Although the combination of electrochemistry and homogeneous catalysis has proven to be a powerful strategy for achieving a diverse array of novel transformations,some challenges such as controlling the diffusion of c...Although the combination of electrochemistry and homogeneous catalysis has proven to be a powerful strategy for achieving a diverse array of novel transformations,some challenges such as controlling the diffusion of catalyst-related species and the instability of catalysts at electrodes remain to be overcome.Herein,we review recent advances in electrochemical homogeneous catalysis,focusing on electrochemical noble-transition-metal catalysis,photoelectrochemical catalysis,and electrochemical enantioselective catalysis.The topics discussed include:(1)how the noblemetal catalystworks in the presence of cathodic hydrogen evolution,(2)how the photocatalyst gets enhanced redox property,and(3)how the enantioselectivity is regulated in a catalytic electrochemical reaction.展开更多
“A journey of a thousand miles begins with a single step.”—Laozi,Chinese philosopher Welcome to the first issue of CCS Chemistry for 2023!We are excited to be starting on our fifth volume of the journal.Since our l...“A journey of a thousand miles begins with a single step.”—Laozi,Chinese philosopher Welcome to the first issue of CCS Chemistry for 2023!We are excited to be starting on our fifth volume of the journal.Since our launch in 2019,we have gained a lot of momentum,reviewed thousands ofmanuscripts,and published some of the best work in chemistry.We have been very fortunate during that time to have Prof.展开更多
Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumpt...Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumption worldwide.However,complicated sul-fur redox reactions and polysulfide shuttling signifi-cantly postpone the applications of lithium-sulfur batteries with rapid capacity decay and low Coulom-bic efficiency.展开更多
A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer conce...A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer concentrations.Various nanoparticlemorphologies such as spheres,worms,and vesicles can be prepared readily in polar and nonpolarmedia.PISA has been well developed in combination with reversible addition-fragmentation chain transfer(RAFT)polymerization.Notably,developments with other polymerization methods are also achieved.In this report,first,we discuss the general principles of RAFT-PISA and the nanoparticles generated from this method.Specifically,new insights into polymer nucleation and subsequent morphological evolution are highlighted.Subsequently,PISA formulations that use other polymerization methods[atom transfer radical polymerization(ATRP),nitroxide-mediated polymerization(NMP),ring-opening metathesis polymerization(ROMP),and ring-opening polymerization(ROP)of N-carboxyanhydrides(NCAs)]are summarized in detail.Finally,more exotic PISA formulations are emphasized:these are based on organotelluriummediated living radical polymerization(TERP),living anionic polymerization(LAP),addition-fragmentation chain transfer(AFCT)polymerization,reversible complexation-mediated polymerization(RCMP),and cobalt-mediated radical polymerization(CMRP),or utilize a comonomer that undergoes radical ringopening polymerization(rROP).This reviewis concluded with a perspective on the status and potential of PISA.展开更多
The use of transition-metal phosphides(TMPs)as catalytic materials to accelerate kinetics of lithium polysulfide(LiPS)conversion has unique advantages.Nevertheless,simple and low-cost preparation strategies are still ...The use of transition-metal phosphides(TMPs)as catalytic materials to accelerate kinetics of lithium polysulfide(LiPS)conversion has unique advantages.Nevertheless,simple and low-cost preparation strategies are still required for the synthesis of novel TMPs with satisfactory performance.Importantly,the in-depth understanding of the effect of intrinsic interaction between catalytic materials and LiPSs on the promoted kinetics remains limited.Herein,a novel structure of tungsten phosphide(WP)nanocrystals decorated on N,P codoped carbon sheets(WP/NPC)with uniform dispersion is designed by a structure-oriented strategy to promote LiPS redox kinetics.The electrochemical kinetics measurements coupled with density functional theory computations and in situ/ex situ characterizations demonstrate that the strong interaction through W–S bonding and the favorable interfacial charge state of WP-LiPSs promote the nucleation and dissociation of Li2S.Benefiting from this superiority,the WP/NPG-based lithium–sulfur batteries indicate significantly improved electrochemical performance with good cycling life and excellent rate capability.This work provides a methodology for the design of TMP-involved electrode materials and a fundamental understanding of the intrinsic mechanism of catalysis.展开更多
After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important ...After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important new concepts have been proposed,such as natural surface charge distribution inhomogeneity,multicavity space limiting effect,incomplete charge transfer effect on the atomic level,alkyne-alkene conversion of a chemical bond,in situ induction of constrained growth,reversible transition from high to low valence state,and so on.These characteristics originating from the special electronic structure and chemical structure of GDY have rapidly promoted the development of GDY science in recent years and produced many exciting results in fundamental and applied science.Therefore,we systematically introduce the recent theoretical and experimental progress of GDY in terms of its new structural,electronic,mechanical,thermal,and optical properties and its promising applications in the energy fields of membrane sciences,catalysis,energy storage,and conversion.Specifically,the great breakthrough of GDY zero-valence atomic catalysts,quantum dots catalysts,and heterostructure catalysts for catalytic applications are discussed in detail.We believe this review will provide some significant guidelines for the design and development of GDYbased high-performance materials and devices in energy fields.展开更多
Owing to the shortcomings of traditional electrode materials in alkalimetal-ion batteries(AIBs),such as limited reversible specific capacity,low power density,and poor cycling performance,it is particularly important ...Owing to the shortcomings of traditional electrode materials in alkalimetal-ion batteries(AIBs),such as limited reversible specific capacity,low power density,and poor cycling performance,it is particularly important to develop new electrode materials.Covalent organic frameworks(COFs)are crystalline porous polymers that incorporate organic building blocks into their periodic structures through dynamic covalent bonds.COFs are superior to organic materials because of their high designability,regular channels,and stable topology.Since the first report of D_(TP)-A_(NDI)-COF as a cathode material for lithium-ion batteries in 2015,research on COF electrode materials has made continuous progress and breakthroughs.This review briefly introduces the characteristics and current challenges associated with COF electrode materials.Furthermore,we summarize the basic reaction types and active sites according to the categories of covalent bonds,including B–O,C=N,C–N,and C=C.Finally,we emphasize the perspectives on basic structure and morphology design,dimension and size design,and conductivity improvement of COFs based on the latest progress in AIBs.We believe that this review provides important guidelines for the development of high-efficiency COF electrode materials and devices for AIBs.展开更多
Next-generation electronics that intimately interact with the human body would play crucial roles in future health monitors and early disease diagnosis.Skin-inspired electronics have been rapidly growing in the past d...Next-generation electronics that intimately interact with the human body would play crucial roles in future health monitors and early disease diagnosis.Skin-inspired electronics have been rapidly growing in the past decade to emulate the remarkable sensory and responsive nature of the human skin tissue.展开更多
Electroreduction of CO_(2)(CO_(2) RR)to value-added chemicals offers a promising approach to balance the global carbon emission,but still remains a signifi-cantchallengeduetohighoverpotential,lowfaradaic efficiency,an...Electroreduction of CO_(2)(CO_(2) RR)to value-added chemicals offers a promising approach to balance the global carbon emission,but still remains a signifi-cantchallengeduetohighoverpotential,lowfaradaic efficiency,and poor selectivity of electrocatalysts systems.展开更多
Tumor-promoting inflammation is accompanied by cancer initiation,progression,and metastasis.Cyclooxygenase-2(COX-2)and its downstream product,prostaglandin E2(PGE2),play critical roles in tumor-promoting inflammation....Tumor-promoting inflammation is accompanied by cancer initiation,progression,and metastasis.Cyclooxygenase-2(COX-2)and its downstream product,prostaglandin E2(PGE2),play critical roles in tumor-promoting inflammation.Several studies have revealed the potential of COX-2 inhibition in improving cancer response to chemotherapy,as well as immunotherapy.Aspirin,a nonsteroidal anti-inflammatory drug,has been reported as a COX-2 inhibitor.However,as a small molecule drug with a carboxyl group,there is still the lack of effective methods of preparing polymer–aspirin conjugates with tumor stimuli-responsive release properties.Herein,we synthesized a reactive oxygen species(ROS)-responsive aspirin polymeric prodrug(P3C-Asp)via Passerini three-component reaction between aspirin,4-formylbenzeneboronic acid pinacol ester,and 5-isocyanopent-1-yne,followed by copper(I)-catalyzed alkyne-azide cycloaddition“click”reaction of the aspirin prodrug with dextran(DEX).The P3C-Asp could release aspirin and salicylic acid in response to tumor-specific stimuli.In the murine colorectal cancer model,P3C-Asp suppressed tumor growth effectively without significant side effects and eradicated tumors when combined with the immune checkpoint inhibitor,anti-PD-1 antibody(aPD-1).Further analysis revealed that the suppression was attributable to changes in the immune microenvironment,including reduced PGE2 content,as well as increased infiltration of CD8+T cells and M1 macrophages.The results mentioned above proved that targeting COX-2 pathway with a proper polymeric prodrug might be a useful strategy for cancer immunotherapy.展开更多
Organic afterglow materials are highly desirable for optoelectronic applications,but they usually suffer from complex preparation process,low quantum efficiency,and short lifetime due to the ultrafast deactivation of ...Organic afterglow materials are highly desirable for optoelectronic applications,but they usually suffer from complex preparation process,low quantum efficiency,and short lifetime due to the ultrafast deactivation of the highly active excited states involved.Here,we succeeded in achieving solventfree thermal syntheses of high-efficiency afterglow CDs@zeolite composite materials by simply grinding the solid raw materials of zeolite and precursor CDs at room temperature,followed by thermal crystallization.This method afforded maximum embedding of CDs into growing zeolite crystals,as well as strong host–guest interaction to surpass the nonradiative transition of CDs,thus producing composite materials with ultralong dual emission of thermally activated delayed fluorescence and room temperature phosphorescence with a record high lifetime of 1.7 and 2.1 s,respectively,and the quantum yield of 90.7%.Furthermore,in a preliminary experiment,we applied the composite materials in alternatingcurrent light-emitting diode supplementary lighting,which exhibited a promising potential in optoelectronic applications.展开更多
Molecular nanotopology—a term we coined recently—is a rapidly developing field of research that is emerging out of the confluence of chemical topology with the mechanical bond.When perusing the increased research ac...Molecular nanotopology—a term we coined recently—is a rapidly developing field of research that is emerging out of the confluence of chemical topology with the mechanical bond.When perusing the increased research activities in this field,it is clear that a new discipline is ready to receive recognition in its own right.In this Mini-Review,we address the historical development of chemical topology and describe how the rational design and practical synthesis of molecular links and knots with mechanical bonds.展开更多
Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to ...Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to construct the C–N bond.Herein,for the first time,we have successfully realized the formation of amides at industrial current density via the anodic coelectrolysis of alcohol and ammonia under ambient conditions.We have proved thatmodulation of the interface microenvironment concentration of nucleophile by electrolyte engineering can regulate the reaction pathways of amides rather than acetic acids.The C-N coupling strategy can be further extended to the electrosynthesis of the long-chain and aryl-ring amide with high selectivity by replacing ammonia with amine.Our work opens up a vast store of information on the utilization of biomass alcohol for high-value N-containing chemicals via an electrocatalytic C-N coupling reaction.展开更多
Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,co...Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.展开更多
Although dynamic covalent chemistry(DCvC)has been widely utilized to synthesize small molecules and polymers,it remains challenging to construct highly ordered polymeric architectures via DCvC.Further exploration of n...Although dynamic covalent chemistry(DCvC)has been widely utilized to synthesize small molecules and polymers,it remains challenging to construct highly ordered polymeric architectures via DCvC.Further exploration of novel dynamic linkages(in addition to commonly used imine and boronate ester)will expand the library of readily accessible dynamic linkages,diversify the polymeric structures,and unlock new functionality.In this mini-review,the DCvC-based synthetic strategies for enhancing the structural orders of polymeric architectures will be discussed from both thermodynamic control and kinetic control aspects.The relationship between the structure,stability,and dynamic behavior of a DCvC bond will be presented.Then recent examples of constructing polymers with DCvC and supramolecular bonding interactions,such as metal-ligand coordination,host-guest binding,and hydrogen bonding,will be reviewed to demonstrate their synergistic relationship.Furthermore,polymers featuring relatively unexplored DCvC will be highlighted to underscore how developing novel dynamic linkages and fundamental DCvC studies can broaden the scope of functional polymeric architectures.In the end,the challenges in the current field and possible future directions will also be discussed.Advancements in using these design principles will undoubtedly lead to the development of intriguing chemistries,polymeric architectures,and functionality.展开更多
Polyolefins(POs,i.e.,polyethylenes,ethylene/α-olefin copolymers,and polypropylenes)are the most ubiquitous synthetic macromolecular materials in modern life.Their widespread use and low recovery rate after extensive ...Polyolefins(POs,i.e.,polyethylenes,ethylene/α-olefin copolymers,and polypropylenes)are the most ubiquitous synthetic macromolecular materials in modern life.Their widespread use and low recovery rate after extensive usage have caused significant resource waste and environmental concerns.Chemical recycling of POs provides an efficient approach to unravelling the polymer chain to various chemicals.However,conventional chemical recycling methods,including pyrolysis,hydrocracking,and oxidation,require high-energy input(typically>500℃)and/or the use of environmentally unfriendly chemicals,leading to complex product distribution.In this minireview,based on recent representative works,we summarize and highlight catalytic strategies addressing these issues in PO recycling from two perspectives:(1)employing advanced catalysts or technique designs to overcome the challenges in conventional chemical deconstruction approaches;and(2)developing novel tandem/cascade catalytic systems for highly selective PO upcycling under relatively mild conditions.We hope that this minireview will help researchers better understand the state of the art of PO chemical recycling and inspire more innovative and efficient ideas for this fast-developing field.展开更多
The efficient synthesis of ultrathin crystalline twodimensional(2D)polymers with well-defined repeating units is essential to realize their broad applications but remains a great challenge.Herein,we report a new strat...The efficient synthesis of ultrathin crystalline twodimensional(2D)polymers with well-defined repeating units is essential to realize their broad applications but remains a great challenge.Herein,we report a new strategy to directly synthesize a series of few-layer 2D triazine-based polymers(2DTPs)via trimerization reaction of aromatic aldoximes in one step with a high yield of 85%using AlCl3 as catalyst under solvent-free conditions.The obtained 2D-TPs show high crystallinity,a lateral size of several micrometers,an ultrathin thickness less than 2 nm,and good dispersibility and processability.Through semi-in situ and detailed control experiments,we reveal that the 2D polymerization reaction is a two-step process of dehydration and then cyclotrimerization,and AlCl3 acts as not only catalyst but also an in situ generated template for promoting the formation of 2D-TPs.When explored as a new polymeric anode for potassium-ion batteries,the 2D-TP displayed an extraordinary reversible specific capacity of 356 mAh g^(−1)at 0.05 A g^(−1),which is among the best performances ever reported,outstanding rate capability(153 mAh g^(−1)at 1 A g^(−1)),and excellent cycling stability with 95.1%capacity retention after 1000 cycles at 1 A g^(−1).展开更多
In recent years,perovskite solar cells(PSCs)have gone through unparalleled rapid expansion and become a candidate for solar cells.Among various PSCs,though typical three-dimensional(3D)halide perovskite-based PSCs del...In recent years,perovskite solar cells(PSCs)have gone through unparalleled rapid expansion and become a candidate for solar cells.Among various PSCs,though typical three-dimensional(3D)halide perovskite-based PSCs deliver the highest efficiency,they are subjected to severe instability,which constrains their commercializability.In comparison,two-dimensional(2D)PSCs have aroused widespread concern due to their superior stability.After that,2D/3D perovskite materials combining high efficiency and good stability have emerged as the times require,which are expected to bring about stable and efficient PSCs.Here,this review focuses on selection of functional spacer cations for efficient and stable 2D/3D PSCs.First,the unique function of different spacer groups and the selection of appropriate spacer cations in 2D perovskites is summarized and proposed.Then,by selecting appropriate cations,the role of 2D perovskites is elaborated,including energy level regulation,ion migration suppression,defect passivation,residual stress release and improved stability.In addition,the preparation methods of 2D/3D perovskites are comprehensively summarized.Finally,current challenges and future opportunities for the further development of 2D/3D perovskites for solar cells are discussed and prospected.展开更多
Organic scintillators that efficiently generate bright triplet excitons are of critical importance for highperformance X-ray-excited luminescence in radiation detection.However,the nature of triplet-singlet spinforbid...Organic scintillators that efficiently generate bright triplet excitons are of critical importance for highperformance X-ray-excited luminescence in radiation detection.However,the nature of triplet-singlet spinforbidden transitions in these materials often result in long-lived phosphorescence,which is undesirable for ultrafast X-ray detection and imaging.Here we demonstrate that the effect of hybridized local and charge-transfer(HLCT)excited states enables organic scintillators to exhibit highly efficient and fast radioluminescence(RL)in response to X-ray irradiation.Our experimental and theoretical investigation shows that the oxidized 1,8-naphthalimide-phenothiazine dyad(OMNI-PTZ 2)with HLCT-excited states has an enhanced overlap integral of the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)on MNIπ-orbitals,and moderate donor–acceptor electron interactions.As a result,the RL of these crystals exhibits a 61-fold increase and its monoexponential decay lifetime is three orders of magnitude faster compared to its corresponding thermally activated delayed fluorescence(TADF)molecule MNI-PTZ 1.We further demonstrate the practical utility of the OMNI-PTZ 2(G)in high-performance X-ray detection and imaging,achieving an X-ray dose sensitivity of 97 nGy s−1 and an exceptional spatial resolution of 20 lp/mm.Our study provides a promising molecular design principle for utilizing triplet excitons to develop high-efficiency and fast X-ray scintillators for the development of next-generation flexible and stretchable X-ray imaging detectors.展开更多
Achieving a straightforward design of tough,printable,and adaptable polymeric eutectogels is still challenging in related fields due to the uncontrollable polymerization and solvent-exchanging processes,and inherent c...Achieving a straightforward design of tough,printable,and adaptable polymeric eutectogels is still challenging in related fields due to the uncontrollable polymerization and solvent-exchanging processes,and inherent contrasting multiple networks.Here,we report a one-step synergistic strategy based on ruthenium chemistry-catalyzed photopolymerization and solvent effect for preparing high-performance eutectogels.This orthogonal ruthenium photochemistry helps multinetworks formation via phenol-coupling of gelatin and copolymerization of acrylamide(AAm)and[2-(methacryloyloxy)ethyl]trimethylammonium tetrafluoroborate(META)monomers in seconds.The obvious difference in the supramolecular interactions of free AAm monomers and polymerized units in P(AAm-co-META)with deep eutectic solvents(DESs)significantly promotes the microphase-separation behavior in eutectogels.Consequently,the in situ polymerization and microphase-separation behavior enable the as-prepared eutectogel materials to have excellent mechanical properties(stress of∼1.2 MPa),toughness(∼4.0 MJ m^(−3)),elasticity,adaptivity,and conductivity(∼0.5 S m^(−1)at room temperature).Also,the critical strength of the resultant eutectogels can be modulated by varying the DES constituents.This rapid and well-controlled synergistic approach is compatible with extrusion printing techniques to make flexible sensors with high sensitivities and response times to detect pressure in a range of 0–500 kPa.Such a general and simple strategy has application potential in biological,engineering,and material sciences.展开更多
基金supported by the National Science Foundation of China(nos.22071105 and 22031008)the Qinglan Project of Jiangsu Education Department.
文摘Although the combination of electrochemistry and homogeneous catalysis has proven to be a powerful strategy for achieving a diverse array of novel transformations,some challenges such as controlling the diffusion of catalyst-related species and the instability of catalysts at electrodes remain to be overcome.Herein,we review recent advances in electrochemical homogeneous catalysis,focusing on electrochemical noble-transition-metal catalysis,photoelectrochemical catalysis,and electrochemical enantioselective catalysis.The topics discussed include:(1)how the noblemetal catalystworks in the presence of cathodic hydrogen evolution,(2)how the photocatalyst gets enhanced redox property,and(3)how the enantioselectivity is regulated in a catalytic electrochemical reaction.
文摘“A journey of a thousand miles begins with a single step.”—Laozi,Chinese philosopher Welcome to the first issue of CCS Chemistry for 2023!We are excited to be starting on our fifth volume of the journal.Since our launch in 2019,we have gained a lot of momentum,reviewed thousands ofmanuscripts,and published some of the best work in chemistry.We have been very fortunate during that time to have Prof.
基金This work was supported by National Key Re-search and Development Program(2016YFA0202500,2015CB932500,and2016YFA0200102)National Natural Scientific Foundation of China(21676160 and 21825501)Tsinghua University Initiative Scientific Research Program.
文摘Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumption worldwide.However,complicated sul-fur redox reactions and polysulfide shuttling signifi-cantly postpone the applications of lithium-sulfur batteries with rapid capacity decay and low Coulom-bic efficiency.
基金This work was funded by the National Natural Science Foundation(NSFC)of China(grant no.21925505 and 21674081)the China Postdoctoral Science Foundation(grant no.2020M671197).
文摘A chemical reaction that drives a physical polymer selfassembly process,namely,polymerization-induced self-assembly(PISA),combines block copolymer synthesis and nanoparticle formation efficiently at high polymer concentrations.Various nanoparticlemorphologies such as spheres,worms,and vesicles can be prepared readily in polar and nonpolarmedia.PISA has been well developed in combination with reversible addition-fragmentation chain transfer(RAFT)polymerization.Notably,developments with other polymerization methods are also achieved.In this report,first,we discuss the general principles of RAFT-PISA and the nanoparticles generated from this method.Specifically,new insights into polymer nucleation and subsequent morphological evolution are highlighted.Subsequently,PISA formulations that use other polymerization methods[atom transfer radical polymerization(ATRP),nitroxide-mediated polymerization(NMP),ring-opening metathesis polymerization(ROMP),and ring-opening polymerization(ROP)of N-carboxyanhydrides(NCAs)]are summarized in detail.Finally,more exotic PISA formulations are emphasized:these are based on organotelluriummediated living radical polymerization(TERP),living anionic polymerization(LAP),addition-fragmentation chain transfer(AFCT)polymerization,reversible complexation-mediated polymerization(RCMP),and cobalt-mediated radical polymerization(CMRP),or utilize a comonomer that undergoes radical ringopening polymerization(rROP).This reviewis concluded with a perspective on the status and potential of PISA.
基金supported by the National Natural Science Foundation of China(grant nos.U21A2077 and 21871164)the Taishan Scholar Project Foundation of Shandong Province(grant no.ts20190908)the Natural Science Foundation of Shandong Province(grant nos.ZR2021ZD05 and ZR2019MB024).
文摘The use of transition-metal phosphides(TMPs)as catalytic materials to accelerate kinetics of lithium polysulfide(LiPS)conversion has unique advantages.Nevertheless,simple and low-cost preparation strategies are still required for the synthesis of novel TMPs with satisfactory performance.Importantly,the in-depth understanding of the effect of intrinsic interaction between catalytic materials and LiPSs on the promoted kinetics remains limited.Herein,a novel structure of tungsten phosphide(WP)nanocrystals decorated on N,P codoped carbon sheets(WP/NPC)with uniform dispersion is designed by a structure-oriented strategy to promote LiPS redox kinetics.The electrochemical kinetics measurements coupled with density functional theory computations and in situ/ex situ characterizations demonstrate that the strong interaction through W–S bonding and the favorable interfacial charge state of WP-LiPSs promote the nucleation and dissociation of Li2S.Benefiting from this superiority,the WP/NPG-based lithium–sulfur batteries indicate significantly improved electrochemical performance with good cycling life and excellent rate capability.This work provides a methodology for the design of TMP-involved electrode materials and a fundamental understanding of the intrinsic mechanism of catalysis.
基金This research was made possible as a result of a generous grant from the National Nature Science Foundation of China(grant nos.21790050,21790051,and 22005310)the National Key Research and Development Project of China(grant no.2018YFA0703501).
文摘After years of development,graphdiyne(GDY)has demonstrated the characteristics of transformative materials in many fields and has promoted great progress in fundamental and applied research.In practice,some important new concepts have been proposed,such as natural surface charge distribution inhomogeneity,multicavity space limiting effect,incomplete charge transfer effect on the atomic level,alkyne-alkene conversion of a chemical bond,in situ induction of constrained growth,reversible transition from high to low valence state,and so on.These characteristics originating from the special electronic structure and chemical structure of GDY have rapidly promoted the development of GDY science in recent years and produced many exciting results in fundamental and applied science.Therefore,we systematically introduce the recent theoretical and experimental progress of GDY in terms of its new structural,electronic,mechanical,thermal,and optical properties and its promising applications in the energy fields of membrane sciences,catalysis,energy storage,and conversion.Specifically,the great breakthrough of GDY zero-valence atomic catalysts,quantum dots catalysts,and heterostructure catalysts for catalytic applications are discussed in detail.We believe this review will provide some significant guidelines for the design and development of GDYbased high-performance materials and devices in energy fields.
基金This work was supported by the National Natural Science Foundation of China(grant no.22179063)Q.Z.gratefully acknowledges the funding support from the City University of Hong Kong(grant nos.9380117,7005620,and 7020040)and Hong Kong Institute for Advanced Study,City University of Hong Kong,Hong Kong,China.
文摘Owing to the shortcomings of traditional electrode materials in alkalimetal-ion batteries(AIBs),such as limited reversible specific capacity,low power density,and poor cycling performance,it is particularly important to develop new electrode materials.Covalent organic frameworks(COFs)are crystalline porous polymers that incorporate organic building blocks into their periodic structures through dynamic covalent bonds.COFs are superior to organic materials because of their high designability,regular channels,and stable topology.Since the first report of D_(TP)-A_(NDI)-COF as a cathode material for lithium-ion batteries in 2015,research on COF electrode materials has made continuous progress and breakthroughs.This review briefly introduces the characteristics and current challenges associated with COF electrode materials.Furthermore,we summarize the basic reaction types and active sites according to the categories of covalent bonds,including B–O,C=N,C–N,and C=C.Finally,we emphasize the perspectives on basic structure and morphology design,dimension and size design,and conductivity improvement of COFs based on the latest progress in AIBs.We believe that this review provides important guidelines for the development of high-efficiency COF electrode materials and devices for AIBs.
文摘Next-generation electronics that intimately interact with the human body would play crucial roles in future health monitors and early disease diagnosis.Skin-inspired electronics have been rapidly growing in the past decade to emulate the remarkable sensory and responsive nature of the human skin tissue.
基金We acknowledge the financial support received from the National Key Research and Development Program of China(2018YFA0208600 and 2017YFA0700100)Key Research Program of Frontier Science,CAS(QYZDJ-SSW-SLH045)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)NSFC(21671188,21871263 and 21520102001)Youth Innovation Promotion Association,CAS(2014265).
文摘Electroreduction of CO_(2)(CO_(2) RR)to value-added chemicals offers a promising approach to balance the global carbon emission,but still remains a signifi-cantchallengeduetohighoverpotential,lowfaradaic efficiency,and poor selectivity of electrocatalysts systems.
基金supported by the National Natural Science Foundation of China(51673185,51973215,51673189,51833010,51829302,and 51520105004)the Jilin Province Science and Technology Development Plan(20170101100JC and 20190103112JH)Ministry of Science and Technology of China(2016YFC1100701).
文摘Tumor-promoting inflammation is accompanied by cancer initiation,progression,and metastasis.Cyclooxygenase-2(COX-2)and its downstream product,prostaglandin E2(PGE2),play critical roles in tumor-promoting inflammation.Several studies have revealed the potential of COX-2 inhibition in improving cancer response to chemotherapy,as well as immunotherapy.Aspirin,a nonsteroidal anti-inflammatory drug,has been reported as a COX-2 inhibitor.However,as a small molecule drug with a carboxyl group,there is still the lack of effective methods of preparing polymer–aspirin conjugates with tumor stimuli-responsive release properties.Herein,we synthesized a reactive oxygen species(ROS)-responsive aspirin polymeric prodrug(P3C-Asp)via Passerini three-component reaction between aspirin,4-formylbenzeneboronic acid pinacol ester,and 5-isocyanopent-1-yne,followed by copper(I)-catalyzed alkyne-azide cycloaddition“click”reaction of the aspirin prodrug with dextran(DEX).The P3C-Asp could release aspirin and salicylic acid in response to tumor-specific stimuli.In the murine colorectal cancer model,P3C-Asp suppressed tumor growth effectively without significant side effects and eradicated tumors when combined with the immune checkpoint inhibitor,anti-PD-1 antibody(aPD-1).Further analysis revealed that the suppression was attributable to changes in the immune microenvironment,including reduced PGE2 content,as well as increased infiltration of CD8+T cells and M1 macrophages.The results mentioned above proved that targeting COX-2 pathway with a proper polymeric prodrug might be a useful strategy for cancer immunotherapy.
基金Foundation of China(grant nos.21621001,21920102005,21835002,and 21671075)the 111 Project of China(B17020)the financial supports.
文摘Organic afterglow materials are highly desirable for optoelectronic applications,but they usually suffer from complex preparation process,low quantum efficiency,and short lifetime due to the ultrafast deactivation of the highly active excited states involved.Here,we succeeded in achieving solventfree thermal syntheses of high-efficiency afterglow CDs@zeolite composite materials by simply grinding the solid raw materials of zeolite and precursor CDs at room temperature,followed by thermal crystallization.This method afforded maximum embedding of CDs into growing zeolite crystals,as well as strong host–guest interaction to surpass the nonradiative transition of CDs,thus producing composite materials with ultralong dual emission of thermally activated delayed fluorescence and room temperature phosphorescence with a record high lifetime of 1.7 and 2.1 s,respectively,and the quantum yield of 90.7%.Furthermore,in a preliminary experiment,we applied the composite materials in alternatingcurrent light-emitting diode supplementary lighting,which exhibited a promising potential in optoelectronic applications.
文摘Molecular nanotopology—a term we coined recently—is a rapidly developing field of research that is emerging out of the confluence of chemical topology with the mechanical bond.When perusing the increased research activities in this field,it is clear that a new discipline is ready to receive recognition in its own right.In this Mini-Review,we address the historical development of chemical topology and describe how the rational design and practical synthesis of molecular links and knots with mechanical bonds.
基金supported by the National Key R&D Program of China(grant no.2020YFA0710000)the National Natural Science Foundation of China(grant no.22122901)+1 种基金the Provincial Natural Science Foundation of Hunan(grant nos.2021JJ0008,2021JJ20024,2021RC3054,and 2020JJ5045)the Shenzhen Science and Technology Program(grant no.JCYJ20210324140610028).
文摘Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to construct the C–N bond.Herein,for the first time,we have successfully realized the formation of amides at industrial current density via the anodic coelectrolysis of alcohol and ammonia under ambient conditions.We have proved thatmodulation of the interface microenvironment concentration of nucleophile by electrolyte engineering can regulate the reaction pathways of amides rather than acetic acids.The C-N coupling strategy can be further extended to the electrosynthesis of the long-chain and aryl-ring amide with high selectivity by replacing ammonia with amine.Our work opens up a vast store of information on the utilization of biomass alcohol for high-value N-containing chemicals via an electrocatalytic C-N coupling reaction.
基金T.T.acknowledges financial support from the Spanish MCIN/AEI/10.13039/501100011033(PID2020-116490GBI00,TED2021-131255B-C43)the Comunidad de Madrid and the Spanish State through the Recovery,Transformation and Resilience Plan[“Materiales Disruptivos Bidimensionales(2D)”(MAD2D-CM)(UAM1)-MRR Materiales Avanzados]+2 种基金the European Union through the Next Generation EU funds.Instituto madrileno de estudios avanzados Nanociencia acknowledges support from the“Severo Ochoa”Programme for Centres of Excellence in R&D(Ministerio de asuntos economicos y transformacion digital,Grant SEV2016-0686)T.T.also acknowledges the Alexander von Humboldt Foundation(Germany)for the A.v.Humboldt-J.C.Mutis Research Award 2023(Ref 3.3-1231125-ESP-GSA)J.L.acknowledgesMinisterio de Eduacion,Cultura y Deporte(MECD),Spain,for an F.P.U.Fellowship.
文摘Over the past few years,the development of nonfullerene acceptors(NFAs)has become a prominent focus in both organic and perovskite solar cell(OSCs and PSCs,respectively)research fields.In this context,porphyrinoids,compounds structurally related to porphyrins,have emerged as promising solar cell candidates.In contrast to the widely used fullerene acceptors,porphyrinoids exhibit strong,broad absorption properties across the UV–vis/NIR spectrum,which can be easily tuned through chemical modifications.Furthermore,they can be prepared and derivatized using cost-effective and straightforward methodologies,allowing for convenient adjustments in thin-film morphology,processability,supramolecular organization,and energy levels.Additionally,these compounds offer higher thermal and photochemical stability,resulting in longer device lifetimes compared to their fullerene-based counterparts.In this review,we outline the utilization of porphyrinoids as NFAs in OSCs and PSCs,discussing essential aspects such as design guidelines,molecular properties,and device configuration.Our goal is to inspire and further promote the development of n-type porphyrinoids,which have not yet fully unleashed their potential.
文摘Although dynamic covalent chemistry(DCvC)has been widely utilized to synthesize small molecules and polymers,it remains challenging to construct highly ordered polymeric architectures via DCvC.Further exploration of novel dynamic linkages(in addition to commonly used imine and boronate ester)will expand the library of readily accessible dynamic linkages,diversify the polymeric structures,and unlock new functionality.In this mini-review,the DCvC-based synthetic strategies for enhancing the structural orders of polymeric architectures will be discussed from both thermodynamic control and kinetic control aspects.The relationship between the structure,stability,and dynamic behavior of a DCvC bond will be presented.Then recent examples of constructing polymers with DCvC and supramolecular bonding interactions,such as metal-ligand coordination,host-guest binding,and hydrogen bonding,will be reviewed to demonstrate their synergistic relationship.Furthermore,polymers featuring relatively unexplored DCvC will be highlighted to underscore how developing novel dynamic linkages and fundamental DCvC studies can broaden the scope of functional polymeric architectures.In the end,the challenges in the current field and possible future directions will also be discussed.Advancements in using these design principles will undoubtedly lead to the development of intriguing chemistries,polymeric architectures,and functionality.
基金support for this research by the National Key R&D Program of China(grant no.2021YFA1501700)the National Natural Science Foundation of China(grant nos.21825109,21821002,22072178,22293013,and 22272114)+1 种基金the CAS Youth Interdisciplinary Team(grant no.JCTD-2021-11)the Fundamental Research Funds from Sichuan University(grant no.2022SCUNL103)is gratefully acknowledged.
文摘Polyolefins(POs,i.e.,polyethylenes,ethylene/α-olefin copolymers,and polypropylenes)are the most ubiquitous synthetic macromolecular materials in modern life.Their widespread use and low recovery rate after extensive usage have caused significant resource waste and environmental concerns.Chemical recycling of POs provides an efficient approach to unravelling the polymer chain to various chemicals.However,conventional chemical recycling methods,including pyrolysis,hydrocracking,and oxidation,require high-energy input(typically>500℃)and/or the use of environmentally unfriendly chemicals,leading to complex product distribution.In this minireview,based on recent representative works,we summarize and highlight catalytic strategies addressing these issues in PO recycling from two perspectives:(1)employing advanced catalysts or technique designs to overcome the challenges in conventional chemical deconstruction approaches;and(2)developing novel tandem/cascade catalytic systems for highly selective PO upcycling under relatively mild conditions.We hope that this minireview will help researchers better understand the state of the art of PO chemical recycling and inspire more innovative and efficient ideas for this fast-developing field.
基金support by the National Natural Science Foundation of China(grant nos.22022510 and 51873039)the Science and Technology Innovation Program of Hunan Province(grant no.2021RC2086).
文摘The efficient synthesis of ultrathin crystalline twodimensional(2D)polymers with well-defined repeating units is essential to realize their broad applications but remains a great challenge.Herein,we report a new strategy to directly synthesize a series of few-layer 2D triazine-based polymers(2DTPs)via trimerization reaction of aromatic aldoximes in one step with a high yield of 85%using AlCl3 as catalyst under solvent-free conditions.The obtained 2D-TPs show high crystallinity,a lateral size of several micrometers,an ultrathin thickness less than 2 nm,and good dispersibility and processability.Through semi-in situ and detailed control experiments,we reveal that the 2D polymerization reaction is a two-step process of dehydration and then cyclotrimerization,and AlCl3 acts as not only catalyst but also an in situ generated template for promoting the formation of 2D-TPs.When explored as a new polymeric anode for potassium-ion batteries,the 2D-TP displayed an extraordinary reversible specific capacity of 356 mAh g^(−1)at 0.05 A g^(−1),which is among the best performances ever reported,outstanding rate capability(153 mAh g^(−1)at 1 A g^(−1)),and excellent cycling stability with 95.1%capacity retention after 1000 cycles at 1 A g^(−1).
基金support from the National Natural Science Foundation of China(NSFC)(grant nos.52163019,22005131,52173169,and U20A20128)support from the China Postdoctoral Science Foundation(grant no.2021M700060)the Postdoctoral Innovative Talents Support Program(grant no.BX2021117).
文摘In recent years,perovskite solar cells(PSCs)have gone through unparalleled rapid expansion and become a candidate for solar cells.Among various PSCs,though typical three-dimensional(3D)halide perovskite-based PSCs deliver the highest efficiency,they are subjected to severe instability,which constrains their commercializability.In comparison,two-dimensional(2D)PSCs have aroused widespread concern due to their superior stability.After that,2D/3D perovskite materials combining high efficiency and good stability have emerged as the times require,which are expected to bring about stable and efficient PSCs.Here,this review focuses on selection of functional spacer cations for efficient and stable 2D/3D PSCs.First,the unique function of different spacer groups and the selection of appropriate spacer cations in 2D perovskites is summarized and proposed.Then,by selecting appropriate cations,the role of 2D perovskites is elaborated,including energy level regulation,ion migration suppression,defect passivation,residual stress release and improved stability.In addition,the preparation methods of 2D/3D perovskites are comprehensively summarized.Finally,current challenges and future opportunities for the further development of 2D/3D perovskites for solar cells are discussed and prospected.
基金supported by the National Key R&D Program of China(grant no.2020YFA0709900)the National Natural Science Foundation of China(grant nos.21971041,22201042,22027805,62134003,and 22104016)+2 种基金the Natural Science Foundation of Fujian Province(grant nos.2020J01447,2022J06008,and 2022J0121)the Research Foundation of Education Bureau of Fujian Province(grant no.JAT210001)the Fuzhou University Testing Fund of Precious Apparatus(grant no.2022T001).
文摘Organic scintillators that efficiently generate bright triplet excitons are of critical importance for highperformance X-ray-excited luminescence in radiation detection.However,the nature of triplet-singlet spinforbidden transitions in these materials often result in long-lived phosphorescence,which is undesirable for ultrafast X-ray detection and imaging.Here we demonstrate that the effect of hybridized local and charge-transfer(HLCT)excited states enables organic scintillators to exhibit highly efficient and fast radioluminescence(RL)in response to X-ray irradiation.Our experimental and theoretical investigation shows that the oxidized 1,8-naphthalimide-phenothiazine dyad(OMNI-PTZ 2)with HLCT-excited states has an enhanced overlap integral of the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)on MNIπ-orbitals,and moderate donor–acceptor electron interactions.As a result,the RL of these crystals exhibits a 61-fold increase and its monoexponential decay lifetime is three orders of magnitude faster compared to its corresponding thermally activated delayed fluorescence(TADF)molecule MNI-PTZ 1.We further demonstrate the practical utility of the OMNI-PTZ 2(G)in high-performance X-ray detection and imaging,achieving an X-ray dose sensitivity of 97 nGy s−1 and an exceptional spatial resolution of 20 lp/mm.Our study provides a promising molecular design principle for utilizing triplet excitons to develop high-efficiency and fast X-ray scintillators for the development of next-generation flexible and stretchable X-ray imaging detectors.
基金the National Natural Science Foundation of China(grant nos.22175141 and 12102342)the Nature Science Foundation of Shaanxi Province(grant nos.2023-JC-JQ-14,2023JC-XJ-21,and 2022JQ-146)+1 种基金Cultivation Program for the Excellent Doctoral Dissertation of Northwest University(grant no.YB2023006)the Young Elite Scientists Sponsorship Program by Xi’an Association for Science and Technology(grant no.095920221324)for the financial support of this work.
文摘Achieving a straightforward design of tough,printable,and adaptable polymeric eutectogels is still challenging in related fields due to the uncontrollable polymerization and solvent-exchanging processes,and inherent contrasting multiple networks.Here,we report a one-step synergistic strategy based on ruthenium chemistry-catalyzed photopolymerization and solvent effect for preparing high-performance eutectogels.This orthogonal ruthenium photochemistry helps multinetworks formation via phenol-coupling of gelatin and copolymerization of acrylamide(AAm)and[2-(methacryloyloxy)ethyl]trimethylammonium tetrafluoroborate(META)monomers in seconds.The obvious difference in the supramolecular interactions of free AAm monomers and polymerized units in P(AAm-co-META)with deep eutectic solvents(DESs)significantly promotes the microphase-separation behavior in eutectogels.Consequently,the in situ polymerization and microphase-separation behavior enable the as-prepared eutectogel materials to have excellent mechanical properties(stress of∼1.2 MPa),toughness(∼4.0 MJ m^(−3)),elasticity,adaptivity,and conductivity(∼0.5 S m^(−1)at room temperature).Also,the critical strength of the resultant eutectogels can be modulated by varying the DES constituents.This rapid and well-controlled synergistic approach is compatible with extrusion printing techniques to make flexible sensors with high sensitivities and response times to detect pressure in a range of 0–500 kPa.Such a general and simple strategy has application potential in biological,engineering,and material sciences.
