Aqueous Zn-ion hybrid supercapacitors(ZHSs)are increasingly being studied as a novel electrochemical energy storage system with prominent electrochemical performance,high safety and low cost.Herein,high-energy and ant...Aqueous Zn-ion hybrid supercapacitors(ZHSs)are increasingly being studied as a novel electrochemical energy storage system with prominent electrochemical performance,high safety and low cost.Herein,high-energy and anti-self-discharge ZHSs are realized based on the fibrous carbon cathodes with hierarchically porous surface and O/N heteroatom functional groups.Hierarchically porous surface of the fabricated free-standing fibrous carbon cathodes not only provides abundant active sites for divalent ion storage,but also optimizes ion transport kinetics.Consequently,the cathodes show a high gravimetric capacity of 156 mAh g^(−1),superior rate capability(79 mAh g^(−1)with a very short charge/discharge time of 14 s)and exceptional cycling stability.Meanwhile,hierarchical pore structure and suitable surface functional groups of the cathodes endow ZHSs with a high energy density of 127 Wh kg−1,a high power density of 15.3 kW kg^(−1)and good anti-self-discharge performance.Mechanism investigation reveals that ZHS electrochemistry involves cation adsorption/desorption and Zn_(4)SO_(4)(OH)_(6)·5H_(2)O formation/dissolution at low voltage and anion adsorption/desorption at high voltage on carbon cathodes.The roles of these reactions in energy storage of ZHSs are elucidated.This work not only paves a way for high-performance cathode materials of ZHSs,but also provides a deeper understanding of ZHS electrochemistry.展开更多
Potassium ion batteries(PIBs)with the prominent advantages of sufficient reserves and economical cost are attractive candidates of new rechargeable batteries for large-grid electrochemical energy storage systems(EESs)...Potassium ion batteries(PIBs)with the prominent advantages of sufficient reserves and economical cost are attractive candidates of new rechargeable batteries for large-grid electrochemical energy storage systems(EESs).However,there are still some obstacles like large size of K+to commercial PIBs applications.Therefore,rational structural design based on appropriate materials is essential to obtain practical PIBs anode with K+accommodated and fast diffused.Nanostructural design has been considered as one of the effective strategies to solve these issues owing to unique physicochemical properties.Accordingly,quite a few recent anode materials with different dimensions in PIBs have been reported,mainly involving in carbon materials,metal-based chalcogenides(MCs),metal-based oxides(MOs),and alloying materials.Among these anodes,nanostructural carbon materials with shorter ionic transfer path are beneficial for decreasing the resistances of transportation.Besides,MCs,MOs,and alloying materials with nanostructures can effectively alleviate their stress changes.Herein,these materials are classified into 0D,1D,2D,and 3D.Particularly,the relationship between different dimensional structures and the corresponding electrochemical performances has been outlined.Meanwhile,some strategies are proposed to deal with the current disadvantages.Hope that the readers are enlightened from this review to carry out further experiments better.展开更多
Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes tha...Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes that originates from dendrite growth,surface passivation and corrosion,severely hinders the further development of ZBs.To tackle these issues,here we report a Janus separator based on a Zn-ion conductive metal-organic framework(MOF)and reduced graphene oxide(rGO),which is able to regulate uniform Zn2+flux and electron conduction simultaneously during battery operation.Facilitated by the MOF/rGO bifunctional interlayers,the Zn anodes demonstrate stable plating/stripping behavior(over 500 h at 1 mA cm^(−2)),high Coulombic efficiency(99.2%at 2 mA cm^(−2) after 100 cycles)and reduced redox barrier.Moreover,it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface.Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells,which deliver nearly 100%capacity retention after 2000 cycles at 4 A g^(−1) and high power density over 10 kW kg^(−1).This work provides a feasible route to the high-performance Zn anodes for ZBs.展开更多
Rechargeable aqueous zinc-ion batteries(ZIB s) have been gaining increasing interest for large-scale energy storage applications due to their high safety,good rate capability,and low cost.However,the further developme...Rechargeable aqueous zinc-ion batteries(ZIB s) have been gaining increasing interest for large-scale energy storage applications due to their high safety,good rate capability,and low cost.However,the further development of ZIB s is impeded by two main challenges:Currently reported cathode materials usually suffer from rapid capacity fading or high toxicity,and meanwhile,unstable zinc stripping/plating on Zn anode seriously shortens the cycling life of ZIBs.In this paper,metal-organic framework(MOF) materials are proposed to simultaneously address these issues and realize high-performance ZIB s with Mn(BTC) MOF cathodes and ZIF-8-coated Zn(ZIF-8@Zn) anodes.Various MOF materials were synthesized,and Mn(BTC) MOF was found to exhibit the best Zn^2+-storage ability with a capacity of 112 mAh g^-1.Zn^2+ storage mechanism of the Mn(BTC) was carefully studied.Besides,ZIF-8@Zn anodes were prepared by coating ZIF-8 MOF material on Zn foils.Unique porous structure of the ZIF-8 coating guided uniform Zn stripping/plating on the surface of Zn anodes.As a result,the ZIF-8@Zn anodes exhibited stable Zn stripping/plating behaviors,with 8 times longer cycle life than bare Zn foils.Based on the above,high-performance aqueous ZIBs were constructed using the Mn(BTC) cathodes and the ZIF-8@Zn anodes,which displayed an excellent long-cycling stability without obvious capacity fading after 900 charge/discharge cycles.This work provides a new opportunity for high-performance energy storage system.展开更多
In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents tha...In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.展开更多
In view of rich potassium resources and their working potential,potassium-ion batteries(PIBs)are deemed as next generation rechargeable batteries.Owing to carbon materials with the preponderance of durability and econ...In view of rich potassium resources and their working potential,potassium-ion batteries(PIBs)are deemed as next generation rechargeable batteries.Owing to carbon materials with the preponderance of durability and economic price,they are widely employed in PIBs anode materials.Currently,porosity design and heteroatom doping as efficacious improvement strategies have been applied to the structural design of carbon materials to improve their electrochemical performances.Herein,nitrogen-doped mesoporous carbon spheres(MCS)are synthesized by a facile hard template method.The MCS demonstrate larger interlayer spacing in a short range,high specific surface area,abundant mesoporous structures and active sites,enhancing K-ion migration and diffusion.Furthermore,we screen out the pyrolysis temperature of 900°C and the pore diameter of 7 nm as optimized conditions for MCS to improve performances.In detail,the optimized MCS-7-900 electrode achieves high rate capacity(107.9 mAh g^(−1) at 5000 mA g^(−1))and stably brings about 3600 cycles at 1000 mA g^(−1).According to electrochemical kinetic analysis,the capacitive-controlled effects play dominant roles in total storage mechanism.Additionally,the full-cell equipped MCS-7-900 as anode is successfully constructed to evaluate the practicality of MCS.展开更多
Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. H...Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. Herein, by incorporating the cobalt-oxide bonds and polyaniline(PANI) with two-dimension zeolitic imidazolate frameworks(ZIFs), a novel bifunctional catalyst(Co-O-ZIF/PANI) for Zn-air battery was designed based on a facile and eco-friendly method. This Co-O-ZIF/PANI with optimized surface adsorption effect and suitable Co^(3+)/Co^(2+)ratio, exhibits eminent electrocatalytic activity toward both oxygen reduction and evolution reaction. The as-assembled liquid ZABs based on Co-O-ZIF/PANI achieves a remarkable maximum power density of 123.1 m W cm^(-2) and low discharge-charge voltage gap of 0.81 V at 5 m A cm^(-2) for over 300 cycles. Operando Raman spectroscopy reveals that the excellent performance origins from the optimized surface chemisorption property of O_(2) and H_(2)O brought by Co–O bonds and PANI. This work provides a novel prospect to develop efficient MOF derived bifunctional electrocatalysts by optimizing surface chemisorption properties.展开更多
As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,ag...As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.展开更多
A composite bone cement based onα-TCP with self-reinforcing characteristics is prepared by compounding cellulose whiskers and polyvinyl alcohol in different proportions.In this system,we are inspired by the sea cucum...A composite bone cement based onα-TCP with self-reinforcing characteristics is prepared by compounding cellulose whiskers and polyvinyl alcohol in different proportions.In this system,we are inspired by the sea cucumber,which can alter the stiffness of their inner dermis reversibly.Through the formation of hydrogen bonds between the hydroxyl groups on the cellulose whiskers and PVA,the bone cement matrix can be strengthened during the curing process of cement.In the process of bone cement blending,there is more water,the hydrogen bond connection is destroyed,so the slurry has better fluidity at this time.As the hydration of the bone cement progresses,the reduction of the water phase leads to the formation of a permeable network structure of hydrogen bond connections between the whiskers.The dual-phase action of PVA and whiskers greatly increases the mechanical strength of the bone cement system(5.5 to 23.8 MPa),while the presence of polyvinyl alcohol improves the toughness of the bone cement system.This work was supposed to explore whether the chemoresponsive materials can be adapted to biomedical materials,for example,bone repair.展开更多
This review intends to introduce the application of lignin-derived catalyst for green organic synthesis over latest two decades and aims to present a renewable alternative for conventional catalyst for future industry...This review intends to introduce the application of lignin-derived catalyst for green organic synthesis over latest two decades and aims to present a renewable alternative for conventional catalyst for future industry application. The structure of lignin is initially introduced in this review. Then, various pretreatment and activation technologies of lignin are systematically presented, which includes physical activation for the formation of well-developed porosity and chemical activation to introduce catalytic active sites. Finally, the catalytic performances of various lignin-derived catalysts are rationally assessed and compared with conventional catalysts, which involves lignin-derived solid acids for hydrolysis, hydration, dehydration(trans)esterification, multi-component reaction and condensation, lignin-derived solid base for Knoevenagel reaction, lignin-derived electro-catalysts for electro-oxidation, oxygen reduction reaction, and lignin-derived supported transition metal catalysts for hydrogenation, oxidation, coupling reaction, tandem reaction, condensation reaction, ring-opening reaction, Friedel-Crafts-type reaction,Fischer–Tropsch synthesis, click reaction, Glaser reaction, cycloaddition and(trans)esterification. The above lignin-derived catalysts thus successfully promote the transformations of organic compounds, carbon dioxide, biomass-based cellulose, saccharide and vegetable oil into valuable chemicals and fuels. At the end of this review, some perspectives are given on the current issues and tendency on the lignin-derived catalysts for green chemistry.展开更多
Rechargeable aqueous zinc-ion batteries(ZIBs) have become a research hotspot in recent years,due to their huge potential for high-energy,fast-rate,safe and low-cost energy storage.To realize good electrochemical prope...Rechargeable aqueous zinc-ion batteries(ZIBs) have become a research hotspot in recent years,due to their huge potential for high-energy,fast-rate,safe and low-cost energy storage.To realize good electrochemical properties of ZIBs,cathode materials with prominent Zn^(2+) storage capability are highly needed.Herein,we report a promising ZIB cathode material based on electrochemically induced transformation of vanadium oxides.Specifically,K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers were synthesized through a simple stirring method at near room temperature and then used as cathode materials for ZIBs in different electrolytes.The cathode presented superior Zn^(2+) storage capability in Zn(OTf)_(2) aqueous electrolyte,including high capacity of 321 mAh/g,fast charge/discharge ability(96 mAh/g delivered in 35 s), high energy density of 235 Wh/kg and good cycling performance.Mechanism analysis evidenced that in Zn(OTf)_(2) electrolyte,Zn^(2+) intercalation in the first discharge process promoted K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers to transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O nanoflakes,and the latter served as the Zn^(2+)-storage host in subsequent charge/discharge processes.Benefiting from open-framework crystal structure and sufficiently exposed surface,the Zn_(3+x)V_(2) O_7(OH)_(2)·2_H2 O nanoflakes exhibited high Zn^(2+) diffusion coefficient,smaller charge-transfer resistance and good reversibility of Zn^(2+) intercalation/de-intercalation,thus leading to superior electrochemical performance.While in ZnS04 aqueous electrolyte,the cathode material cannot sufficiently transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O thereby corresponding to inferior electrochemical behaviors.Underlying mechanism and influencing factors of such a transformation phenomenon was also explored.This work not only reports a high-performance ZIB cathode material based on electrochemically induced transformation of vanadium oxides,but also provides new insights into Zn^(2+)-storage electrochemistry.展开更多
The plasmonic photocatalyst of Pd supported on graphitic carbon nitride(Pd/g-C3N4)exhibits excellent catalytic activity in photo-induced hydrogenation of biomass-based aldehydes with environmental benign reagents of f...The plasmonic photocatalyst of Pd supported on graphitic carbon nitride(Pd/g-C3N4)exhibits excellent catalytic activity in photo-induced hydrogenation of biomass-based aldehydes with environmental benign reagents of formic acid(HCOOH)as proton source and triethylamine(TEA)as sacrificial electron donator.The chemical and configurational properties of the Pd/g-C3N4 were systematically analyzed with XRD,TEM and XPS.Under optimized conditions,27%yield of furfuryl alcohol with the corresponding turnover frequency(TOF)around 3.72 h^(-1) were obtained from furfural and TEA-HCOOH under visible-light irradiation by using Pd/g-C3N4.Our research additionally reveals that Pd atom is the true catalytic active site for the hydrogenation and the photo-promoted reduction mainly occurs through noble metal nanoparticles(NPs)-induced effect of surface plasmon resonance(SPR).The photo-catalytic system of Pd/g-C3N4 thus demonstrates a green and effective method for the hydrogenation of biomass-based aldehydes with sustainable solar energy as a driven force.展开更多
Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural(HMF) to 2,5-dihydroxymethyltetrahydrofuran(DHMTHF) with 96% selectivity and a complete HMF conversion is obtained over palladium catalyst supporte...Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural(HMF) to 2,5-dihydroxymethyltetrahydrofuran(DHMTHF) with 96% selectivity and a complete HMF conversion is obtained over palladium catalyst supported on mesoporous graphitic carbon nitride(Pd/mpg-C_3N_4) under pressured hydrogen atmosphere in aqueous media. The excellent catalytic performance of Pd/mpg-C_3N_4 is attributed to hydrogen bonding-related competitive interactions between reactant HMF and “intermediate” 2,5-dihydroxymethylfuran(DHMF) with the support mpg-C_3N_4, which leads to a deep hydrogenation of DHMF to DHMTHF.展开更多
Implant-associated infections(IAIs)caused by drug-resistant bacteria remain a critical factor in the fail-ure of implant procedures.Therefore,it is urgent to develop an effective anti-infection coating for im-plant su...Implant-associated infections(IAIs)caused by drug-resistant bacteria remain a critical factor in the fail-ure of implant procedures.Therefore,it is urgent to develop an effective anti-infection coating for im-plant surface modification to prevent IAIs.Herein,an antibacterial and anti-adhesive coating(CMP-Ti)constructed on the surface of titanium implants is reported,formed by the nanomaterial CeO_(2)@Mn_(3)O_(4) NRs(CM NRs)with antibacterial activity and the superhydrophilic polymer polyethylene glycol(PEG).The nanocatalyst CM NRs on the surface of CMP-Ti induce ferroptosis-like death of bacteria by catalyzing the production of hydroxyl radical(·OH)and singlet oxygen(^(1)O_(2))and the consumption of glutathione(GSH).The superhydrophilic coating of CMP-Ti can effectively prevent adherence of drug-resistant bac-teria and avoid biofilm formation.By combining the"active offense"antibacterial mechanism with the"passive defense"anti-adhesion mechanism,CMP-Ti can kill bacteria and inhibit biofilm formation.The results of in vivo studies showed that CMP-Ti effectively prevented implant-associated infections caused by Methicillin-resistant Staphylococcus aureus(MRSA),thus promoting tissue repair and osseointegra-tion.Therefore,this multifunctional coating combining"active offense"and"passive defense"provides a promising way to prevent IAIs caused by drug-resistant bacteria and to promote tissue repair in the future.展开更多
Thermal ablation(TA)as an effective method treating hepatocellular carcinoma(HCC)in clinics is facing great challenges of high recurrence and metastasis.Although immune-checkpoint blockade(ICB)-based immuno-therapy ha...Thermal ablation(TA)as an effective method treating hepatocellular carcinoma(HCC)in clinics is facing great challenges of high recurrence and metastasis.Although immune-checkpoint blockade(ICB)-based immuno-therapy has shown potential to inhibit recurrence and metastasis,the combination strategy of ICB and thermal ablation has shown little progress in HCC treatments.The tremendous hurdle for combining ICB with thermal ablation lies with the insufficient antigen internalization and immaturity of tumor-infiltrating dendritic cells(TIDCs)which leads to an inferior immune response to distant tumor growth and metastasis.Herein,an antigen-capturing nanoplatform,whose surface was modified with mannose as a targeting ligand,was constructed for co-delivering tumor-associated antigens(TAAs)and m6A demethylases inhibitor(i.e.,fat mass and obesity asso-ciated gene(FTO)inhibitor)into TIDCs.In vivo results demonstrate that the intratumoral injection of nanodrug followed by HCC thermal ablation promotes dendritic cells(DCs)maturation,improves tumor infiltration of effector T cells and generates immune memory,which synergize with ICB treatment to inhibit the distant tumor growth and lung metastasis.Therefore,the antigen-capturing and FTO-inhibiting nanodrug holds potential to boost the ICB-based immunotherapy against HCC after thermal ablation.展开更多
Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compound...Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compounds suffer from severe electrochemical polarization,agglomeration,and dramatic volume fluctuations.To develop an advanced bismuth-based anode material with high reactivity and durability,in this work,the pyrolysis of Bi-based metal-organic frameworks and in-situ selenization techniques have been successfully used to produce a Bi-based composite with high capacity and unique structure,in which Bi/Bi_(3)Se_(4)nanoparticles are encapsulated in carbon nanorods(Bi/Bi_(3)Se_(4)@CNR).Applied as the anode material of PIBs,the Bi/Bi_(3)Se_(4)@CNR displays fast potassium storage capability with 307.5 m A h g^(-1)at 20 A g^(-1)and durable cycle performance of 2000 cycles at 5 A g^(-1).Notably,the Bi/Bi_(3)Se_(4)@CNR also showed long cycle stability over 1600 cycles when working in a full cell system with potassium vanadate as the cathode material,which further demonstrates its promising potential in the field of PIBs.Additionally,the dual potassium storage mechanism of the Bi/Bi_(3)Se_(4)@CNR based on conversion and alloying reaction has also been revealed by in-situ X-ray diffraction.展开更多
Pore characteristics have been identified as key design parameters for osteoimmunomodulation.The strategy reported here is to create an appropriate immune microenvironment by regulating pore characteristics of scaffol...Pore characteristics have been identified as key design parameters for osteoimmunomodulation.The strategy reported here is to create an appropriate immune microenvironment by regulating pore characteristics of scaffolds,thereby promoting early angiogenesis and enhancing osteogenesis.A series of collagen/nanohydroxyapatite(Col/nHAP)composite scaffolds with ordered lamellar structures and different layer spacings were prepared by mimicking the ordered lamellar topology of the bone matrix.Our research indicated that the layer spacing and ordered topology of the scaffold exerted an important influence on phenotype transformation of macrophages and the secretion of angiogenic factors.The Col/nHAP-O(135)with large layer spacing not only supported cell attachment and diffusion in vitro,but also promoted early angiogenesis by timely switching from M1 to M2 macrophage phenotype.In vivo data showed that the layer spacing and the ordered structure of the scaffold synergistically regulated the inflammatory response and triggered macrophages to secrete more angiogenesis related cytokines.Col/nHAP-O(135)considerably promoted the neovascularization and new bone formation in the defect site,indicating that Col/nHAPO(135)could significantly enhance the osteogenic activity of stem cells with the involvement of macrophages.展开更多
Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global ...Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global climate change.Due to the increased popularity of consumer electronics and electric vehicles,lithium-ion batteries have quickly become the most successful rechargeable batteries in the past three decades,yet growing demands in diversified application scenarios call for new types of rechargeable batteries.Tremendous efforts are made to developing the next-generation post-Li-ion rechargeable batteries,which include,but are not limited to solid-state batteries,lithium–sulfur batteries,sodium-/potassium-ion batteries,organic batteries,magnesium-/zinc-ion batteries,aqueous batteries and flow batteries.Despite the great achievements,challenges persist in precise understandings about the electrochemical reaction and charge transfer process,and optimal design of key materials and interfaces in a battery.This roadmap tends to provide an overview about the current research progress,key challenges and future prospects of various types of rechargeable batteries.New computational methods for materials development,and characterization techniques will also be discussed as they play an important role in battery research.展开更多
Metal-organic frameworks(MOFs)hold significant potential as vehicles for drug delivery due to their expansive specific surface area,biocompatibility,and versatile attributes.Concurrently,magnetically actuated micro/na...Metal-organic frameworks(MOFs)hold significant potential as vehicles for drug delivery due to their expansive specific surface area,biocompatibility,and versatile attributes.Concurrently,magnetically actuated micro/nano-robots(MNRs)offer distinct advantages,such as untethered and precise manipulation.The fusion of these technologies presents a promising avenue for achieving non-invasive targeted drug delivery.Here,we report a MOF-based magnetic microrobot swarm(MMRS)for targeted therapy.Our approach overcomes limitations associated with a single MNR,including limited drug loading and the risk of loss during manipulation.We select Zeolitic Imidazolate Framework-8(ZIF-8)as the drug vehicle for its superior loading potential and p H-sensitive decomposition.Our design incorporates magnetic responsive components into the one-pot synthesis of Fe@ZIF-8,enabling collective behaviors under actuation.Tuning the yaw angle of alternating magnetic fields and nanoparticles'amount,the MMRSs with controllable size achieve instantaneous transformation among different configurations,including vortex-like swarms,chain-like swarms,and elliptical swarms,facilitating adaptation to environmental variations.Transported to the subcutaneous T24 tumor site,the MMRSs with encapsulated doxorubicin(DOX)automatically degrade and release the drug,leading to a dramatic reduction of the tumor in vivo.Our investigation signifies a significant advancement in the integration of biodegradable MOFs into microrobot swarms,ushering in new avenues for accurate and non-invasive targeted drug delivery.展开更多
Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and h...Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.展开更多
基金National Natural Science Foundation of China(No.52002149)Shenzhen Technical Plan Projects(Nos.JC201105201100A and JCYJ20160301154114273)for financial support.
文摘Aqueous Zn-ion hybrid supercapacitors(ZHSs)are increasingly being studied as a novel electrochemical energy storage system with prominent electrochemical performance,high safety and low cost.Herein,high-energy and anti-self-discharge ZHSs are realized based on the fibrous carbon cathodes with hierarchically porous surface and O/N heteroatom functional groups.Hierarchically porous surface of the fabricated free-standing fibrous carbon cathodes not only provides abundant active sites for divalent ion storage,but also optimizes ion transport kinetics.Consequently,the cathodes show a high gravimetric capacity of 156 mAh g^(−1),superior rate capability(79 mAh g^(−1)with a very short charge/discharge time of 14 s)and exceptional cycling stability.Meanwhile,hierarchical pore structure and suitable surface functional groups of the cathodes endow ZHSs with a high energy density of 127 Wh kg−1,a high power density of 15.3 kW kg^(−1)and good anti-self-discharge performance.Mechanism investigation reveals that ZHS electrochemistry involves cation adsorption/desorption and Zn_(4)SO_(4)(OH)_(6)·5H_(2)O formation/dissolution at low voltage and anion adsorption/desorption at high voltage on carbon cathodes.The roles of these reactions in energy storage of ZHSs are elucidated.This work not only paves a way for high-performance cathode materials of ZHSs,but also provides a deeper understanding of ZHS electrochemistry.
基金the Start-up Funding of Jinan University(Grant No.88016105 and Grant No.55800001)the discipline construction outstanding young backbone project(Grant No.12819023)the Fundamental Research Funds for the Central Universities(Grant No.11620317).
文摘Potassium ion batteries(PIBs)with the prominent advantages of sufficient reserves and economical cost are attractive candidates of new rechargeable batteries for large-grid electrochemical energy storage systems(EESs).However,there are still some obstacles like large size of K+to commercial PIBs applications.Therefore,rational structural design based on appropriate materials is essential to obtain practical PIBs anode with K+accommodated and fast diffused.Nanostructural design has been considered as one of the effective strategies to solve these issues owing to unique physicochemical properties.Accordingly,quite a few recent anode materials with different dimensions in PIBs have been reported,mainly involving in carbon materials,metal-based chalcogenides(MCs),metal-based oxides(MOs),and alloying materials.Among these anodes,nanostructural carbon materials with shorter ionic transfer path are beneficial for decreasing the resistances of transportation.Besides,MCs,MOs,and alloying materials with nanostructures can effectively alleviate their stress changes.Herein,these materials are classified into 0D,1D,2D,and 3D.Particularly,the relationship between different dimensional structures and the corresponding electrochemical performances has been outlined.Meanwhile,some strategies are proposed to deal with the current disadvantages.Hope that the readers are enlightened from this review to carry out further experiments better.
基金This work was financially supported by Hong Kong Innovation&Technology Fund(ITS/031/18)National Key R&D Program of China(2016YFB0700600)+1 种基金Soft Science Research Project of Guangdong Province(2017B030301013)Shenzhen Science and Technology Research Grant(ZDSYS201707281026184).
文摘Owing to the merits of low cost,high safety and environmental benignity,rechargeable aqueous Zn-based batteries(ZBs)have gained tremendous attention in recent years.Nevertheless,the poor reversibility of Zn anodes that originates from dendrite growth,surface passivation and corrosion,severely hinders the further development of ZBs.To tackle these issues,here we report a Janus separator based on a Zn-ion conductive metal-organic framework(MOF)and reduced graphene oxide(rGO),which is able to regulate uniform Zn2+flux and electron conduction simultaneously during battery operation.Facilitated by the MOF/rGO bifunctional interlayers,the Zn anodes demonstrate stable plating/stripping behavior(over 500 h at 1 mA cm^(−2)),high Coulombic efficiency(99.2%at 2 mA cm^(−2) after 100 cycles)and reduced redox barrier.Moreover,it is also found that the Zn corrosion can be effectively retarded through diminishing the potential discrepancy on Zn surface.Such a separator engineering also saliently promotes the overall performance of Zn|MnO2 full cells,which deliver nearly 100%capacity retention after 2000 cycles at 4 A g^(−1) and high power density over 10 kW kg^(−1).This work provides a feasible route to the high-performance Zn anodes for ZBs.
基金the financial supports from International Science & Technology Cooperation Program of China (No. 2016YFE0102200)Shenzhen Technical Plan Project (No. JCYJ20160301154114273)+1 种基金National Key Basic Research (973) Program of China (No. 2014CB932400)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N111)。
文摘Rechargeable aqueous zinc-ion batteries(ZIB s) have been gaining increasing interest for large-scale energy storage applications due to their high safety,good rate capability,and low cost.However,the further development of ZIB s is impeded by two main challenges:Currently reported cathode materials usually suffer from rapid capacity fading or high toxicity,and meanwhile,unstable zinc stripping/plating on Zn anode seriously shortens the cycling life of ZIBs.In this paper,metal-organic framework(MOF) materials are proposed to simultaneously address these issues and realize high-performance ZIB s with Mn(BTC) MOF cathodes and ZIF-8-coated Zn(ZIF-8@Zn) anodes.Various MOF materials were synthesized,and Mn(BTC) MOF was found to exhibit the best Zn^2+-storage ability with a capacity of 112 mAh g^-1.Zn^2+ storage mechanism of the Mn(BTC) was carefully studied.Besides,ZIF-8@Zn anodes were prepared by coating ZIF-8 MOF material on Zn foils.Unique porous structure of the ZIF-8 coating guided uniform Zn stripping/plating on the surface of Zn anodes.As a result,the ZIF-8@Zn anodes exhibited stable Zn stripping/plating behaviors,with 8 times longer cycle life than bare Zn foils.Based on the above,high-performance aqueous ZIBs were constructed using the Mn(BTC) cathodes and the ZIF-8@Zn anodes,which displayed an excellent long-cycling stability without obvious capacity fading after 900 charge/discharge cycles.This work provides a new opportunity for high-performance energy storage system.
文摘In contrast to heterogeneous network frameworks(e.g.,covalent organic frameworks and metal‐organic frameworks)and porous organic polymers,porous organic cages(POCs)are soluble molecules in common organic solvents that provide significant potential for homogeneous catalysis.Herein,we report a triphenylphosphine‐derived quasi‐porous organic cage(denoted as POC‐DICP)as an efficient organic molecular cage ligand for Rh/PPh_(3) system‐catalyzed homogeneous hydroformylation reactions.POC‐DICP not only displays enhanced hydroformylation selectivity(aldehyde selectivity as high as 97%and a linear‐to‐branch ratio as high as 1.89)but can also be recovered and reused via a simple precipitation method in homogeneous reaction systems.We speculate that the reason for the high activity and good selectivity is the favorable geometry(cone angle=123.88°)and electronic effect(P site is relatively electron‐deficient)of POC‐DICP,which were also demonstrated by density functional theory calculations and X‐ray absorption fine‐structure characterization.
基金This work was financially supported by the Start-up Funding of Jinan University(88016105 and 55800001)the discipline construction outstanding young backbone project(12819023)+1 种基金the Fundamental Research Funds for the Central Universities(21620317)the Guangdong Basic and Applied Basic Research Foundation(2020A1515110611 and 2021A1515010362).
文摘In view of rich potassium resources and their working potential,potassium-ion batteries(PIBs)are deemed as next generation rechargeable batteries.Owing to carbon materials with the preponderance of durability and economic price,they are widely employed in PIBs anode materials.Currently,porosity design and heteroatom doping as efficacious improvement strategies have been applied to the structural design of carbon materials to improve their electrochemical performances.Herein,nitrogen-doped mesoporous carbon spheres(MCS)are synthesized by a facile hard template method.The MCS demonstrate larger interlayer spacing in a short range,high specific surface area,abundant mesoporous structures and active sites,enhancing K-ion migration and diffusion.Furthermore,we screen out the pyrolysis temperature of 900°C and the pore diameter of 7 nm as optimized conditions for MCS to improve performances.In detail,the optimized MCS-7-900 electrode achieves high rate capacity(107.9 mAh g^(−1) at 5000 mA g^(−1))and stably brings about 3600 cycles at 1000 mA g^(−1).According to electrochemical kinetic analysis,the capacitive-controlled effects play dominant roles in total storage mechanism.Additionally,the full-cell equipped MCS-7-900 as anode is successfully constructed to evaluate the practicality of MCS.
基金financially supported by the National Natural Science Foundation of China (51772135 and 51872124)the Ministry of Education of China (6141A02022516)+6 种基金the Natural Science Foundation of Guangdong Province (2014A030306010)the Natural Science Foundation of Guangdong Province (2021A1515010504)the Natural Science Key Foundation of Guangdong Province (2019B1515120056)the Natural Science Foundation of Guangzhou (201904010049)the Jinan University (88016105)the Innovation Team Project of Foshan City (FS0AA-KJ919-4402-0086)the Fundamental Research Foundation for the Central Universities(21617326 and 11619103)。
文摘Metal organic frameworks(MOFs) have been considered as compelling precursor for miscellaneous applications. However, their unsatisfied electrocatalytic performance limits their direct application as electrocatalyst. Herein, by incorporating the cobalt-oxide bonds and polyaniline(PANI) with two-dimension zeolitic imidazolate frameworks(ZIFs), a novel bifunctional catalyst(Co-O-ZIF/PANI) for Zn-air battery was designed based on a facile and eco-friendly method. This Co-O-ZIF/PANI with optimized surface adsorption effect and suitable Co^(3+)/Co^(2+)ratio, exhibits eminent electrocatalytic activity toward both oxygen reduction and evolution reaction. The as-assembled liquid ZABs based on Co-O-ZIF/PANI achieves a remarkable maximum power density of 123.1 m W cm^(-2) and low discharge-charge voltage gap of 0.81 V at 5 m A cm^(-2) for over 300 cycles. Operando Raman spectroscopy reveals that the excellent performance origins from the optimized surface chemisorption property of O_(2) and H_(2)O brought by Co–O bonds and PANI. This work provides a novel prospect to develop efficient MOF derived bifunctional electrocatalysts by optimizing surface chemisorption properties.
基金the financial support from the National Natural Science Foundation of China(U1810111,51872124 and21676116)Natural Science Foundation of Guangdong Province,China(2018B030311010)+1 种基金the Fundamental Research Funds for the Central Universities(21617431)Key Laboratory of Biomass Chemical Engineering of Ministry of Education,Zhejiang University(2018BCE002)
文摘As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.
基金Supported by the National Natural Science Foundation of China(Nos.31670969,82172440)the Fundamental Research Funds for the Central Universities(Nos.21620417,21621103)+2 种基金the Medical Joint Fund of Jinan University(No.YXJC2022005)the National Key Research and Development Program of China(No.2022YFE0206200)the Funding of Science and Technology Projects in Guangzhou(Nos.202206010158,202201020087)。
文摘A composite bone cement based onα-TCP with self-reinforcing characteristics is prepared by compounding cellulose whiskers and polyvinyl alcohol in different proportions.In this system,we are inspired by the sea cucumber,which can alter the stiffness of their inner dermis reversibly.Through the formation of hydrogen bonds between the hydroxyl groups on the cellulose whiskers and PVA,the bone cement matrix can be strengthened during the curing process of cement.In the process of bone cement blending,there is more water,the hydrogen bond connection is destroyed,so the slurry has better fluidity at this time.As the hydration of the bone cement progresses,the reduction of the water phase leads to the formation of a permeable network structure of hydrogen bond connections between the whiskers.The dual-phase action of PVA and whiskers greatly increases the mechanical strength of the bone cement system(5.5 to 23.8 MPa),while the presence of polyvinyl alcohol improves the toughness of the bone cement system.This work was supposed to explore whether the chemoresponsive materials can be adapted to biomedical materials,for example,bone repair.
基金financial support from National Natural Science Foundation of China (U1810111)Natural Science Foundation of Guangdong Province, China (2018B030311010)+1 种基金Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University (2018BCE002)the Fundamental Research Funds for the Central Universities (21617431)
文摘This review intends to introduce the application of lignin-derived catalyst for green organic synthesis over latest two decades and aims to present a renewable alternative for conventional catalyst for future industry application. The structure of lignin is initially introduced in this review. Then, various pretreatment and activation technologies of lignin are systematically presented, which includes physical activation for the formation of well-developed porosity and chemical activation to introduce catalytic active sites. Finally, the catalytic performances of various lignin-derived catalysts are rationally assessed and compared with conventional catalysts, which involves lignin-derived solid acids for hydrolysis, hydration, dehydration(trans)esterification, multi-component reaction and condensation, lignin-derived solid base for Knoevenagel reaction, lignin-derived electro-catalysts for electro-oxidation, oxygen reduction reaction, and lignin-derived supported transition metal catalysts for hydrogenation, oxidation, coupling reaction, tandem reaction, condensation reaction, ring-opening reaction, Friedel-Crafts-type reaction,Fischer–Tropsch synthesis, click reaction, Glaser reaction, cycloaddition and(trans)esterification. The above lignin-derived catalysts thus successfully promote the transformations of organic compounds, carbon dioxide, biomass-based cellulose, saccharide and vegetable oil into valuable chemicals and fuels. At the end of this review, some perspectives are given on the current issues and tendency on the lignin-derived catalysts for green chemistry.
基金financial support by the National Natural Science Foundation of China (52002149)the Shenzhen Technical Plan Project (JCYJ20160301154114273)Australian Research Council through the ARC Discovery projects (DP16010^(4)340 and DP170100436)。
文摘Rechargeable aqueous zinc-ion batteries(ZIBs) have become a research hotspot in recent years,due to their huge potential for high-energy,fast-rate,safe and low-cost energy storage.To realize good electrochemical properties of ZIBs,cathode materials with prominent Zn^(2+) storage capability are highly needed.Herein,we report a promising ZIB cathode material based on electrochemically induced transformation of vanadium oxides.Specifically,K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers were synthesized through a simple stirring method at near room temperature and then used as cathode materials for ZIBs in different electrolytes.The cathode presented superior Zn^(2+) storage capability in Zn(OTf)_(2) aqueous electrolyte,including high capacity of 321 mAh/g,fast charge/discharge ability(96 mAh/g delivered in 35 s), high energy density of 235 Wh/kg and good cycling performance.Mechanism analysis evidenced that in Zn(OTf)_(2) electrolyte,Zn^(2+) intercalation in the first discharge process promoted K_(2) V_6 O_(16)·1.5 H_(2) O nanofibers to transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O nanoflakes,and the latter served as the Zn^(2+)-storage host in subsequent charge/discharge processes.Benefiting from open-framework crystal structure and sufficiently exposed surface,the Zn_(3+x)V_(2) O_7(OH)_(2)·2_H2 O nanoflakes exhibited high Zn^(2+) diffusion coefficient,smaller charge-transfer resistance and good reversibility of Zn^(2+) intercalation/de-intercalation,thus leading to superior electrochemical performance.While in ZnS04 aqueous electrolyte,the cathode material cannot sufficiently transform into Zn_(3+x)V_(2) O_7(OH)_(2)·2 H_(2) O thereby corresponding to inferior electrochemical behaviors.Underlying mechanism and influencing factors of such a transformation phenomenon was also explored.This work not only reports a high-performance ZIB cathode material based on electrochemically induced transformation of vanadium oxides,but also provides new insights into Zn^(2+)-storage electrochemistry.
基金We are grateful for the financial support from National Natural Science Foundation of China(U1810111,21676089)Natural Science Foundation of Guangdong Province,China(2018B030311010)+1 种基金Youth Science and Technology Innovation Talent of Guangdong TeZhi Plan(2019TQ05L111)Key Laboratory of Biomass Chemical Engineering of Ministry of Education,Zhejiang University(2018BCE002).
文摘The plasmonic photocatalyst of Pd supported on graphitic carbon nitride(Pd/g-C3N4)exhibits excellent catalytic activity in photo-induced hydrogenation of biomass-based aldehydes with environmental benign reagents of formic acid(HCOOH)as proton source and triethylamine(TEA)as sacrificial electron donator.The chemical and configurational properties of the Pd/g-C3N4 were systematically analyzed with XRD,TEM and XPS.Under optimized conditions,27%yield of furfuryl alcohol with the corresponding turnover frequency(TOF)around 3.72 h^(-1) were obtained from furfural and TEA-HCOOH under visible-light irradiation by using Pd/g-C3N4.Our research additionally reveals that Pd atom is the true catalytic active site for the hydrogenation and the photo-promoted reduction mainly occurs through noble metal nanoparticles(NPs)-induced effect of surface plasmon resonance(SPR).The photo-catalytic system of Pd/g-C3N4 thus demonstrates a green and effective method for the hydrogenation of biomass-based aldehydes with sustainable solar energy as a driven force.
基金supported by the National Natural Science Foundation of China(21472189)Natural Science Foundation of Guangdong Province,China(2015A030312007)+1 种基金Science and Technology Planning Project of Guangzhou City,China(201707010238)Jinan Double Hundred Talents Plan
文摘Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural(HMF) to 2,5-dihydroxymethyltetrahydrofuran(DHMTHF) with 96% selectivity and a complete HMF conversion is obtained over palladium catalyst supported on mesoporous graphitic carbon nitride(Pd/mpg-C_3N_4) under pressured hydrogen atmosphere in aqueous media. The excellent catalytic performance of Pd/mpg-C_3N_4 is attributed to hydrogen bonding-related competitive interactions between reactant HMF and “intermediate” 2,5-dihydroxymethylfuran(DHMF) with the support mpg-C_3N_4, which leads to a deep hydrogenation of DHMF to DHMTHF.
基金Natural Science Key Foundation of Guangdong Province(No.2019B1515120056)National Natural Science Foundation of China(No.51872124)+1 种基金Innovation Team Project of Foshan City(No.FS0AA-KJ919-4402-0086)open experimental project by GETRC of Graphene-like Materials and Products(No.GETRCGL-202207).
文摘Implant-associated infections(IAIs)caused by drug-resistant bacteria remain a critical factor in the fail-ure of implant procedures.Therefore,it is urgent to develop an effective anti-infection coating for im-plant surface modification to prevent IAIs.Herein,an antibacterial and anti-adhesive coating(CMP-Ti)constructed on the surface of titanium implants is reported,formed by the nanomaterial CeO_(2)@Mn_(3)O_(4) NRs(CM NRs)with antibacterial activity and the superhydrophilic polymer polyethylene glycol(PEG).The nanocatalyst CM NRs on the surface of CMP-Ti induce ferroptosis-like death of bacteria by catalyzing the production of hydroxyl radical(·OH)and singlet oxygen(^(1)O_(2))and the consumption of glutathione(GSH).The superhydrophilic coating of CMP-Ti can effectively prevent adherence of drug-resistant bac-teria and avoid biofilm formation.By combining the"active offense"antibacterial mechanism with the"passive defense"anti-adhesion mechanism,CMP-Ti can kill bacteria and inhibit biofilm formation.The results of in vivo studies showed that CMP-Ti effectively prevented implant-associated infections caused by Methicillin-resistant Staphylococcus aureus(MRSA),thus promoting tissue repair and osseointegra-tion.Therefore,this multifunctional coating combining"active offense"and"passive defense"provides a promising way to prevent IAIs caused by drug-resistant bacteria and to promote tissue repair in the future.
基金National Natural Science Foundation of China(51933011,31971296,52173125,82102194,81873920,82001930)Key Areas Research and Development Program of Guangzhou(202007020006)+2 种基金Natural Science Foundation of the Guangdong Province(2021A1515010250,2020A1515111206,2021A1515111006)China Postdoctoral Science Foundation(2020M680119,2021M703763)Funding of the Southern Medical University Nanfang Hospital(2019C015).
文摘Thermal ablation(TA)as an effective method treating hepatocellular carcinoma(HCC)in clinics is facing great challenges of high recurrence and metastasis.Although immune-checkpoint blockade(ICB)-based immuno-therapy has shown potential to inhibit recurrence and metastasis,the combination strategy of ICB and thermal ablation has shown little progress in HCC treatments.The tremendous hurdle for combining ICB with thermal ablation lies with the insufficient antigen internalization and immaturity of tumor-infiltrating dendritic cells(TIDCs)which leads to an inferior immune response to distant tumor growth and metastasis.Herein,an antigen-capturing nanoplatform,whose surface was modified with mannose as a targeting ligand,was constructed for co-delivering tumor-associated antigens(TAAs)and m6A demethylases inhibitor(i.e.,fat mass and obesity asso-ciated gene(FTO)inhibitor)into TIDCs.In vivo results demonstrate that the intratumoral injection of nanodrug followed by HCC thermal ablation promotes dendritic cells(DCs)maturation,improves tumor infiltration of effector T cells and generates immune memory,which synergize with ICB treatment to inhibit the distant tumor growth and lung metastasis.Therefore,the antigen-capturing and FTO-inhibiting nanodrug holds potential to boost the ICB-based immunotherapy against HCC after thermal ablation.
基金financially supported by the National Natural Science Foundation of China (22209057)the Guangdong Basic and Applied Basic Research Foundation (2021A1515010362)+1 种基金the Guangzhou Basic and Applied Basic Research Foundation (202102020995)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications (2020B121201005)。
文摘Considering their superior theoretical capacity and low voltage plateau,bismuth(Bi)-based materials are being widely explored for application in potassium-ion batteries(PIBs).Unfortunately,pure Bi and Bibased compounds suffer from severe electrochemical polarization,agglomeration,and dramatic volume fluctuations.To develop an advanced bismuth-based anode material with high reactivity and durability,in this work,the pyrolysis of Bi-based metal-organic frameworks and in-situ selenization techniques have been successfully used to produce a Bi-based composite with high capacity and unique structure,in which Bi/Bi_(3)Se_(4)nanoparticles are encapsulated in carbon nanorods(Bi/Bi_(3)Se_(4)@CNR).Applied as the anode material of PIBs,the Bi/Bi_(3)Se_(4)@CNR displays fast potassium storage capability with 307.5 m A h g^(-1)at 20 A g^(-1)and durable cycle performance of 2000 cycles at 5 A g^(-1).Notably,the Bi/Bi_(3)Se_(4)@CNR also showed long cycle stability over 1600 cycles when working in a full cell system with potassium vanadate as the cathode material,which further demonstrates its promising potential in the field of PIBs.Additionally,the dual potassium storage mechanism of the Bi/Bi_(3)Se_(4)@CNR based on conversion and alloying reaction has also been revealed by in-situ X-ray diffraction.
基金the National Natural Science Foundation of China(No.31971270)the grant of Peak Climbing Project of Foshan Hospital of Traditional Chinese Medicine(CN)(No.202000190).
文摘Pore characteristics have been identified as key design parameters for osteoimmunomodulation.The strategy reported here is to create an appropriate immune microenvironment by regulating pore characteristics of scaffolds,thereby promoting early angiogenesis and enhancing osteogenesis.A series of collagen/nanohydroxyapatite(Col/nHAP)composite scaffolds with ordered lamellar structures and different layer spacings were prepared by mimicking the ordered lamellar topology of the bone matrix.Our research indicated that the layer spacing and ordered topology of the scaffold exerted an important influence on phenotype transformation of macrophages and the secretion of angiogenic factors.The Col/nHAP-O(135)with large layer spacing not only supported cell attachment and diffusion in vitro,but also promoted early angiogenesis by timely switching from M1 to M2 macrophage phenotype.In vivo data showed that the layer spacing and the ordered structure of the scaffold synergistically regulated the inflammatory response and triggered macrophages to secrete more angiogenesis related cytokines.Col/nHAP-O(135)considerably promoted the neovascularization and new bone formation in the defect site,indicating that Col/nHAPO(135)could significantly enhance the osteogenic activity of stem cells with the involvement of macrophages.
基金supported by the CAS Project for Young Scientists in Basic Research(YSBR-058)the Basic Science Center Project of National Natural Science Foundation of China(52388201)+57 种基金the Beijing Natural Science Foundation(JQ22005)financially supported by the National Key R&D Program of China(2022YFB2404400)the National Natural Science Foundation of China(92263206,21875007,21975006,21974007,and U19A2018)the Youth Beijing Scholars program(PXM2021_014204_000023)the Beijing Natural Science Foundation(2222001 and KZ202010005007)supported by the National Key R&D Program of China(2021YFB2400200)the Youth Innovation Promotion Association CAS(2023040)the National Natural Science Foundation of China(22279148 and 21905286)the Beijing Natural Science Foundation(Z220021)supported by Beijing Municipal Natural Science Foundation(Z200011)National Key Research and Development Program(2021YFB2500300,2021YFB2400300)National Natural Science Foundation of China(22308190,22109084,22108151,22075029,and 22061132002)Key Research and Development Program of Yunnan Province(202103AA080019)the S&T Program of Hebei Province(22344402D)China Postdoctoral Science Foundation(2022TQ0165)Tsinghua-Jiangyin Innovation Special Fund(TJISF)Tsinghua-Toyota Joint Research Fundthe Institute of Strategic Research,Huawei Technologies Co.,LtdOrdos-Tsinghua Innovative&Collaborative Research Program in Carbon Neutralitythe Shuimu Tsinghua Scholar Program of Tsinghua Universityfinancially supported by the National Key R&D Program of China(2021YFB2400300)National Natural Science Foundation of China(22179083)Program of Shanghai Academic Research Leader(20XD1401900)Key-Area Research and Development Program of Guangdong Province(2019B090908001)financially supported by the National Key R&D Program of China(2020YFE0204500)the National Natural Science Foundation of China(52071311,52271140)Jilin Province Science and Technology Development Plan Funding Project(20220201112GX)Changchun Science and Technology Development Plan Funding Project(21ZY06)Youth Innovation Promotion Association CAS(2020230,2021223)supported by the National Natural Science Foundation of China(51971124,52171217,52202284 and 52250710680)the State Key Laboratory of Electrical Insulation and Power Equipment,Xi’an Jiaotong University(EIPE22208)Zhejiang Natural Science Foundation(LZ21E010001,LQ23E020002)Wenzhou Natural Science Foundation(G20220019,G20220021,ZG2022032,G2023027)Science and Technology Project of State Grid Corporation of China(5419-202158503A-0-5-ZN)Wenzhou Key Scientific and Technological Innovation Research Projects(ZG2023053)Cooperation between industry and education project of Ministry of Education(220601318235513)supported by the Australian Research Council(DP210101486 and FL210100050)supported by the National Natural Science Foundation of China(22179135,22109168,52072195,and 21975271)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA22010603,XDA22010600)Taishan Scholars Program for Young Expert of Shandong Province(tsqn202103145)Shandong Energy Institute(SEI I202108 and SEI I202127)the China Postdoctoral Science Foundation(BX20200344,2020M682251)supported by the National Key R&D Program of China(2022YFB2402200)the National Natural Science Foundation of China(22121005,22020102002,and 21835004)the Frontiers Science Center for New Organic Matter of Nankai University(63181206)the Haihe Laboratory of Sustainable Chemical Transformationssupported by National Key Research and Development Program of China(2022YFB2404500)Shenzhen Outstanding Talents Training Fundsupported by the National Key R&D Program of China(2019YFA0705104)GRF under the project number City U 11305218supported from National Natural Science Foundation of China(22078313,21925804)Free exploring basic research project of Liaoning(2022JH6/100100005)Youth Innovation Promotion Association CAS(2019182)supported from the Research Center for industries of the Future(RCIF)at Westlake Universitythe start-up fund from Westlake Universitysupported by the National Key R&D Program of China(2020YFB2007400)the National Natural Science Foundation of China(22075317)the Strategic Priority Research Program(B)(XDB07030200)of Chinese Academy of Sciences。
文摘Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global climate change.Due to the increased popularity of consumer electronics and electric vehicles,lithium-ion batteries have quickly become the most successful rechargeable batteries in the past three decades,yet growing demands in diversified application scenarios call for new types of rechargeable batteries.Tremendous efforts are made to developing the next-generation post-Li-ion rechargeable batteries,which include,but are not limited to solid-state batteries,lithium–sulfur batteries,sodium-/potassium-ion batteries,organic batteries,magnesium-/zinc-ion batteries,aqueous batteries and flow batteries.Despite the great achievements,challenges persist in precise understandings about the electrochemical reaction and charge transfer process,and optimal design of key materials and interfaces in a battery.This roadmap tends to provide an overview about the current research progress,key challenges and future prospects of various types of rechargeable batteries.New computational methods for materials development,and characterization techniques will also be discussed as they play an important role in battery research.
基金supported by the National Natural Science Foundation of China(22275073,22005119,21731002,2197510422150004)the Guangdong Major Project of Basic and Applied Research(2019B030302009)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(2020A1515110404)the Guangzhou Basic and Applied Basic Research Foundation(2024A04J3597,202102020444)the Fundamental Research Funds for the Central Universities(21622409)。
文摘Metal-organic frameworks(MOFs)hold significant potential as vehicles for drug delivery due to their expansive specific surface area,biocompatibility,and versatile attributes.Concurrently,magnetically actuated micro/nano-robots(MNRs)offer distinct advantages,such as untethered and precise manipulation.The fusion of these technologies presents a promising avenue for achieving non-invasive targeted drug delivery.Here,we report a MOF-based magnetic microrobot swarm(MMRS)for targeted therapy.Our approach overcomes limitations associated with a single MNR,including limited drug loading and the risk of loss during manipulation.We select Zeolitic Imidazolate Framework-8(ZIF-8)as the drug vehicle for its superior loading potential and p H-sensitive decomposition.Our design incorporates magnetic responsive components into the one-pot synthesis of Fe@ZIF-8,enabling collective behaviors under actuation.Tuning the yaw angle of alternating magnetic fields and nanoparticles'amount,the MMRSs with controllable size achieve instantaneous transformation among different configurations,including vortex-like swarms,chain-like swarms,and elliptical swarms,facilitating adaptation to environmental variations.Transported to the subcutaneous T24 tumor site,the MMRSs with encapsulated doxorubicin(DOX)automatically degrade and release the drug,leading to a dramatic reduction of the tumor in vivo.Our investigation signifies a significant advancement in the integration of biodegradable MOFs into microrobot swarms,ushering in new avenues for accurate and non-invasive targeted drug delivery.
基金National Natural Science Foundation of China(No.52002149)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515111202)the fellowship of China Postdoctoral Science Foundation(2020M683186)。
文摘Zn-based electrochemical energy storage(EES)systems have received tremendous attention in recent years,but their zinc anodes are seriously plagued by the issues of zinc dendrite and side reactions(e.g.,corrosion and hydrogen evolution).Herein,we report a novel strategy of employing zincophilic Cu nanowire networks to stabilize zinc anodes from multiple aspects.According to experimental results,COMSOL simulation and density functional theory calculations,the Cu nanowire networks covering on zinc anode surface not only homogenize the surface electric field and Zn^(2+)concentration field,but also inhibit side reactions through their hydrophobic feature.Meanwhile,facets and edge sites of the Cu nanowires,especially the latter ones,are revealed to be highly zincophilic to induce uniform zinc nucleation/deposition.Consequently,the Cu nanowire networks-protected zinc anodes exhibit an ultralong cycle life of over 2800 h and also can continuously operate for hundreds of hours even at very large charge/discharge currents and areal capacities(e.g.,10 mA cm^(-2)and 5 mAh cm^(-2)),remarkably superior to bare zinc anodes and most of currently reported zinc anodes,thereby enabling Zn-based EES devices to possess high capacity,16,000-cycle lifespan and rapid charge/discharge ability.This work provides new thoughts to realize long-life and high-rate zinc anodes.