Heteronanostructures(HNs)with precise components and interfaces are important for many applications,such as designing efficient and robust solar-to-fuel catalysts via integrating specific semiconductors with favorable...Heteronanostructures(HNs)with precise components and interfaces are important for many applications,such as designing efficient and robust solar-to-fuel catalysts via integrating specific semiconductors with favorable band alignments.However,rationally endowing such features with rigorous framework control remains a synthetic bottleneck.Herein,we report a modular divergent creation of dual-cocatalysts integrated semiconducting sulfide nanotriads(NTds),comprising both isolated Pd_(x)S oxidation(ox)and MoS_(2) reduction(red)domains within each single CdS counterpart,which exhibit superior photocatalytic activity and stability for hydrogen evolution reaction(HER).The stepwise constructed Pd_(x)S_((ox))−CdS−MoS_(2(red)) NTds possess dualinterfaces facilitating continuous charge separation and segregated active sites accelerating redox reactions,respectively,achieving the HER rate up to 9 mmol·h^(−1)·g^(−1),which is about 60 times higher than that of bare CdS,and show no evidence of deactivation after long-term cycling.This design principle and transformation protocol provide predictable retrosynthetic pathways to HNs with increased degree of complexity and more elaborate functionalities that are otherwise inaccessible.展开更多
Metallic-phase transition-metal dichalcogenides(TMDCs)exhibit unusual physicochemical properties compared with their semiconducting counterparts.However,they are thermodynamically unstable to access and it is even mor...Metallic-phase transition-metal dichalcogenides(TMDCs)exhibit unusual physicochemical properties compared with their semiconducting counterparts.However,they are thermodynamically unstable to access and it is even more challenging to construct their metastable-phase heterostructures.Herein,we demonstrate a general solution protocol for phase-controlled synthesis of distorted octahedral 1T WS2-based(1T structure denotes an octahedral coordination for W atom)multidimensional hybrid nanostructures from two-dimensional(2D),one-dimensional(1D),and zero-dimensional(0D)templates.This is realized by tuning the reactivity of tungsten precursor and the interaction between crystal surface and ligands.As a conceptual study on crystal phase-and dimensionality-dependent applications,we find that the three-dimensional(3D)hierarchical architectures achieved,comprising 1T WS2 and 2D Ni3S4,are very active and stable for catalyzing hydrogen evolution.Our results open up a new way to rationally design phase-controlled nanostructures with increased complexity and more elaborate functionalities.展开更多
CONSPECTUS:Programming nanoscale functional objects into complex,sophisticated heterostructures that tremendously outperform their solo objects and even bring about exotic chemical/physical properties offers exciting ...CONSPECTUS:Programming nanoscale functional objects into complex,sophisticated heterostructures that tremendously outperform their solo objects and even bring about exotic chemical/physical properties offers exciting routes toward a spectrum of applications in photonics and electronics.The development in synthetic chemistry over past decades has enabled a library of hybrid nanostructures,such as core−shell,patchy,dimer,hierarchical/branched ones,etc.Nevertheless,the material combinations of these non-van der Waals solids are largely limited by the rule of lattice-matched epitaxy thereof.As an emerging class of heterostructures,axially segmented nanowires(ASNWs)offer an alternative but effective approach to epitaxially integrating the conventional non-van der Waals solids.The large lattice-mismatch tolerance in ASNWs permits vast material combinations,broad size modulations,and flexible interfacial strain engineering,signifying the great potentials for engineering their photon utilizations,band structures,features of charge carriers or excitons,and some other emerging properties.Unfortunately,ASNWs with on-demand,high-precision control over composition,shape,dimension,crystal phase,interface,and periodicity remain so far synthetically challenging.By steering the chemoselective reactions,one has access to high-precision ASNWs.In this Account,we describe the state-of-the-art synthetic strategies for chemoselectivity control.We categorize them into(i)unidirectional/bidirectional sequential additions,which include selective area epitaxy,catalyzed growth,and end-facet-seeded growth,and(ii)regiospecific one-off transformations,which include ionic exchange reaction,strain/thermal induced phase segregation and transition,Plateau-Rayleigh instability,regioselective heterogeneous nucleation as ruled by lattice match,defect,and surface charges,and nanomasking.We uncover the chemical principles behind from thermodynamic and kinetic aspects.Then we further offer insights into their fundamental physics(including carrier/photon/phonon confinement,mixed dimensionality,quantum dot−nanowire interaction,and interdot coupling effect)that are strongly correlated with a spectrum of applications,highlighting how the precise control of compositions and structures ultimately dictates their properties and functions.In the end,we conclude by describing current challenges and future directions of this field in terms of material synthesis,growth mechanism,exotic physics,and performance optimization.By crafting ASNWs at atomic precision,high-performance ASNWs with sophisticated electronic and phonon structures can be envisioned ultimately for applications in diverse fields,spanning from solar energy conversion and thermoelectrics to optoelectronics and quantum communications.展开更多
基金the National Natural Science Foundation of China(Nos.21431006,U1932213,21905261,and 22171065)the National key Research and Development Program of China(Nos.2018YFE0202201 and 2021YFA0715700)+5 种基金the University Synergy Innovation Program of Anhui Province(No.GXXT-2019-028)the Science and Technology Major Project of Anhui Province(No.201903a05020003)S.K.H.acknowledges the Anhui Province Key Research and Development Plan(No.202104e11020005)the Hefei National Laboratory for Physical Sciences at the Microscale(No.KF2020005).C.G.acknowledges the National Postdoctoral Program for Innovative Talents(No.BX20180284)the China Postdoctoral Science Foundation(No.2019M660155).
文摘Heteronanostructures(HNs)with precise components and interfaces are important for many applications,such as designing efficient and robust solar-to-fuel catalysts via integrating specific semiconductors with favorable band alignments.However,rationally endowing such features with rigorous framework control remains a synthetic bottleneck.Herein,we report a modular divergent creation of dual-cocatalysts integrated semiconducting sulfide nanotriads(NTds),comprising both isolated Pd_(x)S oxidation(ox)and MoS_(2) reduction(red)domains within each single CdS counterpart,which exhibit superior photocatalytic activity and stability for hydrogen evolution reaction(HER).The stepwise constructed Pd_(x)S_((ox))−CdS−MoS_(2(red)) NTds possess dualinterfaces facilitating continuous charge separation and segregated active sites accelerating redox reactions,respectively,achieving the HER rate up to 9 mmol·h^(−1)·g^(−1),which is about 60 times higher than that of bare CdS,and show no evidence of deactivation after long-term cycling.This design principle and transformation protocol provide predictable retrosynthetic pathways to HNs with increased degree of complexity and more elaborate functionalities that are otherwise inaccessible.
基金supported by the National Natural Science Foundation of China(grant nos.21431006,21521001,and 21761132008)the Key Research Program of Frontier Sciences,CAS(grant no.QYZDJ-SSW-SLH036)+5 种基金the National Basic Research Program of China(grant no.2014CB931800)the Users with Excellence and Scientific Research Grant of Hefei Science Centre of CAS(grant no.2015HSC-UE007)S-K.H.acknowledges the Fundamental Research Funds for the Central Universities(grant no.PA2018GDQT0013)C.G.acknowledges the National Natural Science Foundation of China(grant no.21905261)the National Postdoctoral Program for Innovative Talents(grant no.BX20180284)the China Postdoctoral Science Foundation(grant no.2019M660155).
文摘Metallic-phase transition-metal dichalcogenides(TMDCs)exhibit unusual physicochemical properties compared with their semiconducting counterparts.However,they are thermodynamically unstable to access and it is even more challenging to construct their metastable-phase heterostructures.Herein,we demonstrate a general solution protocol for phase-controlled synthesis of distorted octahedral 1T WS2-based(1T structure denotes an octahedral coordination for W atom)multidimensional hybrid nanostructures from two-dimensional(2D),one-dimensional(1D),and zero-dimensional(0D)templates.This is realized by tuning the reactivity of tungsten precursor and the interaction between crystal surface and ligands.As a conceptual study on crystal phase-and dimensionality-dependent applications,we find that the three-dimensional(3D)hierarchical architectures achieved,comprising 1T WS2 and 2D Ni3S4,are very active and stable for catalyzing hydrogen evolution.Our results open up a new way to rationally design phase-controlled nanostructures with increased complexity and more elaborate functionalities.
基金This work was supported by the National Natural Science Foundation of China(Grants 51732011,21431006,21761132008,81788101,11227901)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(Grant 21521001)+1 种基金the Key Research Program of Frontier Sciences,CAS(Grant QYZDJ-SSWSLH036)the Users with Excellence and Scientific Research Grant of Hefei Science Center of CAS(2015HSCUE007).
文摘CONSPECTUS:Programming nanoscale functional objects into complex,sophisticated heterostructures that tremendously outperform their solo objects and even bring about exotic chemical/physical properties offers exciting routes toward a spectrum of applications in photonics and electronics.The development in synthetic chemistry over past decades has enabled a library of hybrid nanostructures,such as core−shell,patchy,dimer,hierarchical/branched ones,etc.Nevertheless,the material combinations of these non-van der Waals solids are largely limited by the rule of lattice-matched epitaxy thereof.As an emerging class of heterostructures,axially segmented nanowires(ASNWs)offer an alternative but effective approach to epitaxially integrating the conventional non-van der Waals solids.The large lattice-mismatch tolerance in ASNWs permits vast material combinations,broad size modulations,and flexible interfacial strain engineering,signifying the great potentials for engineering their photon utilizations,band structures,features of charge carriers or excitons,and some other emerging properties.Unfortunately,ASNWs with on-demand,high-precision control over composition,shape,dimension,crystal phase,interface,and periodicity remain so far synthetically challenging.By steering the chemoselective reactions,one has access to high-precision ASNWs.In this Account,we describe the state-of-the-art synthetic strategies for chemoselectivity control.We categorize them into(i)unidirectional/bidirectional sequential additions,which include selective area epitaxy,catalyzed growth,and end-facet-seeded growth,and(ii)regiospecific one-off transformations,which include ionic exchange reaction,strain/thermal induced phase segregation and transition,Plateau-Rayleigh instability,regioselective heterogeneous nucleation as ruled by lattice match,defect,and surface charges,and nanomasking.We uncover the chemical principles behind from thermodynamic and kinetic aspects.Then we further offer insights into their fundamental physics(including carrier/photon/phonon confinement,mixed dimensionality,quantum dot−nanowire interaction,and interdot coupling effect)that are strongly correlated with a spectrum of applications,highlighting how the precise control of compositions and structures ultimately dictates their properties and functions.In the end,we conclude by describing current challenges and future directions of this field in terms of material synthesis,growth mechanism,exotic physics,and performance optimization.By crafting ASNWs at atomic precision,high-performance ASNWs with sophisticated electronic and phonon structures can be envisioned ultimately for applications in diverse fields,spanning from solar energy conversion and thermoelectrics to optoelectronics and quantum communications.
