Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)cal...Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)calculations and molecular dynamics(MD)simulations,we demonstrated that polar solvents not only provide an important environment to stabilize clusters,but they can also dramatically alter the electronic property of cluster anions forming novel superhalogen anions.Such a regulation effect was first verified in small model gas-phase pure and doped gold cluster anions,which was further evidenced in a real experimentally synthesized Au18 nanocluster.Different solvation models reveal that the solvent field,which is a noninvasive methodology different from conventional electron-counting rules,can be considered as a novel external field to remarkably increase the electron-binding capability of cluster anions while maintaining their geometrical and electronic structures.Considering the indispensability and convenient availability of the solvents,present findings may boost the potential applications of superatoms in constructing super oxidizers in the condensed phase.展开更多
Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,wh...Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.展开更多
Oxygen vacancy(O_(v))as well as Ov migration in metal oxide are of great importance in structural evolution of active center in single-atom catalysts(SACs).Here,the interplay between invasive single Pt atom and native...Oxygen vacancy(O_(v))as well as Ov migration in metal oxide are of great importance in structural evolution of active center in single-atom catalysts(SACs).Here,the interplay between invasive single Pt atom and native O_(v) in SA-Pt/rutile TiO_(2)(110)surface,as well as their synergetic effect on water dissociation are investigated by density functional theory(DFT)calculations.We show that importing Pt atom as Pt-ads,Pt_(2c),Pt_(5c) and Pt6c modes could decelerate the O_(v) migration effectively,especially in Pt6c mode.Under oxygen-rich conditions,Pt6c substitution could make oxygen Ov formation easier,but migration harder.On Pt_(6c)/Ti_(1-y)O_(2-x1)(110)surface,as a bimetal center,Pt_(4c)-Ti_(5c) concave could not make water dissociation process easier;however,the O2c closed to Pt become a good proton acceptor to make water dissociation on Ti_(5c)-O_(2c) more convenient with the aid of topmost Ti_(5c).展开更多
基金supported by the National Natural Science Foundation of China(NSFC,No.92161101)the Taishan Scholars Project of Shandong Province(No.ts201712011)the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032).
文摘Condensed-phase synthesis of atomically precise clusters has become a vital branch of cluster science,where solvents are indispensable in the synthesis process.Herein,by employing the density functional theory(DFT)calculations and molecular dynamics(MD)simulations,we demonstrated that polar solvents not only provide an important environment to stabilize clusters,but they can also dramatically alter the electronic property of cluster anions forming novel superhalogen anions.Such a regulation effect was first verified in small model gas-phase pure and doped gold cluster anions,which was further evidenced in a real experimentally synthesized Au18 nanocluster.Different solvation models reveal that the solvent field,which is a noninvasive methodology different from conventional electron-counting rules,can be considered as a novel external field to remarkably increase the electron-binding capability of cluster anions while maintaining their geometrical and electronic structures.Considering the indispensability and convenient availability of the solvents,present findings may boost the potential applications of superatoms in constructing super oxidizers in the condensed phase.
基金supported by the Taishan Scholars Project of Shandong Province(No.ts201712011)the National Natural Science Foundation of China(NSFC)(Nos.21603119 and 21705093)+3 种基金the Natural Science Foundation of Jiangsu Province(No.BK20170396)the Natural Science Foundation of Shandong Province(No.ZR2020ZD35)the Young Scholars Program of Shandong University(YSPSDU)(No.2018WLJH48)the Qilu Youth Scholar Funding of Shandong University.
文摘Superatoms are considered as promising building blocks for customizing superatomic molecules and cluster-assembly nanomaterials due to their tunable electronic structures and functionalities.Electron counting rules,which mainly adjust the shell-filling of clusters,are classical strategies in designing superatoms.Here,by employing the density functional theory(DFT)calculations,we proved that the 1,4-phenylene diisocyanide(CNC_(6)H_(4)NC)ligand could dramatically reduce the adiabatic ionization potentials(AlPs)of the aluminum-based clusters,which have 39,40,and 41 valence electrons,respectively,to give rise to superalkali species without changing their shell-filling.Moreover,the rigid structure of the ligand can be used as a bridge firmly linking the same or different aluminum-based clusters to form superatomic molecules and nanowires.In particular,the bridging process was observed to enhance their nonlinear optical(NLO)responses,which can be further promoted by the oriented external electric field(OEEF).Also,the stable cluster-assembly XAl_(12)(CNC_(6)H_(4)NC)(X=Al,C,and P)nanowires were constructed,which exhibit strong absorption in the visible light region.These findings not only suggest an effective ligand-field strategy in superatom design but also unveil the geometrical and electronic evolution from the CNC_(6)H_(4)NC-based superatoms to superatomic molecules and nanomaterials.
基金supported by the 2115 Talent Development Program of China Agricultural University.
文摘Oxygen vacancy(O_(v))as well as Ov migration in metal oxide are of great importance in structural evolution of active center in single-atom catalysts(SACs).Here,the interplay between invasive single Pt atom and native O_(v) in SA-Pt/rutile TiO_(2)(110)surface,as well as their synergetic effect on water dissociation are investigated by density functional theory(DFT)calculations.We show that importing Pt atom as Pt-ads,Pt_(2c),Pt_(5c) and Pt6c modes could decelerate the O_(v) migration effectively,especially in Pt6c mode.Under oxygen-rich conditions,Pt6c substitution could make oxygen Ov formation easier,but migration harder.On Pt_(6c)/Ti_(1-y)O_(2-x1)(110)surface,as a bimetal center,Pt_(4c)-Ti_(5c) concave could not make water dissociation process easier;however,the O2c closed to Pt become a good proton acceptor to make water dissociation on Ti_(5c)-O_(2c) more convenient with the aid of topmost Ti_(5c).
