CONSPECTUS:Nature presents us with numerous complex topological structures,among which ordered bicontinuous structures are widely found in biological systems and exhibit numerous functions,as exemplified by the vibran...CONSPECTUS:Nature presents us with numerous complex topological structures,among which ordered bicontinuous structures are widely found in biological systems and exhibit numerous functions,as exemplified by the vibrant wings of butterflies and the robust skeletons of knobby starfish.In recent decades,significant strides have been made in preparing functional materials with bicontinuous porous structures,e.g.,cubosomes�spherical colloidal particles,which encompass continuous pores and frameworks arranged in a cubic crystal lattice.These cubosomes exhibit many remarkable advantages due to their unique periodic topological structure.(1)The three-dimensional(3D)interconnected pores facilitate the smooth transport of substances throughout the material,resulting in at least a three times higher utilization ratio of internal active sites compared to that of their unconnected pore or nonporous counterparts.Their complex,tortuous,and periodic porous configuration can enhance energy capture,such as solar/electric energy.(2)The 3D continuous pore channels and frameworks provide“highways”for ion and electron transport,leading to an order-of-magnitude reduction in charge-transfer resistance and an over 3-fold increase in the ion diffusion coefficient compared to those of nonporous analogues,thereby improving the electrochemical kinetics of electrodes.(3)Cubosomes have emerged as unique mechanical metamaterials,exhibiting a remarkable capability to alleviate mechanical stress and strain.(4)Their negative-Gaussian-curvature surfaces facilitate the adsorption/desorption of reaction intermediates,thereby lowering the reaction free energy in catalytic reaction processes.Additionally,this distinctive surface structure can enhance the electric field intensity at material interfaces,significantly promoting ion adsorption.With these advantages,functional cubosomes show potential for application in the field of energy storage and conversion.However,due to the big challenges in their preparation,there have been limited studies on their structure−activity relationships in energy-related applications.Therefore,there has not yet been a review regarding functional cubosomes.In this Account,we summarize mainly our latest progress in the study of functional cubosomes.First,we introduce the preparation of polymer cubosomes(PCs)through the self-assembly of block copolymers in solution,along with plotting their morphological phase diagram.Then,the Account describes nanocasting approaches in which polymer cubosomes are employed as templates to prepare a variety of functional cubosomes,including polymers,covalent organic frameworks(COFs),metal−organic frameworks(MOFs),metal−phenolic networks,carbons,inorganic metal compounds,and metals.Finally,to elucidate the application prospects of the functional cubosomes,this Account discusses their advantages in different energy storage and conversion applications,highlighting efficient material and energy utilization,fast mass and electron transport,negative-Gaussian-curvature surfaces,and excellent mechanical stability.We anticipate that this Account will demystify functional cubosomes with bicontinuous porous structures and stimulate their broad interest in the fields of materials science,chemistry,and energy,among others.展开更多
Transition metal dichalcogenides(TMDs)have been regarded as promising cathodes for aqueous zinc-ion batteries(AZIBs)but suffer from sluggish reaction kinetics due to their poor conductivity and the strong electrostati...Transition metal dichalcogenides(TMDs)have been regarded as promising cathodes for aqueous zinc-ion batteries(AZIBs)but suffer from sluggish reaction kinetics due to their poor conductivity and the strong electrostatic interaction between Zn-ion and cathode materials.Herein,a well-defined structure with MoSSe nanosheets vertically anchored on graphene is used as the cathode for AZIBs.The dissolution of Se into MoS2 lattice together with heterointerface design via developing C-O-Mo bonds improves the inherent conductivity,enlarges interlayer spacing,and generates abundant anionic vacancies.As a result,the Zn2+intercalation/deintercalation process is greatly improved,which is confirmed by theoretical modeling and ex-situ experimental results.Remarkably,the assembled AZIBs exhibit high-rate capability(124.2 mAh·g^(−1)at 5 A·g^(−1))and long cycling life(83%capacity retention after 1,200 cycles at 2 A·g^(−1)).Moreover,the assembled quasi-solid-state Zn-ion batteries demonstrate a stable cycling performance over 100 cycles and high capacity retention over 94%after 2,500 bending cycles.This study provides a new strategy to unlock the electrochemical activity of TMDs via interface design and atomic engineering,which can also be applied to other TMDs for multivalent batteries.展开更多
基金supported by the National Natural Science Foundation of China(22225501,W2412102,52421006,22305149,52303275,and 52203268)the Shanghai Municipal Science and Technology Major Project,and SJTU 2030B plan(WH510207202).
文摘CONSPECTUS:Nature presents us with numerous complex topological structures,among which ordered bicontinuous structures are widely found in biological systems and exhibit numerous functions,as exemplified by the vibrant wings of butterflies and the robust skeletons of knobby starfish.In recent decades,significant strides have been made in preparing functional materials with bicontinuous porous structures,e.g.,cubosomes�spherical colloidal particles,which encompass continuous pores and frameworks arranged in a cubic crystal lattice.These cubosomes exhibit many remarkable advantages due to their unique periodic topological structure.(1)The three-dimensional(3D)interconnected pores facilitate the smooth transport of substances throughout the material,resulting in at least a three times higher utilization ratio of internal active sites compared to that of their unconnected pore or nonporous counterparts.Their complex,tortuous,and periodic porous configuration can enhance energy capture,such as solar/electric energy.(2)The 3D continuous pore channels and frameworks provide“highways”for ion and electron transport,leading to an order-of-magnitude reduction in charge-transfer resistance and an over 3-fold increase in the ion diffusion coefficient compared to those of nonporous analogues,thereby improving the electrochemical kinetics of electrodes.(3)Cubosomes have emerged as unique mechanical metamaterials,exhibiting a remarkable capability to alleviate mechanical stress and strain.(4)Their negative-Gaussian-curvature surfaces facilitate the adsorption/desorption of reaction intermediates,thereby lowering the reaction free energy in catalytic reaction processes.Additionally,this distinctive surface structure can enhance the electric field intensity at material interfaces,significantly promoting ion adsorption.With these advantages,functional cubosomes show potential for application in the field of energy storage and conversion.However,due to the big challenges in their preparation,there have been limited studies on their structure−activity relationships in energy-related applications.Therefore,there has not yet been a review regarding functional cubosomes.In this Account,we summarize mainly our latest progress in the study of functional cubosomes.First,we introduce the preparation of polymer cubosomes(PCs)through the self-assembly of block copolymers in solution,along with plotting their morphological phase diagram.Then,the Account describes nanocasting approaches in which polymer cubosomes are employed as templates to prepare a variety of functional cubosomes,including polymers,covalent organic frameworks(COFs),metal−organic frameworks(MOFs),metal−phenolic networks,carbons,inorganic metal compounds,and metals.Finally,to elucidate the application prospects of the functional cubosomes,this Account discusses their advantages in different energy storage and conversion applications,highlighting efficient material and energy utilization,fast mass and electron transport,negative-Gaussian-curvature surfaces,and excellent mechanical stability.We anticipate that this Account will demystify functional cubosomes with bicontinuous porous structures and stimulate their broad interest in the fields of materials science,chemistry,and energy,among others.
基金supported by the National Natural Science Foundation of China(No.52172217)Natural Science Foundation of Guangdong Province(No.2021A1515010144)+4 种基金Natural Science Foundation of Shanghai(No.17ZR1414100)the Shenzhen Science and Technology Program(No.JCYJ20210324120400002)G.M.Z.appreciates the support from the National Key Research and Development Program of China(No.2019YFA0705700)Joint Funds of the National Natural Science Foundation of China(No.U21A20174)the Overseas Research Cooperation Fund of Tsinghua Shenzhen International Graduate School.
文摘Transition metal dichalcogenides(TMDs)have been regarded as promising cathodes for aqueous zinc-ion batteries(AZIBs)but suffer from sluggish reaction kinetics due to their poor conductivity and the strong electrostatic interaction between Zn-ion and cathode materials.Herein,a well-defined structure with MoSSe nanosheets vertically anchored on graphene is used as the cathode for AZIBs.The dissolution of Se into MoS2 lattice together with heterointerface design via developing C-O-Mo bonds improves the inherent conductivity,enlarges interlayer spacing,and generates abundant anionic vacancies.As a result,the Zn2+intercalation/deintercalation process is greatly improved,which is confirmed by theoretical modeling and ex-situ experimental results.Remarkably,the assembled AZIBs exhibit high-rate capability(124.2 mAh·g^(−1)at 5 A·g^(−1))and long cycling life(83%capacity retention after 1,200 cycles at 2 A·g^(−1)).Moreover,the assembled quasi-solid-state Zn-ion batteries demonstrate a stable cycling performance over 100 cycles and high capacity retention over 94%after 2,500 bending cycles.This study provides a new strategy to unlock the electrochemical activity of TMDs via interface design and atomic engineering,which can also be applied to other TMDs for multivalent batteries.
