The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we re...The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs(PtNi@HCS)as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water.Using both density functional theory calculations and molecular dynamics simulations,the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored.Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism,with oxidative addition of an O-H bond of water to the catalyst surface being the rate-determining step.The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions,using in situ-generated H_(2) from ammonia borane with high efficiency.The concerted design,theoretical calculations,and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.展开更多
Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports...Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports the approach to preparing tunable hollow TiO_(2) nanospheres by utilization of spherical polyelectrolyte brushes(SPB)as nanoreactors and templates.During the preparation,the evolution of the structure was characterized by small angle X-ray scattering(SAXS),and in combination with dynamic light scattering and transmission electron microscopy.The formation of TiO_(2) shell within the brush(SPB@TiO_(2))is confirmed by the significant increase of the electron density,and its internal structure has been analyzed by fitting SAXS data,which can be influenced by Titanium precursors and ammonia concentration.After calcining SPB@TiO_(2) in a muffle furnace,hollow TiO_(2) nanospheres are produced,and their transition to the anatase crystal form is triggered,as confirmed by X-ray diffraction analysis.Utilizing the advantages of their hollow structure,these TiO_(2) nanospheres exhibit exceptional catalytic degradation efficiency of methylene blue(MB),tetracycline(TC),and 2,4-dichlorophenoxyacetic acid(2,4-D),and also demonstrate excellent recyclability.展开更多
The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosyn...The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.展开更多
Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improv...Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.展开更多
Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic a...Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic acid(TA),iron ion(Fe^(3+)),and docetaxel(DOC)wi+microtubule inhibition,reactive oxygen species(ROS)generation,and gluta+ione peroxidase 4(GPX4)inhibition,is prepared for ferroptosis/apoptosis treatment.After internalization by CT26 cells,+e DOC@TA-Fe^(3+)nanoreactor escapes from+e lysosomes to release payloads.+e subsequent Fe^(3+)/Fe^(2+)conversion mediated by TA reducibility can trigger+e Fenton reaction to enhance+e ROS concentration.Additionally,Fe^(3+)can consume gluta+ione to repress+e activity of GPX4 to induce ferroptosis.Meanwhile,+e released DOC controls microtubule dynamics to activate+e apoptosis pa+way.+e superior in vivo antitumor efficacy of DOC@TA-Fe^(3+)nanoreactor in terms of tumor grow+inhibition and improved survival is verified in CT26 tumor-bearing mouse model.+erefore,+e nanoreactor can act as an effective apoptosis and ferroptosis inducer for application in colorectal cancer+erapy.展开更多
Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic...Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic performance and phosphating degree of precursors.In this work,using Co3O4@SiO2 as precursor,core-shell structured CoP@SiO2 nanoreactors with outstanding oxygen evolution reaction performance were synthesized through a facile calcination method.The electrocatalytic performance of CoP@SiO2 modified electrode that treated with 500 mg NaH2PO2 was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm2 and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO2 with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.展开更多
The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bioni...The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bionic cascaded-enzyme nanoreactor based on Ti_(3)C_(2)nanosheets for combined tumor enzyme dynamic therapy(EDT),phototherapy and deoxygenation-activated chemotherapy.Briefly,glucose oxidase(GOX)and chloroperoxidase(CPO)were chemically conjugated onto Ti_(3)C_(2)nanosheets,where the deoxygenation-activated drug tirapazamine(TPZ)was also loaded,and the Ti_(3)C_(2)-GOX-CPO/TPZ(TGCT)was embedded into nanosized cancer cell-derived membrane vesicles with high-expressed CD47(m_eTGCT).Due to biomimetic membrane camouflage and CD47 overexpression,m_eTGCT exhibited superior immune escape and homologous targeting capacities,which could effectively enhance the tumor preferential targeting and internalization.Once internalized into tumor cells,the cascade reaction of GOX and CPO could generate HClO for efficient EDT.Simultaneously,additional laser irradiation could accelerate the enzymic-catalytic reaction rate and increase the generation of singlet oxygen(~1O_(2)).Furthermore,local hypoxia environment with the oxygen depletion by EDT would activate deoxygenation-sensitive prodrug for additional chemotherapy.Consequently,m_eTGCT exhibits amplified synergistic therapeutic effects of tumor phototherapy,EDT and chemotherapy for efficient tumor inhibition.This intelligent cascaded-enzyme nanoreactor provides a promising approach to achieve concurrent and significant antitumor therapy.展开更多
Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐s...Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐shell structured nanoparticles as nanoreactors for various chemical reactions.A very brief overview of synthetic strategies is provided with emphasis on recent research progress in the last five years.Catalytic applications of these yolk‐shell structured nanoreactors are then discussed by covering photocatalysis,methane reforming and electrochemical conversion.The state of the art research and perspective in future development are also highlighted.展开更多
An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction o...An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene,alcohol,enamine,and aldehydes is reported.Dihydropyridine derivatives based on neat adduct of diketene,alcohols and aldehydes using SBA-15/SO_3H nanoreactor as catalyst via a four-component reactions are also synthesized.The advantages of the present method include the use of a small amount catalyst,simple procedure with an easy filterable work-up,waste-free,green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.展开更多
Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartme...Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartment structure to achieve the combination of unique chemical properties and structural feature is still challenging due to the synthetic difficulties.Herein,we designed and synthesized a catalytically active,PTC gold(Au)@polydopamine(PDA)nanoreactor driven by infrared irradiation using assembled PS-b-P2VP nanosphere as soft template.The particles exhibit multi-compartment structure which is revealed by 3D electron tomography characterization technique.They feature permeable shells with tunable shell thickness.Full kinetics for the reduction reaction of 4-nitrophenol has been investigated using these particles as nanoreactors and compared with other reported systems.Notably,a remarkable acceleration of the catalytic reaction upon near-infrared irradiation is demonstrated,which reveals for the first time the importance of the synergistic effect of photothermal conversion and complex inner structure to the kinetics of the catalytic reduction.The ease of synthesis and fresh insights into catalysis will promote a new platform for novel nanoreactor studies.展开更多
Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxida...Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxidase(HRP)-like nanozyme(Fe-aminoclay) was in situ synthesized on the surface of alkali-activated halloysite nanotubes and the natural enzyme(glucose oxidase, GOx) was immobilized on it to construct a high-efficiency GOx-Fe AC@AHNTs cascade nanoreactor. In which, Fe AC@AHNTs can not only be used as a carrier for immobilized enzymes, but also help its catalytic activity to cooperate with glucose oxidase in a cascade reaction. The microcompartments and substrate channel effect of this enzyme-nanozyme microsystem exhibit a superior catalytic performance than that of natural enzyme system, and exhibits excellent long-term stability and recyclability. Subsequently, the GOx-Fe AC@AHNTs cascade nanoreactor was employed as a glucose colorimetric platform, which displayed a low detection limit(0.47 μmol/L)in glucose detection. This enzyme-nanoenzyme nanoreactor provides a simple and effective example for constructing a multi-enzyme system with limited space, and lays the foundation for subsequent research in the fields of biological analysis and catalysis.展开更多
The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO2(JS) and to encapsulate metal oxide nanoparticles(Co3O4) int...The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO2(JS) and to encapsulate metal oxide nanoparticles(Co3O4) into nanoreactors(SiO2).ZIF-67 crystals provide a cobalt species;SiO2 was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co3O4@SiO2 with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co3(OH)4Si2O5.Subsequently,CoSx and CoP-SiO2 were fabricated through sulfuration and phosphorization.The results in this work show that nanoreactors derived from metal-organic frameworks(MOFs) with a rational structure have broad development prospects.展开更多
Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andco...Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andcompensating for hydrogen peroxide (H2O2) and acidity in thetumor microenvironment is crucial for enhancing the effectivenessof CO therapy. In this study, a tumor microenvironment-responsive core-shell structured cascade nanoreactorwas designed and synthesized using mesoporous polydopamine(MPDA) as a nanocarrier, followed by loading ofMnCO and glucose oxidase-encapsulated zeolite imidazolateframework-8 (GOx@ZIF-8) nanoparticles. Upon enteringcancer cells, the protective shell of GOx@ZIF-8 degrades inresponse to the acidic tumor environment, releasing GOx.GOx catalyzes the conversion of endogenous glucose intogluconic acid and H2O2, accelerating energy starvation in tumorcells. This process, in turn, promotes the reaction betweenMnCO and H2O2, resulting in in-situ amplified release of CO.Additionally, the excellent photothermal properties of MPDAenable photothermal therapy. This comprehensive antitumorstrategy represents a promising advancement in the field ofCO-based cancer therapy.展开更多
Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited cat...Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited catalytic performance due to the confinement of their active components in the“nanochamber”.Herein,low-content active metal(AM,AM=Pd,Cu)decorated yolk-shelled FeCoNiOx(AM/FeCoNiOx)nanoreactors with magnetic recycling properties are synthesized through a simple two-step method.The obtained AM/FeCoNiOxnanospheres are characterized by their distinctive structure and the integration of two kinds of catalytically active components,namely the active FeCoNiOxsubstrate and the well-dispersed AMs in the whole yolk-shelled substrate.These nanospheres can be utilized as nanoreactors in two types of organic reactions(i.e.,reduction and oxidation).During the catalytic reduction of prototypical nitrogen-containing unsaturated organic compounds(e.g.,4-nitrophenol)using sodium borohydride,the Pd/FeCoNiOxnanoreactors demonstrate high activity over Cu/FeCoNiOxand FeCoNiOxcounterparts.The catalytic efficiency significantly surpasses that of a variety of magnetic metalbased nanocatalysts reported recently.Meanwhile,the Pd/FeCoNiOxnanoreactors demonstrate remarkable stability and broadspectrum catalytic capability towards reduction of the other nitrogen-containing unsaturated compounds,including eight substituted nitrobenzenes and two azo dyes.Furthermore,the Pd/FeCoNiOxnanoreactors exhibit exceptional catalytic activity and selectivity in promoting the oxidation of benzyl alcohol.This research provides an effective strategy for the rational design and fabrication of a dual-active-component nanoreactor with simple recycling,which is of practical significance for future sustainable industrial applications.展开更多
Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,th...Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,the MOF coating significantly reduces the NC catalytic efficiency due to the diffusion barriers and the confined microenvironments.Herein,a hierarchically engineered MOF nanoreactor was constructed by controlled structural etching for NC immobilization.This nanoreactor possesses hierarchical pores to accelerate the diffusion rate of reactants and creates hollow structures to unleash the confined NC molecules from the rigid MOF network to a capacious microenvironment.The enhanced mass transfer,improved freedom of NCs,and outstanding stability collectively boosted the catalytic activity of the nanoreactor.By controlling the etching time,freestanding Pd8@zeolitic imidazolate framework-8(ZIF-8)-TA10 displayed a catalytic efficiency that was 3.17 times greater than that of the initial confined Pd8@ZIF-8 and even better than free Pd8.This work opens a new strategy to reduce the inherent limitations of porous matrixes for developing high-performance catalysts.展开更多
Yolk-shell and hollow structures are powerful platforms for controlled release,confined nanocatalysis,and optical and electronic applications.This contribution describes a fabrication strategy for a yolk-shell nanorea...Yolk-shell and hollow structures are powerful platforms for controlled release,confined nanocatalysis,and optical and electronic applications.This contribution describes a fabrication strategy for a yolk-shell nanoreactor(NR)using a post decoration approach.The widely studied yolk-shell structure of silica-coated TiO_(2)(TiO_(2)@SiO_(2))was used as a model.At first,anatase TiO_(2)spheres were prepared,and subsequently were given a continuous coating of carbonaceous and silica layers.Finally,the carbonaceous layer was removed to produce a yolk-shell structure TiO_(2)@SiO_(2).By using an in-situ photodeposition method,Pt-encased spheres(Pt-TiO_(2)@SiO_(2))were synthesized with Pt nanoparticles grown on the surface of the TiO_(2)core,which contained void spaces suitable for use as NRs.The NR showed enhanced hydrogen production with a rate of 24.56 mmol·g^(-1)·h^(-1)in the presence of a sacrificial agent under simulated sunlight.This strategy holds the potential to be extended for the synthesis of other yolk-shell photocatalytic NRs with different metal oxides.展开更多
Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,w...Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,we report the assembling of yttrium-decorated bimetallic MOFs via one-step hydrothermal strategy,which can act as a sensitized nanoreactor for syngas production under y-ray irradiation.The flower-shaped CuNi-MOF matrix with tunable metal centers exposed plentiful cooperative active sites for CO_(2)binding,and its nanopetals enabled the well dispersion of Y_(2)O_(3)nanoparticles on the surfaces.The introduction of high-Z element Y enhanced the secondary electron scattering and promoted the water radiolysis to produce more hydrated electrons(e_(aq)^(-)),thus accelerating the initial CO_(2)activation to CO_(2)^(·-).Moreover,the in situ formed coupling interlayer provided a fast charge transfer channel between Y_(2)O_(3)and the MOF framework,which facilitated the interfacial electron migration for intermediate generation and subsequent CO_(2)conversion.By regulating the contents of Cu and Y_(2)O_(3)within the nanocomposites,the affinity toward CO_(2)and the product compositions could be modulated.As a result,the optimal 7CN-2Y catalyst achieved a high syngas evolution rate of 311.07μmol g^(-1)with a H_(2)/CO ratio of 2.7:1 at an absorbed dose of 4 kGy.The present study offered a feasible route for the efficient transformation of CO_(2)into valuable chemicals and the design of viable catalysts for ionizing radiation.展开更多
Covalent organic frameworks(COFs)-based nanoreactors have attracted broad interest in many fields due to their voidconfinement effects.However,the inherent drawback of conventional nanoreactors is the lack of internal...Covalent organic frameworks(COFs)-based nanoreactors have attracted broad interest in many fields due to their voidconfinement effects.However,the inherent drawback of conventional nanoreactors is the lack of internal active sites,which limits their widespread utilization.Herein,we report the construction of hierarchical COF(EB-TFP)nanoreactor with pre-synthesized polyoxometalates(POM,[PV_(2)W_(10)O_(40)]^(5–)(PV_(2)W_(10)))clusters encapsulated inside of COF(POM@COF).PV_(2)W_(10)@EB-TFP anchors nucleophilic-group(Br–ions)and PV_(2)W_(10)anion cluster within the COF framework via electrostatic interactions,which not only simplifies the reaction system but also enhances catalytic efficiency.The reaction performance of the PV_(2)W_(10)@EB-TFP nanoreactor can be tuned to achieve excellent catalytic activity in CO_(2)cycloaddition reaction(CCR)for~97.63%conversion and~100%selectivity under visible light irradiation.A mechanistic study based on density functional theory(DFT)calculations and insitu characterization was also carried out.In summary,we have reported a method for achieving the uniform dispersion of POM single clusters into COF nanoreactor,demonstrating the potential of POM@COF nanoreactor for synergistic photothermal catalytic CO_(2)cycloaddition.展开更多
SO_(2)poisoning is a common problem in the catalytic combustion of volatile organic compounds(VOCs).In this work,we took three-dimensionally ordered macroporous and mesoporous(3DOM)SiO_(2)as the nanoreactor to protect...SO_(2)poisoning is a common problem in the catalytic combustion of volatile organic compounds(VOCs).In this work,we took three-dimensionally ordered macroporous and mesoporous(3DOM)SiO_(2)as the nanoreactor to protect active sites from SO_(2)erosion in the catalytic combustion of benzene.Simultaneously,the confined growth of metal active nanoparticles in the multi-stage pore is also full of challenges.And we successfully confined Co_(3)O_(4)nanoparticles(NPs)in macroporous and mesoporous channels.Interestingly,the precursors’growth in the pore was controlled and nanoreactors with different pore sizes were prepared by adjusting the loading amount and preparation methods.It is discovered that the Co_(3)O_(4)NPs confined in 3DOM SiO_(2)nanoreactor showed superior sulfur and water resistance.Density functional theory(DFT)calculations verified that the Co-Si catalyst had high SO_(2)adsorption energy(-0.48 eV),which illustrated that SO_(2)was hard to attach to the surface of the Co-Si catalyst.The SiO_(2)nanoreactor had low SO_(2)adsorption energy(-5.15 eV),which indicated that SO_(2)was easily absorbed on SiO_(2)nanoreactor.This illustrated that the SiO_(2)nanoreactor could protect effectively active sites from SO_(2)erosion.展开更多
Tumor microenvironment(TME),as the“soil”of tumor growth and metastasis,exhibits significant differences from normal physiological conditions.However,how to manipulate the distinctions to achieve the accurate therapy...Tumor microenvironment(TME),as the“soil”of tumor growth and metastasis,exhibits significant differences from normal physiological conditions.However,how to manipulate the distinctions to achieve the accurate therapy of primary and metastatic tumors is still a challenge.Herein,an innovative nanoreactor(AH@MBTF)is developed to utilize the apparent differences(copper concentration and H_(2)O_(2)level)between tumor cells and normal cells to eliminate primary tumor based on H_(2)O_(2)-dependent photothermal-chemodynamic therapy and suppress metastatic tumor through copper complexation.This nanoreactor is constructed using functionalized MSN incorporating benzoyl thiourea(BTU),triphenylphosphine(TPP),and folic acid(FA),while being co-loaded with horseradish peroxidase(HRP)and its substrate ABTS.During therapy,the BTU moieties on AH@MBTF could capture excessive copper(highly correlated with tumor metastasis),presenting exceptional anti-metastasis activity.Simultaneously,the complexation between BTU and copper triggers the formation of cuprous ions,which further react with H_(2)O_(2)to generate cytotoxic hydroxyl radical(•OH),inhibiting tumor growth via che-modynamic therapy.Additionally,the stepwise targeting of FA and TPP guides AH@MBTF to accurately accu-mulate in tumor mitochondria,containing abnormally high levels of H_(2)O_(2).As a catalyst,HRP mediates the oxidation reaction between ABTS and H_(2)O_(2)to yield activated ABTS•^(+).Upon 808 nm laser irradiation,the activated ABTS•^(+)performs tumor-specific photothermal therapy,achieving the ablation of primary tumor by raising the tissue temperature.Collectively,this intelligent nanoreactor possesses profound potential in inhib-iting tumor progression and metastasis.展开更多
基金Financial support was received from the National Key R&D Program of China (2021YFC2902505)the start-up funding by Beijing University of Technology (Changlong Wang)。
文摘The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs(PtNi@HCS)as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water.Using both density functional theory calculations and molecular dynamics simulations,the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored.Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism,with oxidative addition of an O-H bond of water to the catalyst surface being the rate-determining step.The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions,using in situ-generated H_(2) from ammonia borane with high efficiency.The concerted design,theoretical calculations,and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.
基金funded by the National Key Research and Development Program of China,grant number 2023YFD1700303.
文摘Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports the approach to preparing tunable hollow TiO_(2) nanospheres by utilization of spherical polyelectrolyte brushes(SPB)as nanoreactors and templates.During the preparation,the evolution of the structure was characterized by small angle X-ray scattering(SAXS),and in combination with dynamic light scattering and transmission electron microscopy.The formation of TiO_(2) shell within the brush(SPB@TiO_(2))is confirmed by the significant increase of the electron density,and its internal structure has been analyzed by fitting SAXS data,which can be influenced by Titanium precursors and ammonia concentration.After calcining SPB@TiO_(2) in a muffle furnace,hollow TiO_(2) nanospheres are produced,and their transition to the anatase crystal form is triggered,as confirmed by X-ray diffraction analysis.Utilizing the advantages of their hollow structure,these TiO_(2) nanospheres exhibit exceptional catalytic degradation efficiency of methylene blue(MB),tetracycline(TC),and 2,4-dichlorophenoxyacetic acid(2,4-D),and also demonstrate excellent recyclability.
基金supported by the National Natural Science Foundation of China(Grant Nos.21908052 and 22108200)the Key Program of the Natural Science Foundation of Hebei Province(Grant No.B2020209017)+2 种基金the Project of Science and Technology Innovation Team,Tangshan(Grant No.20130203D)the Natural Science Foundation of Zhejiang Province(Grant No.LQ22B060013)and the Science and Technology Project of Hebei Education Department(Grant No.QN2021113).
文摘The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.
基金financially supported by the National Natural Science Foundation of China (22372001)Starting Fund for Scientific Research of High-Level Talents, Anhui Agricultural University (rc382108)+1 种基金Anhui Provincial Key Research and Development Plan (2022e07020037)Innovation and Entrepreneurship Training Program for College Students (X202310364204, S202210364046, X202310364209)
文摘Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.
基金supported by the National Natural Science Foundation of China(Grant Nos.:31971308,81960769,and U1903211)National S&T Major Project(Grant No.:2019ZX09301-147),Luzhou Science and Technology Plan(Grant No.:2018CDLZ10)Sichuan Science and Technology Program(Grant No.:2021YFS0081).
文摘Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic acid(TA),iron ion(Fe^(3+)),and docetaxel(DOC)wi+microtubule inhibition,reactive oxygen species(ROS)generation,and gluta+ione peroxidase 4(GPX4)inhibition,is prepared for ferroptosis/apoptosis treatment.After internalization by CT26 cells,+e DOC@TA-Fe^(3+)nanoreactor escapes from+e lysosomes to release payloads.+e subsequent Fe^(3+)/Fe^(2+)conversion mediated by TA reducibility can trigger+e Fenton reaction to enhance+e ROS concentration.Additionally,Fe^(3+)can consume gluta+ione to repress+e activity of GPX4 to induce ferroptosis.Meanwhile,+e released DOC controls microtubule dynamics to activate+e apoptosis pa+way.+e superior in vivo antitumor efficacy of DOC@TA-Fe^(3+)nanoreactor in terms of tumor grow+inhibition and improved survival is verified in CT26 tumor-bearing mouse model.+erefore,+e nanoreactor can act as an effective apoptosis and ferroptosis inducer for application in colorectal cancer+erapy.
基金supported by the National Natural Science Foundation of China(Nos.U1904215,21671170 and 21673203)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+4 种基金Program for New Century Excellent Talents of the University in China(No.NCET-13-0645)the Six Talent Plan(No.2015XCL-030)Qinglan Project of JiangsuProgram for Colleges Natural Science Research in Jiangsu Province(No.18KJB150036)the Science and Technology Innovation Foster Foundation of Yangzhou University(No.2016CXJ010)。
文摘Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic performance and phosphating degree of precursors.In this work,using Co3O4@SiO2 as precursor,core-shell structured CoP@SiO2 nanoreactors with outstanding oxygen evolution reaction performance were synthesized through a facile calcination method.The electrocatalytic performance of CoP@SiO2 modified electrode that treated with 500 mg NaH2PO2 was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm2 and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO2 with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.
基金This work was supported by the National Natural Science Foundation of China(51773231)Shenzhen Science and Technology Project(JCYJ20190807160801664)the Project of Key Laboratory of Sensing Technology and Biomedical Instruments of Guangdong Province(2011A060901013).
文摘The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bionic cascaded-enzyme nanoreactor based on Ti_(3)C_(2)nanosheets for combined tumor enzyme dynamic therapy(EDT),phototherapy and deoxygenation-activated chemotherapy.Briefly,glucose oxidase(GOX)and chloroperoxidase(CPO)were chemically conjugated onto Ti_(3)C_(2)nanosheets,where the deoxygenation-activated drug tirapazamine(TPZ)was also loaded,and the Ti_(3)C_(2)-GOX-CPO/TPZ(TGCT)was embedded into nanosized cancer cell-derived membrane vesicles with high-expressed CD47(m_eTGCT).Due to biomimetic membrane camouflage and CD47 overexpression,m_eTGCT exhibited superior immune escape and homologous targeting capacities,which could effectively enhance the tumor preferential targeting and internalization.Once internalized into tumor cells,the cascade reaction of GOX and CPO could generate HClO for efficient EDT.Simultaneously,additional laser irradiation could accelerate the enzymic-catalytic reaction rate and increase the generation of singlet oxygen(~1O_(2)).Furthermore,local hypoxia environment with the oxygen depletion by EDT would activate deoxygenation-sensitive prodrug for additional chemotherapy.Consequently,m_eTGCT exhibits amplified synergistic therapeutic effects of tumor phototherapy,EDT and chemotherapy for efficient tumor inhibition.This intelligent cascaded-enzyme nanoreactor provides a promising approach to achieve concurrent and significant antitumor therapy.
文摘Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐shell structured nanoparticles as nanoreactors for various chemical reactions.A very brief overview of synthetic strategies is provided with emphasis on recent research progress in the last five years.Catalytic applications of these yolk‐shell structured nanoreactors are then discussed by covering photocatalysis,methane reforming and electrochemical conversion.The state of the art research and perspective in future development are also highlighted.
文摘An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene,alcohol,enamine,and aldehydes is reported.Dihydropyridine derivatives based on neat adduct of diketene,alcohols and aldehydes using SBA-15/SO_3H nanoreactor as catalyst via a four-component reactions are also synthesized.The advantages of the present method include the use of a small amount catalyst,simple procedure with an easy filterable work-up,waste-free,green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.
基金support from the DFG through SFB 951 Hybrid Inorganic/Organic Systems for OptoElectronics(HIOS)funding by the European Research Council(ERC)Consolidator Grant with Project Number 646659-NANOREACTORthe Joint Lab for Structural Research at the Integrative Research Institute for the Sciences(IRIS Adlershof).
文摘Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartment structure to achieve the combination of unique chemical properties and structural feature is still challenging due to the synthetic difficulties.Herein,we designed and synthesized a catalytically active,PTC gold(Au)@polydopamine(PDA)nanoreactor driven by infrared irradiation using assembled PS-b-P2VP nanosphere as soft template.The particles exhibit multi-compartment structure which is revealed by 3D electron tomography characterization technique.They feature permeable shells with tunable shell thickness.Full kinetics for the reduction reaction of 4-nitrophenol has been investigated using these particles as nanoreactors and compared with other reported systems.Notably,a remarkable acceleration of the catalytic reaction upon near-infrared irradiation is demonstrated,which reveals for the first time the importance of the synergistic effect of photothermal conversion and complex inner structure to the kinetics of the catalytic reduction.The ease of synthesis and fresh insights into catalysis will promote a new platform for novel nanoreactor studies.
基金supported by the National Natural Science Foundation of China (NSFC,Nos.42061134018,42011530085 and 41877323)the Russian Science Foundation (RSF,No.21-4700019,Russia)the Sichuan Science and Technology Program (No.2019JDJQ0056,China)。
文摘Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxidase(HRP)-like nanozyme(Fe-aminoclay) was in situ synthesized on the surface of alkali-activated halloysite nanotubes and the natural enzyme(glucose oxidase, GOx) was immobilized on it to construct a high-efficiency GOx-Fe AC@AHNTs cascade nanoreactor. In which, Fe AC@AHNTs can not only be used as a carrier for immobilized enzymes, but also help its catalytic activity to cooperate with glucose oxidase in a cascade reaction. The microcompartments and substrate channel effect of this enzyme-nanozyme microsystem exhibit a superior catalytic performance than that of natural enzyme system, and exhibits excellent long-term stability and recyclability. Subsequently, the GOx-Fe AC@AHNTs cascade nanoreactor was employed as a glucose colorimetric platform, which displayed a low detection limit(0.47 μmol/L)in glucose detection. This enzyme-nanoenzyme nanoreactor provides a simple and effective example for constructing a multi-enzyme system with limited space, and lays the foundation for subsequent research in the fields of biological analysis and catalysis.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.21671170,21673203)the Topnotch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+2 种基金Program for New Century Excellent Talents of the University in China(NCET,No.13-0645)the Six Talent Plan(No.2015-XCL-030)Qinglan Project。
文摘The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO2(JS) and to encapsulate metal oxide nanoparticles(Co3O4) into nanoreactors(SiO2).ZIF-67 crystals provide a cobalt species;SiO2 was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co3O4@SiO2 with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co3(OH)4Si2O5.Subsequently,CoSx and CoP-SiO2 were fabricated through sulfuration and phosphorization.The results in this work show that nanoreactors derived from metal-organic frameworks(MOFs) with a rational structure have broad development prospects.
基金supported by the National Natural Science Foundation of China (21971153 and 22371172)the Major Basic Research Projects of Shandong Provincial Natural Science Foundation (ZR2020ZD32)+2 种基金the Taishan Scholars Climbing Program of Shandong Provincethe Natural Science Foundation of Shandong Province (ZR2021QB035)the financial support from the China Scholarship Council (202108370157)。
文摘Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andcompensating for hydrogen peroxide (H2O2) and acidity in thetumor microenvironment is crucial for enhancing the effectivenessof CO therapy. In this study, a tumor microenvironment-responsive core-shell structured cascade nanoreactorwas designed and synthesized using mesoporous polydopamine(MPDA) as a nanocarrier, followed by loading ofMnCO and glucose oxidase-encapsulated zeolite imidazolateframework-8 (GOx@ZIF-8) nanoparticles. Upon enteringcancer cells, the protective shell of GOx@ZIF-8 degrades inresponse to the acidic tumor environment, releasing GOx.GOx catalyzes the conversion of endogenous glucose intogluconic acid and H2O2, accelerating energy starvation in tumorcells. This process, in turn, promotes the reaction betweenMnCO and H2O2, resulting in in-situ amplified release of CO.Additionally, the excellent photothermal properties of MPDAenable photothermal therapy. This comprehensive antitumorstrategy represents a promising advancement in the field ofCO-based cancer therapy.
基金supported by the Key Research and Development Program of Hubei Province(Grant No.2022BAA026)the Open/Innovation Project of Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry(Grant No.2022BEEA06)。
文摘Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited catalytic performance due to the confinement of their active components in the“nanochamber”.Herein,low-content active metal(AM,AM=Pd,Cu)decorated yolk-shelled FeCoNiOx(AM/FeCoNiOx)nanoreactors with magnetic recycling properties are synthesized through a simple two-step method.The obtained AM/FeCoNiOxnanospheres are characterized by their distinctive structure and the integration of two kinds of catalytically active components,namely the active FeCoNiOxsubstrate and the well-dispersed AMs in the whole yolk-shelled substrate.These nanospheres can be utilized as nanoreactors in two types of organic reactions(i.e.,reduction and oxidation).During the catalytic reduction of prototypical nitrogen-containing unsaturated organic compounds(e.g.,4-nitrophenol)using sodium borohydride,the Pd/FeCoNiOxnanoreactors demonstrate high activity over Cu/FeCoNiOxand FeCoNiOxcounterparts.The catalytic efficiency significantly surpasses that of a variety of magnetic metalbased nanocatalysts reported recently.Meanwhile,the Pd/FeCoNiOxnanoreactors demonstrate remarkable stability and broadspectrum catalytic capability towards reduction of the other nitrogen-containing unsaturated compounds,including eight substituted nitrobenzenes and two azo dyes.Furthermore,the Pd/FeCoNiOxnanoreactors exhibit exceptional catalytic activity and selectivity in promoting the oxidation of benzyl alcohol.This research provides an effective strategy for the rational design and fabrication of a dual-active-component nanoreactor with simple recycling,which is of practical significance for future sustainable industrial applications.
基金financial support by the National Natural Science Foundation of China(Nos.22305003 and 21972001)the China Postdoctoral Science Foundation(No.2023M740009).
文摘Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,the MOF coating significantly reduces the NC catalytic efficiency due to the diffusion barriers and the confined microenvironments.Herein,a hierarchically engineered MOF nanoreactor was constructed by controlled structural etching for NC immobilization.This nanoreactor possesses hierarchical pores to accelerate the diffusion rate of reactants and creates hollow structures to unleash the confined NC molecules from the rigid MOF network to a capacious microenvironment.The enhanced mass transfer,improved freedom of NCs,and outstanding stability collectively boosted the catalytic activity of the nanoreactor.By controlling the etching time,freestanding Pd8@zeolitic imidazolate framework-8(ZIF-8)-TA10 displayed a catalytic efficiency that was 3.17 times greater than that of the initial confined Pd8@ZIF-8 and even better than free Pd8.This work opens a new strategy to reduce the inherent limitations of porous matrixes for developing high-performance catalysts.
基金We thank the Natural Science Foundation of Zhejiang Province(Grant No.LZ22C100002)the 521 Talent Project of Zhejiang Sci-Tech University for providing financial support.
文摘Yolk-shell and hollow structures are powerful platforms for controlled release,confined nanocatalysis,and optical and electronic applications.This contribution describes a fabrication strategy for a yolk-shell nanoreactor(NR)using a post decoration approach.The widely studied yolk-shell structure of silica-coated TiO_(2)(TiO_(2)@SiO_(2))was used as a model.At first,anatase TiO_(2)spheres were prepared,and subsequently were given a continuous coating of carbonaceous and silica layers.Finally,the carbonaceous layer was removed to produce a yolk-shell structure TiO_(2)@SiO_(2).By using an in-situ photodeposition method,Pt-encased spheres(Pt-TiO_(2)@SiO_(2))were synthesized with Pt nanoparticles grown on the surface of the TiO_(2)core,which contained void spaces suitable for use as NRs.The NR showed enhanced hydrogen production with a rate of 24.56 mmol·g^(-1)·h^(-1)in the presence of a sacrificial agent under simulated sunlight.This strategy holds the potential to be extended for the synthesis of other yolk-shell photocatalytic NRs with different metal oxides.
基金financially supported by the National Natural Science Foundation of China(No.21908092)the Natural Science Foundation of Jiangsu Province(No.BK20242043)+2 种基金the China Postdoctoral Science Foundation(No.2022M711614)Jiangsu Funding Program for Excellent Postdoctoral Talent(No.2022ZB194)the Fundamental Research Funds for the Central Universities at NUAA(No.NZ2024038)
文摘Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,we report the assembling of yttrium-decorated bimetallic MOFs via one-step hydrothermal strategy,which can act as a sensitized nanoreactor for syngas production under y-ray irradiation.The flower-shaped CuNi-MOF matrix with tunable metal centers exposed plentiful cooperative active sites for CO_(2)binding,and its nanopetals enabled the well dispersion of Y_(2)O_(3)nanoparticles on the surfaces.The introduction of high-Z element Y enhanced the secondary electron scattering and promoted the water radiolysis to produce more hydrated electrons(e_(aq)^(-)),thus accelerating the initial CO_(2)activation to CO_(2)^(·-).Moreover,the in situ formed coupling interlayer provided a fast charge transfer channel between Y_(2)O_(3)and the MOF framework,which facilitated the interfacial electron migration for intermediate generation and subsequent CO_(2)conversion.By regulating the contents of Cu and Y_(2)O_(3)within the nanocomposites,the affinity toward CO_(2)and the product compositions could be modulated.As a result,the optimal 7CN-2Y catalyst achieved a high syngas evolution rate of 311.07μmol g^(-1)with a H_(2)/CO ratio of 2.7:1 at an absorbed dose of 4 kGy.The present study offered a feasible route for the efficient transformation of CO_(2)into valuable chemicals and the design of viable catalysts for ionizing radiation.
基金supported by the National Natural Science Foundation of China(No.22101289)Hundred Talents Programs in Chinese Academy of Sciences,the National Key Research and Development Program of China(No.2021YFA1502200)+2 种基金Bellwethers Project of Zhejiang Research and Development Plan(No.2022C01158)Ningbo S&T Innovation 2025 Major Special Program(Nos.2020Z107 and 2022Z205)Ningbo Yongjiang Talent Introduction Programme(Nos.2021A-111-G and 2021A-036-B).
文摘Covalent organic frameworks(COFs)-based nanoreactors have attracted broad interest in many fields due to their voidconfinement effects.However,the inherent drawback of conventional nanoreactors is the lack of internal active sites,which limits their widespread utilization.Herein,we report the construction of hierarchical COF(EB-TFP)nanoreactor with pre-synthesized polyoxometalates(POM,[PV_(2)W_(10)O_(40)]^(5–)(PV_(2)W_(10)))clusters encapsulated inside of COF(POM@COF).PV_(2)W_(10)@EB-TFP anchors nucleophilic-group(Br–ions)and PV_(2)W_(10)anion cluster within the COF framework via electrostatic interactions,which not only simplifies the reaction system but also enhances catalytic efficiency.The reaction performance of the PV_(2)W_(10)@EB-TFP nanoreactor can be tuned to achieve excellent catalytic activity in CO_(2)cycloaddition reaction(CCR)for~97.63%conversion and~100%selectivity under visible light irradiation.A mechanistic study based on density functional theory(DFT)calculations and insitu characterization was also carried out.In summary,we have reported a method for achieving the uniform dispersion of POM single clusters into COF nanoreactor,demonstrating the potential of POM@COF nanoreactor for synergistic photothermal catalytic CO_(2)cycloaddition.
基金supported by the National Natural Science Foundation of China(No.52070182)the DNL Cooperation Found,CAS(No.DNL202004)+3 种基金the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLU-DNL)(No.202206)Talents of Innovation and Entrepreneurship Project of Lanzhou,China(No.2022-RC-26)Major Program of the Lanzhou Institute of Chemical Physics,CAS(No.ZYFZFX-10)Key talent project of Gansu Province.
文摘SO_(2)poisoning is a common problem in the catalytic combustion of volatile organic compounds(VOCs).In this work,we took three-dimensionally ordered macroporous and mesoporous(3DOM)SiO_(2)as the nanoreactor to protect active sites from SO_(2)erosion in the catalytic combustion of benzene.Simultaneously,the confined growth of metal active nanoparticles in the multi-stage pore is also full of challenges.And we successfully confined Co_(3)O_(4)nanoparticles(NPs)in macroporous and mesoporous channels.Interestingly,the precursors’growth in the pore was controlled and nanoreactors with different pore sizes were prepared by adjusting the loading amount and preparation methods.It is discovered that the Co_(3)O_(4)NPs confined in 3DOM SiO_(2)nanoreactor showed superior sulfur and water resistance.Density functional theory(DFT)calculations verified that the Co-Si catalyst had high SO_(2)adsorption energy(-0.48 eV),which illustrated that SO_(2)was hard to attach to the surface of the Co-Si catalyst.The SiO_(2)nanoreactor had low SO_(2)adsorption energy(-5.15 eV),which indicated that SO_(2)was easily absorbed on SiO_(2)nanoreactor.This illustrated that the SiO_(2)nanoreactor could protect effectively active sites from SO_(2)erosion.
基金supported by the National High Level Talents Special Support Plan(X.C.)the National Natural Science Foundation of China(82272141 to X.C.)+4 种基金the“Young Talent Support Plan”of Xi’an Jiaotong University(X.C.)the Shaanxi Innovative Research Team of Science and Technology(S2023-ZC-TD-0152)the Natural Science Foundation of Shaanxi Province(2022JZ-48 to X.C.)the National Key Research and Development Program of China(2023YFC2509104 to X.C.)the Postdoctoral Science Foundation of China(2023M732812 to T.L.).
文摘Tumor microenvironment(TME),as the“soil”of tumor growth and metastasis,exhibits significant differences from normal physiological conditions.However,how to manipulate the distinctions to achieve the accurate therapy of primary and metastatic tumors is still a challenge.Herein,an innovative nanoreactor(AH@MBTF)is developed to utilize the apparent differences(copper concentration and H_(2)O_(2)level)between tumor cells and normal cells to eliminate primary tumor based on H_(2)O_(2)-dependent photothermal-chemodynamic therapy and suppress metastatic tumor through copper complexation.This nanoreactor is constructed using functionalized MSN incorporating benzoyl thiourea(BTU),triphenylphosphine(TPP),and folic acid(FA),while being co-loaded with horseradish peroxidase(HRP)and its substrate ABTS.During therapy,the BTU moieties on AH@MBTF could capture excessive copper(highly correlated with tumor metastasis),presenting exceptional anti-metastasis activity.Simultaneously,the complexation between BTU and copper triggers the formation of cuprous ions,which further react with H_(2)O_(2)to generate cytotoxic hydroxyl radical(•OH),inhibiting tumor growth via che-modynamic therapy.Additionally,the stepwise targeting of FA and TPP guides AH@MBTF to accurately accu-mulate in tumor mitochondria,containing abnormally high levels of H_(2)O_(2).As a catalyst,HRP mediates the oxidation reaction between ABTS and H_(2)O_(2)to yield activated ABTS•^(+).Upon 808 nm laser irradiation,the activated ABTS•^(+)performs tumor-specific photothermal therapy,achieving the ablation of primary tumor by raising the tissue temperature.Collectively,this intelligent nanoreactor possesses profound potential in inhib-iting tumor progression and metastasis.
