“Science has a simple faith,which transcends utility.It is the faith that it is the privilege of man to learn to understand,and that this is his mission.”1—Vannevar Bush,American Engineer(1890–1974)As New Years ce...“Science has a simple faith,which transcends utility.It is the faith that it is the privilege of man to learn to understand,and that this is his mission.”1—Vannevar Bush,American Engineer(1890–1974)As New Years celebrations ensue around the globe welcoming in 2026,we want to introduce and celebrate the accomplishments of the newest academicians elected to the Chinese Academy of Sciences(CAS)at the end of 2025.展开更多
Patrick J.Walsh Prof.Walsh is currently the Rhodes-Thompson Professor of Chemistry at the University of Pennsylvania(UPenn),USA.He is a native of San Diego and graduated from the University of California San Diego(UCS...Patrick J.Walsh Prof.Walsh is currently the Rhodes-Thompson Professor of Chemistry at the University of Pennsylvania(UPenn),USA.He is a native of San Diego and graduated from the University of California San Diego(UCSD),USA,where he worked under Prof.Charles L.Perrin.He received his Ph.D.from the University of California Berkeley,USA,under Prof.Robert G.Bergman,where he developed the chemistry of fascinating Zr=N–R containing compounds.He was a National Science Foundation Postdoctoral Fellow,working with Prof.K.Barry Sharpless at Scripps Research Institute in La Jolla,California,USA.He began his independent career at San Diego State University(SDSU),USA from 1994 to 1999 and move to UPenn in 1999.展开更多
Janus polymer nanorods with tunable compositions and microstructures possess directionally specific interactions,enabling their self-assembly into hierarchically structured materials(e.g.,biomimetic pillared nanostruc...Janus polymer nanorods with tunable compositions and microstructures possess directionally specific interactions,enabling their self-assembly into hierarchically structured materials(e.g.,biomimetic pillared nanostructures).Traditional synthesis methods usually require highly dilute conditions(<1 mg/mL)to prevent aggregation.Herein,we report the synthesis of Janus polymer nanorods by electrostatics-mediated reversible addition-fragmentation chain transfer copolymerization of cross-linkers and monomers from polymer bottlebrushes.This method achieves an unprecedentedly high solid content over 100 mg/mL,that is,two orders of magnitude higher than that attainable by conventional approaches.The composition,microstructure(e.g.,multilayered architecture),and characteristic dimension of the nanorods are broadly tunable.As a representative example,AB-type Janus nanorods are derived by orthogonal modifications of the end blocks,introducing desired functional groups to drive directional interactions.The Janus nanorods serve as building blocks to self-assemble into diverse superstructures from nanowires to continuous networks,providing a facile platform for the in-situ construction of functional materials within suitable matrices.展开更多
Monolayer-protected metal nanoclusters(NCs)are ultrasmall nanoparticles with a<3 nm core and capped by a protecting shell of metal–ligand motifs.Due to their ultrasmall size and atomically precise molecule-like st...Monolayer-protected metal nanoclusters(NCs)are ultrasmall nanoparticles with a<3 nm core and capped by a protecting shell of metal–ligand motifs.Due to their ultrasmall size and atomically precise molecule-like structure,metal NCs exhibit unique properties,including a discrete electronic structure,strong luminescence,programmable catalytic activity,and excellent biocompatibility.Within the unique core-shell structure of metal NCs,the protecting shell plays a pivotal role in defining their physicochemical properties.In this review,we summarize recent advances in the surface engineering of metal NCs that have tailored both the structure of the protecting shell and molecular properties of metal NCs at the molecular level.We first deciphered the protecting shell of metal NCs based on a three-layer structure hierarchy and examined the methodologies for modifying the protecting shell based on the hierarchical structure model.We then discuss strategies for tailoring cluster properties through surface engineering,aiming to establish a reliable structure-property relationship for metal NCs.Additionally,we explore the potential of surface engineering in promoting the crystallization of metal NCs.This review aims to provide valuable insights into customizing the properties of metal NCs through surface engineering and to guide future development in the crystallization of metal NCs.展开更多
Nanotips with high local electric fields,optimized reaction environment,and exceptional reactivity toward electrocatalysis have become an emerging frontier over the last decade.Along with significant breakthroughs in ...Nanotips with high local electric fields,optimized reaction environment,and exceptional reactivity toward electrocatalysis have become an emerging frontier over the last decade.Along with significant breakthroughs in the synthesis and application of nanotips with multiple architectures,the limited structure-function relationship is often underemphasized,posing amagnificent challenge in meeting the practical requirements.Generally,the synthetic method determines the structure of nanotips,which plays a decisive role in determining their performance.A comprehensive and systematic review is urgently needed to summarize the recent progress in the synthesis,properties,and application of nanomaterials with tip-effect,encompassing both supports and active sites.Herein,this review first summarizes the properties of curved supports with different dimensions from the perspective of experiments and theoretical calculations.Subsequently,the structure-function relationship of active sites is delineated,including the construction of multiple structured nanocrystals with different tip curvature radii,physicochemical properties of nanocrystals with different configurations and curvatures,and their application in electrocatalysis.Finally,the challenges and prospects for nanomaterials with tipeffect are discussed.This review facilitates a fundamental understanding of the tip-enhanced electric field and the following promoted mass transfer and charge delivery and provides guidance for constructing high performance electrocatalysts with tip-effect.展开更多
Helicenes are a quintessential class of aromatic molecules characterized by their inherent chirality.In recent years,helicene-derived macrocycles have attracted significant attention and witnessed rapid advancements d...Helicenes are a quintessential class of aromatic molecules characterized by their inherent chirality.In recent years,helicene-derived macrocycles have attracted significant attention and witnessed rapid advancements due to their unique conjugated geometries and topological structures,which endow them with intriguing properties such as chirality,selfassembly,and supramolecular organization.However,these macrocycles still face several challenges,including synthetic difficulties stemming from high strain energy,a limited understanding of structureproperty relationships,and restricted practical applications.This review is the first to highlight recent progress in helicene-derived macrocycles,categorizing them based on their geometric configurations.It provides an in-depth analysis of their synthetic strategies and explores the correlation between their structures and properties.Furthermore,the potential future directions and applications are discussed.展开更多
Selective electrosynthesis of industrially important alkenols in water(H_(2)O)offers a sustainable and highly efficient route to conventional thermocatalysis.Despite great progress in this area,the procedure is still ...Selective electrosynthesis of industrially important alkenols in water(H_(2)O)offers a sustainable and highly efficient route to conventional thermocatalysis.Despite great progress in this area,the procedure is still unsatisfactory because current electrocatalysts inevitably cause further overhydrogenation into industrially unfavorable alkanols.In this work,we propose a new enzyme-like electrocatalyst structurally composed of an umbrella-like Au core and a porous Cu shell for robust alkenol electrosynthesis.With 2-methyl-3-butyn-2-ol(MBY)as a substrate,porous Au@Cu heterojunctions(HJs)delivered remarkable performance for efficient 2-methyl-3-buten-2-ol(MBE)electrosynthesis,including∼100%of MBY conversion,>97.0%of MBE selectivity,and excellent stability,reaching 10 cycles.Mechanistic studies and density functional theory calculations revealed that active hydrogen radicals were electrocatalytically split on shell Cu sites and spilled over to and further stabilized on adjacent core Au sites,which thus promoted selective hydrogenation of MBY into MBE without further overhydrogenation into undesired byproduct.Further,hydrogen spillover on enzyme-like Au@Cu HJs was universally available for robust electrosynthesis of various alkenols with high alkynols conversion of>98%and impressive alkenol selectivity of>95%.In this work,we propose a new route to engineer hydrogen spillover by designing enzyme-like core-shell HJs for selective electrosynthesis of industrially important alkenols in a sustainable manner.展开更多
Polyolefins are widely used across industries due to their low cost and excellent stability.However,their inert C–C and C–H bonds pose a significant challenge for functional modification.Meanwhile,the environmental ...Polyolefins are widely used across industries due to their low cost and excellent stability.However,their inert C–C and C–H bonds pose a significant challenge for functional modification.Meanwhile,the environmental impact of polyolefin waste represents a significant and intensifying issue,rendering its disposal a major challenge.Herein,we developed renewable,recyclable,and durable resins while sustaining the capability to modularly construct various functionalities,called the“LEGO strategy,”via upcycling polyethylene(PE)into multifunctional materials through a two-step process:controlled degradation into macromolecular PE blocks containing active groups,followed by reconstruction with functional blocks via dynamic imine bonds.This approach enabled the incorporation of diverse functionalities,such as flame retardancy,ultraviolet shielding,antistatic performance,and cationic dyeability in an on-demand manner,while enhancing mechanical performance.Moreover,the dynamic nature of the imine bonds and the hydrophobic property of PE chains imparts both excellent water stability and recyclability.This approach offers a new pathway for upcycling polyolefins into diverse functional materials,addressing both environmental concerns and application demands.展开更多
The synthesis of nonbenzenoid nanographenes(NGs)with a high density of nonhexagonal rings remains a significant challenge,leaving this structural class largely unexplored.In this work,we report the efficient synthesis...The synthesis of nonbenzenoid nanographenes(NGs)with a high density of nonhexagonal rings remains a significant challenge,leaving this structural class largely unexplored.In this work,we report the efficient synthesis of a novel nonbenzenoid isomer of decacyclene,namely cyclopenta[cd]azulene trimer(CPAT),derived from the natural product guaiazulene.The key step involves an acid–base bufferassisted cyclotrimerization of cyclopenta[cd]azulen-2(1H)-one that can be further extended to produce halogenated derivative,enabling structural tunability.The resulting molecules feature a unique backbone comprising nine nonhexagonal rings arranged around a central benzenoid core,representing the highest pentagon–heptagon ring density among all reportedπ-extended NGs with ten or more fused rings.Compared to the pristine decacyclene,the synthesized compounds exhibit excellent ambient stability,narrower bandgaps,and distinct aromaticity profiles.Moreover,femtosecond transient absorption measurements of CPAT-a reveal an ultrafast singlet-state relaxation(∼14 ps),significantly shorter than that of decacyclene,highlighting the pronounced impact of nonbenzenoid topology on excited-state dynamics.This study introduces a new family of nonbenzenoid NGs and paves the way for the synthesis of newsp2 carbon allotrope featuring exclusively nonhexagonal ring systems.展开更多
A directing-group-on-leaving-group strategy(DGLG)was applied to stereospecific synthesis of 2-deoxy-2-fluoroglycosides via S_(N)2 glycosylation.This strategy utilized 2-deoxy-2-fluoroglycosyl donors featuring a chrome...A directing-group-on-leaving-group strategy(DGLG)was applied to stereospecific synthesis of 2-deoxy-2-fluoroglycosides via S_(N)2 glycosylation.This strategy utilized 2-deoxy-2-fluoroglycosyl donors featuring a chromenone-based leaving group,which is activated rapidly under exceedingly mild conditions to achieve complete stereochemical inversion at the donor anomeric position.This method readily applies to 2-deoxy-2-fluoroglucose,2-deoxy-2-fluorogalactose,2,6-dideoxy-2-fluoroglucose,2-deoxy-2-fluoroarabinose,and 2-deoxy-2-fluororibose,delivering high yields and complete stereochemical inversion,despite the presence of a neighboring deactivating fluoro group and the potential adverse fluorine directing effect.This method addresses the unmet challenges in constructing 1,2-cis glycosidic linkages in 2-deoxy-2-fluorosugars with stereospecificity.It also represents a major advance by enabling stereospecific synthesis of 2-deoxo-2-fluoroarabinofuranosides and 2-deoxy-2-fluororibofuranosides with either anαor aβanomeric configuration,showcasing the versatility of the DGLG approach.It offers by far the only stereospecific construction of these fluorinated glycosides of significant interest in glycoscience research.With the employment of excess donors permitted,this approach can be readily adopted to multistep sequential glycosylations,enabling streamlined and stereospecific access to complex fluorinated glycans.展开更多
Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simpl...Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simple and effective strategy for constructing a porphyrin-based supramolecular system to enhance the photosensitizing efficiency of porphyrins through a coordination-driven self-assembly process.In this work,a monofunctionalized tetraphenylethene(TPE)-based cage(1)with a pyridine group and a hydrophobic cavity was designed and synthesized.This covalent molecular cage can interact with zinc tetraphenyl porphyrin(2)through axial coordination of pyridine with the zinc ion,forming a coordinated complex(3).In solution,the ditopic complex 3,with both host and vip moieties,spontaneously assembles into a cyclic[c2]daisy chain(3_(2)).The self-assembly of 3_(2) combines the advantages of TPE and porphyrin units,leading to improved charge separation,efficient intersystem crossing,and stable triplet states.These features highly enhance the generation of reactive oxygen species(ROS).As a result,3_(2),as a photocatalyst,exhibits rapid catalytic oxidation of nicotinamide adenine dinucleotide(NADH),with a high turnover frequency of 13.4 min^(−1).By combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH,3_(2) functions as a supramolecular photosensitizer that demonstrates effective photodynamic therapy with good biocompatibility and biosafety in a hypoxic environment.展开更多
Dual-atom catalysts(DACs)exhibit strong oxygen reduction reaction(ORR)activity due to their unique electronic configurations.However,the coordination of metal atoms with highly electronegative nitrogen atoms results i...Dual-atom catalysts(DACs)exhibit strong oxygen reduction reaction(ORR)activity due to their unique electronic configurations.However,the coordination of metal atoms with highly electronegative nitrogen atoms results in a detrimental environment for the desorption of OH*from active sites.It is feasible to achieve precise modulation of the electronic structure and spin state of the active sites by regulating the bridging atoms of DACs.In this study,two Febased DACs with Fe-O_(2)-Fe and Fe-N_(2)-Fe structures have been successfully constructed,and the former shows higher ORR activity with half-wave potential of 0.930 V than the latter.Moreover,the Fe-O_(2)-Fe-based Zn-air battery demonstrates remarkable stability with continuous operation for 350 h.The superior performance is attributed to the Fe-O_(2)-Fe structure weakening the O–O bond via a peroxidelike bridge adsorption configuration,as well as the bridged oxygen atoms modifying Fe2 coordination,which lowers the spin state and d-band center,ultimately enhancing reaction kinetics.This study provides a foundation for the strategic development of Fe-based DACs by manipulating the spin states of Fe through the control of bridging atoms.展开更多
The surface property advantages of oxo-polyethylene(OPE)compared with virgin polyethylene(PE)make it a premium functional polyolefin material,yet its controllable synthesis remains a major challenge.Here,we report a s...The surface property advantages of oxo-polyethylene(OPE)compared with virgin polyethylene(PE)make it a premium functional polyolefin material,yet its controllable synthesis remains a major challenge.Here,we report a strategy for upgrading PE into OPE through a sequential catalytic process composed of transfer dehydrogenation and(reductive)hydroformylation with syngas.In contrast to the conventional oxidation-induced processes wherein breaking of the polymer chains is inevitable due to radicalβ-scission,this strong oxidant-free,dehydrogenation-enabled method produced OPE with no significant change in molecular weight.The manipulation of the sequential process allowed chemoselective synthesis of aldehyde-containing monofunctional PE(ald-PE)or alcohol-containing monofunctional PE(alc-PE)with microstructures featuring pendent functionalities in lieu of in-chain functionalities reported previously.The resulting polymers exhibited tunable bulk properties and superior surface properties,showing potential applications in compatibilizers,fluorescent,and photodegradable materials.The upgrading of various post-consumer PE materials into highervalue OPE demonstrated the applicability of this method in the upcycling of PE plastic wastes.展开更多
The increasing industrial demand for high-performance materials has exposed critical limitations in conventional manufacturing approaches,particularly regarding energy efficiency and environmental sustainability.Synth...The increasing industrial demand for high-performance materials has exposed critical limitations in conventional manufacturing approaches,particularly regarding energy efficiency and environmental sustainability.Synthetic biology has emerged as a transformative solution to address these challenges by engineering biological systems,specifically via precision engineering of microbial chassis,systematic optimization of metabolic pathways,and rational redesign of enzymatic machinery.This review systematically summarizes how these approaches have driven breakthroughs across material categories.For inorganic materials,engineered biomineralization systems combining protein display technologies have achieved exceptional metal recovery efficiencies while generating functional composites with self-repairing properties.Moreover,synthetic biology tools,including chassis design,enzyme engineering,and pathway optimization have significantly advanced both the efficiency and fidelity production of proteins and nucleic acids for multifunctional material applications.Notably,the development of optimized enzyme cascades and evolved synthase variants has produced sustainable biopolymers with enhanced thermal stability,greatly promoting industrial applications.Finally,this review assesses persistent challenges and emerging research directions enabled by the integration of synthetic biology,artificial intelligence,and automation.This synergistic integration drives the development of nextgeneration circular bioeconomy frameworks from sustainable raw material processing to advanced applications.展开更多
The prevalence of difluoroalkyl functionalities in drug discovery has stimulated tremendous advances in difluoroalkylation reactions.However,the dearomative hydrodifluoroalkylation of arenes remains an unsolved task d...The prevalence of difluoroalkyl functionalities in drug discovery has stimulated tremendous advances in difluoroalkylation reactions.However,the dearomative hydrodifluoroalkylation of arenes remains an unsolved task due to the severe challenges in breaking aromaticity and controlling intricate selectivities.Herein,we report a selective dearomative hydrodifluoroalkylation via η^(6)-coordination activation,enabling the direct conversion of nonactivated benzenes into high-value difluoroalkyl-containing 1,3-cyclohexadienes.Remarkably,the η^(6)-coordination mode exhibits exclusive activation selectivity for inert benzene substructures overcoming naphthalene and heteroaromatic rings,thus reversing the conventional dearomatization order of aromatic rings.The switchable synthesis of difluoroalkylated cyclohexadiene isomers as well as the extension to dearomative 1,2-deuterodifluoroalkylation further highlight the versatility.A reasonable reaction mechanism was proposed based on detailed intermediate tracking experiments.The synthetic utility was well demonstrated by high efficiency,broad scope,latestage modifications,downstream synthetic applications,and chromium recovery.展开更多
Chiral molecules bearing multiple stereocenters are prevalent in natural products and pharmaceuticals,with their absolute and relative configurations critically influencing biological activity.Consequently,the stereod...Chiral molecules bearing multiple stereocenters are prevalent in natural products and pharmaceuticals,with their absolute and relative configurations critically influencing biological activity.Consequently,the stereodivergent synthesis of all possible stereoisomers is of great importance,especially for comprehensive structure-activity relationship studies.However,conventional asymmetric catalytic methods typically favor the formation of a single major diastereomer,rendering access to the complete set of stereoisomers highly challenging.In recent years,synergistic dual catalysis has emerged as an effective strategy to this challenge.This approach employs a combination of two distinct chiral catalysts,such as metal/organo,metal/metal,or organo/organo catalytic systems,to enable precise control over enantio-and diastereoselectivity at two stereocenters.This minireview summarizes recent advances in synergistic dual catalytic strategies for the stereodivergent synthesis of multistereocentric compounds.Key aspects include catalyst types,reaction classes,mechanistic insights,and current limitations.In addition,perspectives on future opportunities and challenges in this rapidly evolving field are also discussed.展开更多
Photomechanical crystals,capable of transforming light energy into mechanical work,hold significant promise for applications in intelligent actuating devices,artificial muscles,and microrobots,but this calls for more ...Photomechanical crystals,capable of transforming light energy into mechanical work,hold significant promise for applications in intelligent actuating devices,artificial muscles,and microrobots,but this calls for more research on the influence of irradiation wavelengths.Here we report a discrete Cd(II)-based complex[Cd_(2)(CH_(2)OH-1,3-bpeb)_(4)(3,5-FBA)_(4)](1;CH_(2)OH-1,3-bpeb=5-hydroxymethyl-1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene,3,5-FBA=3,5-difluorobenzoate)which undergoes stepwise[2+2]photocycloaddition reactions under visible and ultraviolet light,forming mono-and di-cyclobutane products,respectively,through a single-crystal-to-singlecrystal transformation.This wavelength-controlled process involved the cleavage and subsequent reconstruction of Cd–O bonds within the crystal framework,along with the corresponding lattice contraction and expansion.Those photochemical reactions at different wavelengths initiate various crystal motions,which stem from the stress within the unit cell caused by anisotropic contraction/expansion.This work opens a new avenue for regulating wavelengths to achieve photocontrolled structural transformations and macroscopic photomechanical motions of molecular crystals.展开更多
The efficient recovery of rhenium(Re),a scarce metal closely associated with the energy and aerospace industries,is essential for alleviating global Re resource tension.For the first time,we propose a radiosensitizati...The efficient recovery of rhenium(Re),a scarce metal closely associated with the energy and aerospace industries,is essential for alleviating global Re resource tension.For the first time,we propose a radiosensitization reduction method to selectively reclaim ReO_(4)^(−) as ReO_(2) from its aqueous solutions,utilizing a stable Hf-based metal–organic framework,Hf-BPY,as an effective radiation sensitizer.While interacting withγ-rays or electron beams(EBs),Hf-BPY provides Hf6-cluster arrays with high atomic number,exhibiting radiation attenuation ability that enhances the radiolysis of water,which further increases the yield of reductive hydrated electrons(eaq^(−))from 2.80×10^(−7) to 4.05×10^(−7) mol/J.As a clean reduction method,the reaction is propelled directly by the enriched eaq^(−),without the need for any sacrificial agents.Pure ReO_(2) is obtained with resistance to reoxidation and redissolution.This laboratory-proven approach is further scaled up to liter scale,achieving the recovery of 0.568 and 0.468 g/L of ReO_(2) usingγ-ray and EB irradiation,respectively.Along with its cyclic ability to maintain a stable reduction ratio over seven radiation cycles,this approach holds great potential for industrial Re recovery.The feasibility of radiosensitization reduction for the decontamination of heavy metal pollution is further confirmed,adding to the evidence of its prospects for broad application.展开更多
An efficient Pd-catalyzed cascade cyclocarbonylation of 1,4-enynes with formic acid is described.A wide variety of bicyclic fused butenolides can be readily obtained in one pot in up to 76%yield under mild reaction co...An efficient Pd-catalyzed cascade cyclocarbonylation of 1,4-enynes with formic acid is described.A wide variety of bicyclic fused butenolides can be readily obtained in one pot in up to 76%yield under mild reaction conditions.The reaction process is operationally simple and requires no handling of CO gas.展开更多
Li-rich layered oxides(LRLOs)materials have been considered as one of the most promising cathode materials for next-generation lithium-ion batteries.However,LRLOs suffer from continuous phase transition from the layer...Li-rich layered oxides(LRLOs)materials have been considered as one of the most promising cathode materials for next-generation lithium-ion batteries.However,LRLOs suffer from continuous phase transition from the layered to rock-salt phase during cycling,and its origin still remains unclear.Here,we reveal that the accumulation of rock-salt phases originates from the compressive strain induced by phase transitions in which the initial surface rock-salt phase compresses its neighboring layered phase and further causes lattice contraction of the layered phase.This compressed layered phase always existed on the particle surface,leading to the rocksalt phase not completely covering the surface of the LRLOs particles.Also,the compressed layered phase can serve as an oxygen loss channel to lure the generation of more rock-salt phase,resulting in the phase transition gradually extending inwards.Based on this finding,we construct a uniform coherent spinel structure as a surface protection layer to suppress oxygen loss and the interior extension of rock-salt phase during cycling.As a result,the improved cathode materials demonstrate 99%voltage retention after 100 cycles.This work solves the surface inhomogeneous phase evolution of LRLOs,contributing to enhanced sustainability of high energy density cathode materials.展开更多
文摘“Science has a simple faith,which transcends utility.It is the faith that it is the privilege of man to learn to understand,and that this is his mission.”1—Vannevar Bush,American Engineer(1890–1974)As New Years celebrations ensue around the globe welcoming in 2026,we want to introduce and celebrate the accomplishments of the newest academicians elected to the Chinese Academy of Sciences(CAS)at the end of 2025.
文摘Patrick J.Walsh Prof.Walsh is currently the Rhodes-Thompson Professor of Chemistry at the University of Pennsylvania(UPenn),USA.He is a native of San Diego and graduated from the University of California San Diego(UCSD),USA,where he worked under Prof.Charles L.Perrin.He received his Ph.D.from the University of California Berkeley,USA,under Prof.Robert G.Bergman,where he developed the chemistry of fascinating Zr=N–R containing compounds.He was a National Science Foundation Postdoctoral Fellow,working with Prof.K.Barry Sharpless at Scripps Research Institute in La Jolla,California,USA.He began his independent career at San Diego State University(SDSU),USA from 1994 to 1999 and move to UPenn in 1999.
基金supported by the National Natural Science Foundation of China(grant nos.52293472 and 51833005)the National Key Research and Development Program of China(grant no.2021YFC2102800)start-up funding by Tsinghua University(grant no.53330100120).
文摘Janus polymer nanorods with tunable compositions and microstructures possess directionally specific interactions,enabling their self-assembly into hierarchically structured materials(e.g.,biomimetic pillared nanostructures).Traditional synthesis methods usually require highly dilute conditions(<1 mg/mL)to prevent aggregation.Herein,we report the synthesis of Janus polymer nanorods by electrostatics-mediated reversible addition-fragmentation chain transfer copolymerization of cross-linkers and monomers from polymer bottlebrushes.This method achieves an unprecedentedly high solid content over 100 mg/mL,that is,two orders of magnitude higher than that attainable by conventional approaches.The composition,microstructure(e.g.,multilayered architecture),and characteristic dimension of the nanorods are broadly tunable.As a representative example,AB-type Janus nanorods are derived by orthogonal modifications of the end blocks,introducing desired functional groups to drive directional interactions.The Janus nanorods serve as building blocks to self-assemble into diverse superstructures from nanowires to continuous networks,providing a facile platform for the in-situ construction of functional materials within suitable matrices.
基金supported by the National Natural Science Foundation of China(grant no.22371204)the Ministry of Education,Singapore(grant no.A-8000054-01-00)+1 种基金the Centre for Hydrogen Innovations at the National University of Singapore(NUSgrant no.CHIP2023-01).
文摘Monolayer-protected metal nanoclusters(NCs)are ultrasmall nanoparticles with a<3 nm core and capped by a protecting shell of metal–ligand motifs.Due to their ultrasmall size and atomically precise molecule-like structure,metal NCs exhibit unique properties,including a discrete electronic structure,strong luminescence,programmable catalytic activity,and excellent biocompatibility.Within the unique core-shell structure of metal NCs,the protecting shell plays a pivotal role in defining their physicochemical properties.In this review,we summarize recent advances in the surface engineering of metal NCs that have tailored both the structure of the protecting shell and molecular properties of metal NCs at the molecular level.We first deciphered the protecting shell of metal NCs based on a three-layer structure hierarchy and examined the methodologies for modifying the protecting shell based on the hierarchical structure model.We then discuss strategies for tailoring cluster properties through surface engineering,aiming to establish a reliable structure-property relationship for metal NCs.Additionally,we explore the potential of surface engineering in promoting the crystallization of metal NCs.This review aims to provide valuable insights into customizing the properties of metal NCs through surface engineering and to guide future development in the crystallization of metal NCs.
基金supported by the Jiangsu Provincial Natural Science Foundation of China(grant no.BK20230198)the National Natural Science Foundation of China(grant nos.91963206,21932004,and 51678291).
文摘Nanotips with high local electric fields,optimized reaction environment,and exceptional reactivity toward electrocatalysis have become an emerging frontier over the last decade.Along with significant breakthroughs in the synthesis and application of nanotips with multiple architectures,the limited structure-function relationship is often underemphasized,posing amagnificent challenge in meeting the practical requirements.Generally,the synthetic method determines the structure of nanotips,which plays a decisive role in determining their performance.A comprehensive and systematic review is urgently needed to summarize the recent progress in the synthesis,properties,and application of nanomaterials with tip-effect,encompassing both supports and active sites.Herein,this review first summarizes the properties of curved supports with different dimensions from the perspective of experiments and theoretical calculations.Subsequently,the structure-function relationship of active sites is delineated,including the construction of multiple structured nanocrystals with different tip curvature radii,physicochemical properties of nanocrystals with different configurations and curvatures,and their application in electrocatalysis.Finally,the challenges and prospects for nanomaterials with tipeffect are discussed.This review facilitates a fundamental understanding of the tip-enhanced electric field and the following promoted mass transfer and charge delivery and provides guidance for constructing high performance electrocatalysts with tip-effect.
基金supported by the National Key R&D Program of China(grant no.2023YFB3609000)the National Natural Science Foundation of China(grant no.22322502)the Natural Science Foundation of Shanghai(grant no.23ZR1405100).
文摘Helicenes are a quintessential class of aromatic molecules characterized by their inherent chirality.In recent years,helicene-derived macrocycles have attracted significant attention and witnessed rapid advancements due to their unique conjugated geometries and topological structures,which endow them with intriguing properties such as chirality,selfassembly,and supramolecular organization.However,these macrocycles still face several challenges,including synthetic difficulties stemming from high strain energy,a limited understanding of structureproperty relationships,and restricted practical applications.This review is the first to highlight recent progress in helicene-derived macrocycles,categorizing them based on their geometric configurations.It provides an in-depth analysis of their synthetic strategies and explores the correlation between their structures and properties.Furthermore,the potential future directions and applications are discussed.
基金supported by the National Natural Science Foundation of China(grant nos.22575159 and 22405169)the National Key Research and Development Program of China(grant no.2023YFC3905002)the Fundamental Research Funds for the Central Universities.
文摘Selective electrosynthesis of industrially important alkenols in water(H_(2)O)offers a sustainable and highly efficient route to conventional thermocatalysis.Despite great progress in this area,the procedure is still unsatisfactory because current electrocatalysts inevitably cause further overhydrogenation into industrially unfavorable alkanols.In this work,we propose a new enzyme-like electrocatalyst structurally composed of an umbrella-like Au core and a porous Cu shell for robust alkenol electrosynthesis.With 2-methyl-3-butyn-2-ol(MBY)as a substrate,porous Au@Cu heterojunctions(HJs)delivered remarkable performance for efficient 2-methyl-3-buten-2-ol(MBE)electrosynthesis,including∼100%of MBY conversion,>97.0%of MBE selectivity,and excellent stability,reaching 10 cycles.Mechanistic studies and density functional theory calculations revealed that active hydrogen radicals were electrocatalytically split on shell Cu sites and spilled over to and further stabilized on adjacent core Au sites,which thus promoted selective hydrogenation of MBY into MBE without further overhydrogenation into undesired byproduct.Further,hydrogen spillover on enzyme-like Au@Cu HJs was universally available for robust electrosynthesis of various alkenols with high alkynols conversion of>98%and impressive alkenol selectivity of>95%.In this work,we propose a new route to engineer hydrogen spillover by designing enzyme-like core-shell HJs for selective electrosynthesis of industrially important alkenols in a sustainable manner.
基金supported financially by the National Natural Science Foundation of China(grant no.22293063)the Fundamental Research Funds for the Central Universities,China,and the Institutional Research Fund from Sichuan University,China(grant no.2020SCUNL205)the innovation-based 111 project initiated by the Ministry of Education of China(grant no.B20001).
文摘Polyolefins are widely used across industries due to their low cost and excellent stability.However,their inert C–C and C–H bonds pose a significant challenge for functional modification.Meanwhile,the environmental impact of polyolefin waste represents a significant and intensifying issue,rendering its disposal a major challenge.Herein,we developed renewable,recyclable,and durable resins while sustaining the capability to modularly construct various functionalities,called the“LEGO strategy,”via upcycling polyethylene(PE)into multifunctional materials through a two-step process:controlled degradation into macromolecular PE blocks containing active groups,followed by reconstruction with functional blocks via dynamic imine bonds.This approach enabled the incorporation of diverse functionalities,such as flame retardancy,ultraviolet shielding,antistatic performance,and cationic dyeability in an on-demand manner,while enhancing mechanical performance.Moreover,the dynamic nature of the imine bonds and the hydrophobic property of PE chains imparts both excellent water stability and recyclability.This approach offers a new pathway for upcycling polyolefins into diverse functional materials,addressing both environmental concerns and application demands.
基金supported by the EU Graphene Flagship(Graphene Core 3,881603)EIC-2022-Pathfinder Open(ATYPIQUAL,101099098)+3 种基金the Center for Advancing Electronics Dresden(cfaed)the National Natural Science Foundation of China for funding(grant no.92463307)support for funding this project by providing computing time through the Center for Information Services and HPC(ZIH)at TU DresdenThis research was also made possible as a result of a generous grant from XYZ Foundation(grant no.123567).
文摘The synthesis of nonbenzenoid nanographenes(NGs)with a high density of nonhexagonal rings remains a significant challenge,leaving this structural class largely unexplored.In this work,we report the efficient synthesis of a novel nonbenzenoid isomer of decacyclene,namely cyclopenta[cd]azulene trimer(CPAT),derived from the natural product guaiazulene.The key step involves an acid–base bufferassisted cyclotrimerization of cyclopenta[cd]azulen-2(1H)-one that can be further extended to produce halogenated derivative,enabling structural tunability.The resulting molecules feature a unique backbone comprising nine nonhexagonal rings arranged around a central benzenoid core,representing the highest pentagon–heptagon ring density among all reportedπ-extended NGs with ten or more fused rings.Compared to the pristine decacyclene,the synthesized compounds exhibit excellent ambient stability,narrower bandgaps,and distinct aromaticity profiles.Moreover,femtosecond transient absorption measurements of CPAT-a reveal an ultrafast singlet-state relaxation(∼14 ps),significantly shorter than that of decacyclene,highlighting the pronounced impact of nonbenzenoid topology on excited-state dynamics.This study introduces a new family of nonbenzenoid NGs and paves the way for the synthesis of newsp2 carbon allotrope featuring exclusively nonhexagonal ring systems.
基金support of the National Science Foundation(NSF CHE-2247934)the National Institute of General Medical Science(NIGMS R35GM139640)+1 种基金NSF MRI-1920299 enabled us to acquire the Bruker 500 MHz and 400 MHz NMR instrumentsthe HR-MS analysis was performed by a LS-MS instrument funded by the office of Navy Research Award N00014-23-2197.
文摘A directing-group-on-leaving-group strategy(DGLG)was applied to stereospecific synthesis of 2-deoxy-2-fluoroglycosides via S_(N)2 glycosylation.This strategy utilized 2-deoxy-2-fluoroglycosyl donors featuring a chromenone-based leaving group,which is activated rapidly under exceedingly mild conditions to achieve complete stereochemical inversion at the donor anomeric position.This method readily applies to 2-deoxy-2-fluoroglucose,2-deoxy-2-fluorogalactose,2,6-dideoxy-2-fluoroglucose,2-deoxy-2-fluoroarabinose,and 2-deoxy-2-fluororibose,delivering high yields and complete stereochemical inversion,despite the presence of a neighboring deactivating fluoro group and the potential adverse fluorine directing effect.This method addresses the unmet challenges in constructing 1,2-cis glycosidic linkages in 2-deoxy-2-fluorosugars with stereospecificity.It also represents a major advance by enabling stereospecific synthesis of 2-deoxo-2-fluoroarabinofuranosides and 2-deoxy-2-fluororibofuranosides with either anαor aβanomeric configuration,showcasing the versatility of the DGLG approach.It offers by far the only stereospecific construction of these fluorinated glycosides of significant interest in glycoscience research.With the employment of excess donors permitted,this approach can be readily adopted to multistep sequential glycosylations,enabling streamlined and stereospecific access to complex fluorinated glycans.
基金supported by the National Natural Science Foundation of China(grant nos.22371229 and 22301241)the National Key R&D Program of China,Synthetic Biology Research(grant no.2023YFA0913600).
文摘Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simple and effective strategy for constructing a porphyrin-based supramolecular system to enhance the photosensitizing efficiency of porphyrins through a coordination-driven self-assembly process.In this work,a monofunctionalized tetraphenylethene(TPE)-based cage(1)with a pyridine group and a hydrophobic cavity was designed and synthesized.This covalent molecular cage can interact with zinc tetraphenyl porphyrin(2)through axial coordination of pyridine with the zinc ion,forming a coordinated complex(3).In solution,the ditopic complex 3,with both host and vip moieties,spontaneously assembles into a cyclic[c2]daisy chain(3_(2)).The self-assembly of 3_(2) combines the advantages of TPE and porphyrin units,leading to improved charge separation,efficient intersystem crossing,and stable triplet states.These features highly enhance the generation of reactive oxygen species(ROS).As a result,3_(2),as a photocatalyst,exhibits rapid catalytic oxidation of nicotinamide adenine dinucleotide(NADH),with a high turnover frequency of 13.4 min^(−1).By combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH,3_(2) functions as a supramolecular photosensitizer that demonstrates effective photodynamic therapy with good biocompatibility and biosafety in a hypoxic environment.
基金supported by the Natural Science Foundation of Jilin Province(grant no.20220101051JC)the National Natural Science Foundation of China(grant no.22075099).
文摘Dual-atom catalysts(DACs)exhibit strong oxygen reduction reaction(ORR)activity due to their unique electronic configurations.However,the coordination of metal atoms with highly electronegative nitrogen atoms results in a detrimental environment for the desorption of OH*from active sites.It is feasible to achieve precise modulation of the electronic structure and spin state of the active sites by regulating the bridging atoms of DACs.In this study,two Febased DACs with Fe-O_(2)-Fe and Fe-N_(2)-Fe structures have been successfully constructed,and the former shows higher ORR activity with half-wave potential of 0.930 V than the latter.Moreover,the Fe-O_(2)-Fe-based Zn-air battery demonstrates remarkable stability with continuous operation for 350 h.The superior performance is attributed to the Fe-O_(2)-Fe structure weakening the O–O bond via a peroxidelike bridge adsorption configuration,as well as the bridged oxygen atoms modifying Fe2 coordination,which lowers the spin state and d-band center,ultimately enhancing reaction kinetics.This study provides a foundation for the strategic development of Fe-based DACs by manipulating the spin states of Fe through the control of bridging atoms.
基金support from the National Key R&D Program of China(grant no.2021YFA1501700)National Natural Science Foundation of China(grant nos.22425012 and 22293013)+7 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(CASgrant no.XDB0610000)CAS Project for Young Scientists in Basic Research(grant no.YSBR-094)Science and Technology Commission of Shanghai Municipality(grant no.23JC1404400)and the Shanghai Sailing Program(grant no.24YF2756700)support from the Analytical Instrumentation Center(#SPST-AIC10112914)the School of Physical Science and Technology(SPST)Shanghai Tech University.
文摘The surface property advantages of oxo-polyethylene(OPE)compared with virgin polyethylene(PE)make it a premium functional polyolefin material,yet its controllable synthesis remains a major challenge.Here,we report a strategy for upgrading PE into OPE through a sequential catalytic process composed of transfer dehydrogenation and(reductive)hydroformylation with syngas.In contrast to the conventional oxidation-induced processes wherein breaking of the polymer chains is inevitable due to radicalβ-scission,this strong oxidant-free,dehydrogenation-enabled method produced OPE with no significant change in molecular weight.The manipulation of the sequential process allowed chemoselective synthesis of aldehyde-containing monofunctional PE(ald-PE)or alcohol-containing monofunctional PE(alc-PE)with microstructures featuring pendent functionalities in lieu of in-chain functionalities reported previously.The resulting polymers exhibited tunable bulk properties and superior surface properties,showing potential applications in compatibilizers,fluorescent,and photodegradable materials.The upgrading of various post-consumer PE materials into highervalue OPE demonstrated the applicability of this method in the upcycling of PE plastic wastes.
基金supported by the National Key R&D Program of China(grant no.2024YFA0919300 for K.L.)the National Nature Science Foundation of China(grant nos.22020102003 and 22388101 for H.J.Z.,22125701 for K.L.,52222214 and 52372274 for F.W.,22422704 and 22377121 for J.J.L.,52472112 and 22207104 for Y.W.L.,T2322025 and 82272161 for J.J.S.,and 22407071 for H.J.C.)+3 种基金the China Postdoctoral Science Foundation(grant no.2024M753180 for Y.Y.L.)the Natural Science Foundation of Jilin Province,China(grant no.20240101175JC for F.W.)the Xiangfu Lab Research Project(grant no.XF012022C0200 for K.L.)the National High Level Hospital Clinical Research Funding and Fundamental Research Funds for the Central Universities(grant no.BJ-2023-118 for J.J.S.).
文摘The increasing industrial demand for high-performance materials has exposed critical limitations in conventional manufacturing approaches,particularly regarding energy efficiency and environmental sustainability.Synthetic biology has emerged as a transformative solution to address these challenges by engineering biological systems,specifically via precision engineering of microbial chassis,systematic optimization of metabolic pathways,and rational redesign of enzymatic machinery.This review systematically summarizes how these approaches have driven breakthroughs across material categories.For inorganic materials,engineered biomineralization systems combining protein display technologies have achieved exceptional metal recovery efficiencies while generating functional composites with self-repairing properties.Moreover,synthetic biology tools,including chassis design,enzyme engineering,and pathway optimization have significantly advanced both the efficiency and fidelity production of proteins and nucleic acids for multifunctional material applications.Notably,the development of optimized enzyme cascades and evolved synthase variants has produced sustainable biopolymers with enhanced thermal stability,greatly promoting industrial applications.Finally,this review assesses persistent challenges and emerging research directions enabled by the integration of synthetic biology,artificial intelligence,and automation.This synergistic integration drives the development of nextgeneration circular bioeconomy frameworks from sustainable raw material processing to advanced applications.
基金support from the National Natural Science Foundation of China(grant nos.22271251 and 22471238)the Fundamental Research Funds for the Central Universities(grant no.226-2023-00016).
文摘The prevalence of difluoroalkyl functionalities in drug discovery has stimulated tremendous advances in difluoroalkylation reactions.However,the dearomative hydrodifluoroalkylation of arenes remains an unsolved task due to the severe challenges in breaking aromaticity and controlling intricate selectivities.Herein,we report a selective dearomative hydrodifluoroalkylation via η^(6)-coordination activation,enabling the direct conversion of nonactivated benzenes into high-value difluoroalkyl-containing 1,3-cyclohexadienes.Remarkably,the η^(6)-coordination mode exhibits exclusive activation selectivity for inert benzene substructures overcoming naphthalene and heteroaromatic rings,thus reversing the conventional dearomatization order of aromatic rings.The switchable synthesis of difluoroalkylated cyclohexadiene isomers as well as the extension to dearomative 1,2-deuterodifluoroalkylation further highlight the versatility.A reasonable reaction mechanism was proposed based on detailed intermediate tracking experiments.The synthetic utility was well demonstrated by high efficiency,broad scope,latestage modifications,downstream synthetic applications,and chromium recovery.
基金the National Key R&D Program of China(grant no.2023YFA1506700)the National Natural Science Foundation of China(grant nos.22371216 and 22501173)China Postdoctoral Science Foundation(grant nos.2025M770979 and 2025T180266)for financial support.
文摘Chiral molecules bearing multiple stereocenters are prevalent in natural products and pharmaceuticals,with their absolute and relative configurations critically influencing biological activity.Consequently,the stereodivergent synthesis of all possible stereoisomers is of great importance,especially for comprehensive structure-activity relationship studies.However,conventional asymmetric catalytic methods typically favor the formation of a single major diastereomer,rendering access to the complete set of stereoisomers highly challenging.In recent years,synergistic dual catalysis has emerged as an effective strategy to this challenge.This approach employs a combination of two distinct chiral catalysts,such as metal/organo,metal/metal,or organo/organo catalytic systems,to enable precise control over enantio-and diastereoselectivity at two stereocenters.This minireview summarizes recent advances in synergistic dual catalytic strategies for the stereodivergent synthesis of multistereocentric compounds.Key aspects include catalyst types,reaction classes,mechanistic insights,and current limitations.In addition,perspectives on future opportunities and challenges in this rapidly evolving field are also discussed.
基金support from the National Natural Science Foundation of China(grant nos.U24A20507,22271203,and 22301204)the State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry(grant no.2024KF005)+2 种基金Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Collaborative Innovation Centre of Suzhou Nano Science and Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions,the Project of Scientific and Technologic Infrastructure of Suzhou(grant no.SZS201905)Soochow University Starting Grant(grant no.NH10902124 to Q.L.)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(grant no.KYCX23_3232).
文摘Photomechanical crystals,capable of transforming light energy into mechanical work,hold significant promise for applications in intelligent actuating devices,artificial muscles,and microrobots,but this calls for more research on the influence of irradiation wavelengths.Here we report a discrete Cd(II)-based complex[Cd_(2)(CH_(2)OH-1,3-bpeb)_(4)(3,5-FBA)_(4)](1;CH_(2)OH-1,3-bpeb=5-hydroxymethyl-1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene,3,5-FBA=3,5-difluorobenzoate)which undergoes stepwise[2+2]photocycloaddition reactions under visible and ultraviolet light,forming mono-and di-cyclobutane products,respectively,through a single-crystal-to-singlecrystal transformation.This wavelength-controlled process involved the cleavage and subsequent reconstruction of Cd–O bonds within the crystal framework,along with the corresponding lattice contraction and expansion.Those photochemical reactions at different wavelengths initiate various crystal motions,which stem from the stress within the unit cell caused by anisotropic contraction/expansion.This work opens a new avenue for regulating wavelengths to achieve photocontrolled structural transformations and macroscopic photomechanical motions of molecular crystals.
基金support from the National Natural Science Foundation of China(grant nos.12205009,12375336,and U20B2019).
文摘The efficient recovery of rhenium(Re),a scarce metal closely associated with the energy and aerospace industries,is essential for alleviating global Re resource tension.For the first time,we propose a radiosensitization reduction method to selectively reclaim ReO_(4)^(−) as ReO_(2) from its aqueous solutions,utilizing a stable Hf-based metal–organic framework,Hf-BPY,as an effective radiation sensitizer.While interacting withγ-rays or electron beams(EBs),Hf-BPY provides Hf6-cluster arrays with high atomic number,exhibiting radiation attenuation ability that enhances the radiolysis of water,which further increases the yield of reductive hydrated electrons(eaq^(−))from 2.80×10^(−7) to 4.05×10^(−7) mol/J.As a clean reduction method,the reaction is propelled directly by the enriched eaq^(−),without the need for any sacrificial agents.Pure ReO_(2) is obtained with resistance to reoxidation and redissolution.This laboratory-proven approach is further scaled up to liter scale,achieving the recovery of 0.568 and 0.468 g/L of ReO_(2) usingγ-ray and EB irradiation,respectively.Along with its cyclic ability to maintain a stable reduction ratio over seven radiation cycles,this approach holds great potential for industrial Re recovery.The feasibility of radiosensitization reduction for the decontamination of heavy metal pollution is further confirmed,adding to the evidence of its prospects for broad application.
基金supported by the National Natural Science Foundation of China(grant nos.22271024 and 21632005)the Natural Science Foundation of Jiangsu Province(grant no.BK20190929)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(grant no.KYCX24_3208).
文摘An efficient Pd-catalyzed cascade cyclocarbonylation of 1,4-enynes with formic acid is described.A wide variety of bicyclic fused butenolides can be readily obtained in one pot in up to 76%yield under mild reaction conditions.The reaction process is operationally simple and requires no handling of CO gas.
基金supported by the Natural Science Foundation of Tianjin(grant nos.24JCJQJC00220 and 24ZXZSSS00390)the National Natural Science Foundation of China(grant nos.22479080,22121005,92372203,and 92372001)+1 种基金the Open Foundation of Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(grant no.JDSX2023003)the Fundamental Research Funds for the Central Universities of Nankai University(grant nos.63241206 and 9242000710).
文摘Li-rich layered oxides(LRLOs)materials have been considered as one of the most promising cathode materials for next-generation lithium-ion batteries.However,LRLOs suffer from continuous phase transition from the layered to rock-salt phase during cycling,and its origin still remains unclear.Here,we reveal that the accumulation of rock-salt phases originates from the compressive strain induced by phase transitions in which the initial surface rock-salt phase compresses its neighboring layered phase and further causes lattice contraction of the layered phase.This compressed layered phase always existed on the particle surface,leading to the rocksalt phase not completely covering the surface of the LRLOs particles.Also,the compressed layered phase can serve as an oxygen loss channel to lure the generation of more rock-salt phase,resulting in the phase transition gradually extending inwards.Based on this finding,we construct a uniform coherent spinel structure as a surface protection layer to suppress oxygen loss and the interior extension of rock-salt phase during cycling.As a result,the improved cathode materials demonstrate 99%voltage retention after 100 cycles.This work solves the surface inhomogeneous phase evolution of LRLOs,contributing to enhanced sustainability of high energy density cathode materials.
