properties at the atomic level.
文摘Developing new templates to evaluate the ligand engineering effect in manipulating nanoclusters from both molecular and supramolecular aspects remains highly desired in cluster science because it allows for an in-depth understanding of structure-property correlations.We herein presented the secondary ligand(i.e.,the phosphine ligand)engineering based on an Ag_(29) nanocluster template and its dual effects on intracluster structures and intercluster aggregates.The“dissociationcombination equilibrium”of phosphine ligands on the nanocluster surface was controlled by tailoring the C-H…πinteractions within the ligand shell,which led to the fabrication of a family of[Ag_(29)(BDT)_(12)(PR_(3))_(x)]^(3-)nanoclusters.On the molecular level,the dissociation of phosphine ligands contracted the nanocluster framework,while the overall configuration of[Ag_(29)(BDT)_(12)]^(3-)was retained.On the supramolecular level,the complete dissociation of phosphine ligands yielded a bare nanocluster,which followed a chiral crystallization mode,and its crystals displayed high optical activity,derived from circular dichroism and circularly polarized luminescence characterizations.Overall,this work presents the peripheral ligand effects in directionally controlling intracluster configurations and intercluster aggregations,which hopefully benefit future design and preparation of new nanoclusters or cluster-based nanomaterials with customized structures and performances.
基金We acknowledge the financial support of the NSFC(21631001,21871001,and 22101001)the Ministry of Education,and the University Synergy Innovation Program of Anhui Province(GXXT-2020-053).
文摘Developing new approaches to fulfill the enantioseparation of nanocluster racemates and construct cluster-based nanomaterials with optical activity remains highly desired in cluster science,because it is an essential prerequisite for fundamental research and extensive applications of these nanomaterials.We herein propose a strategy termed“active-site exposing and partly re-protecting”to trigger the symmetry breaking of highly symmetrical nanoclusters and to render cluster crystals optically active.The vertex PPh_(3)of the symmetrical Ag_(29)(SSR)_(12)(PPh_(3))_(4)(SSR=1,3-benzenedithiol)nanocluster was firstly dissociated in the presence of counterions with large steric hindrance,and then the exposed Ag active sites of the obtained Ag_(29)(SSR)_(12)nanocluster were partly re-protected by Ag^(+),yielding an Ag_(29)(SSR)_(12)-Ag_(2)nanocluster with a symmetry-breaking construction.Ag_(29)(SSR)_(12)-Ag_(2)followed a chiral crystallization mode,and its crystal displayed strong optical activity,derived from CD and CPL characterizations.Overall,this work presents a new approach(i.e.,active-site exposing and partly re-protecting)for the symmetry breaking of highly symmetrical nanoclusters,the enantioseparation of nanocluster racemates,and the achievement of highly optical activity.
