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 Co_(3)O_(4)@SiO_(2)as precursor,core-shell structured CoP@SiO_(2)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 NaH_(2)PO_(2)was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm^(2)and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO_(2)with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.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
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@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_...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@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_(4))into nanoreactors(SiO_(2)).ZIF-67 crystals provide a cobalt species;SiO_(2)was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co_(3)O_(4)@SiO_(2)with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co_(3)(OH)4Si_(2)O_(5).Subsequently,CoSx and CoP-SiO_(2)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
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
Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence ...Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence spectroscopy.Owing to the determined cavity size and excellent optical performance of cages,the resulting supramolecular cages were confirmed to be the light-harvesting system based on Foster resonance energy-transfer(FRET).The developed cages display good water solubilities and can act as nanoreactors and light-harvesting systems to catalyze the difluoromethylation of quinoxalin-2(1H)-ones with sodium difluoromethanesulfinate under the irradiation of sunlight.Compared with eosin Y alone,this system displayed enhanced catalytic activity in catalyzing the difluoromethylation,which realizes the simulation of the photosynthesis process.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
Despite great progress of lithium-sulfur(Li-S)battery performance at the laboratory-level,both key parameters and challenges at cell scales to achieve practical high energy density require high-sulfur-loading cathodes...Despite great progress of lithium-sulfur(Li-S)battery performance at the laboratory-level,both key parameters and challenges at cell scales to achieve practical high energy density require high-sulfur-loading cathodes and lean electrolytes.Herein,a novel carbon foam integrated by hollow carbon bubble nanoreactors with ultrahigh pore volume of 6.9 cm3·g−1 is meticulously designed for ultrahigh sulfur content up to 96 wt.%.Tailoring polysulfide trapping and ion/electron transport kinetics during the charge-discharge process can be achieved by adjusting the wall thickness of hollow carbon bubbles.And a further in-depth understanding of electrochemical reaction mechanism for the cathode is impelled by the in-situ Raman spectroscopy.As a result,the as-prepared cathode delivers high specific capacitances of 1,269 and 695 mAh·g−1 at 0.1 and 5 C,respectively.Furthermore,Li-S pouch cells with high areal sulfur loading of 6.9 mg·cm−2 yield exceptional practical energy density of 382 Wh·kg−1 under lean electrolyte of 3.5µL·mg−1,which demonstrates the great potential for realistic high-energy Li-S batteries.展开更多
Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the s...Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the shells. In this study, we show that Pt nanoparticles （NPs） can be embedded into few-layer hexagonal boron nitride （h-BN） overlayers, forming Pt@h-BN core-shell nanocatalysts. The h-BN shells not only protect the Pt NPs under harsh conditions but also allow gaseous molecules such as CO and 02 to access a large part of the Pt surfaces through a facile intercalation process. As a result, the Pt@h-BN nanostructures act as nanoreactors, and CO oxidation reactions with improved activity, selectivity, and stability occur at the core-shell interfaces. The confinement effect exerted by the h-BN shells promotes the Pt-catalyzed reactions. Our work suggests that two-dimensional shells can function as robust but flexible covers on nanocatalyst surfaces and tune the surface reactivity.展开更多
One-dimensional(1D)oxide nanofibers have attracted much attention in recent years but are still hampered by the difficulty in the expansion to 2D or 3D dimensions.Herein,ultrathin CeO_(2)/SiO_(2)nanofibers with intrig...One-dimensional(1D)oxide nanofibers have attracted much attention in recent years but are still hampered by the difficulty in the expansion to 2D or 3D dimensions.Herein,ultrathin CeO_(2)/SiO_(2)nanofibers with intriguing core-sheath structures were simply fabricated by a facile single-spinneret electrospinning method and were subsequently integrated as 2D nanofi-brous mats and 3D sponges.Introducing secondary oxide(i.e.,SiO_(2))could induce a unique fine structure and further inhibit the sintering of CeO_(2)nanocrystals,endowing the resultant dual-oxide nanofibers with high porosity,good flexibility,and enriched oxygen defects.Benefiting from the core-sheath structure and dual-oxide component,the CeO_(2)/SiO_(2)nanofibers could stabilize 2.59 nm-Pt clusters against sintering at 600℃.Once assembled into a 2D mat,the nanofibers could efficiently decrease the soot oxidation temperature by 63℃.Moreover,the core-sheath CeO_(2)/SiO_(2)nanofibers can be readily integrated with graphene nanosheets into a 3D sponge via a gas foaming protocol,showing 218.5 mg/g of adsorption capacity toward Rhodamine B molecules.This work shed lights on the versatile applications of oxide nanofibers toward clean energy ultili-zation and low-carbon development.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
Multienzyme cascades enable the sequential synthesis of complex chemicals by combining multiple catalytic processes in one pot,offering considerable time and cost savings compared to a series of separate batch reactio...Multienzyme cascades enable the sequential synthesis of complex chemicals by combining multiple catalytic processes in one pot,offering considerable time and cost savings compared to a series of separate batch reactions.However,challenges related to coordination and regulatory interplay among multiple enzymes reduce the catalytic efficiency of such cascades.Herein,we genetically programmed a scaffold framework that selectively and orthogonally recruits enzymes as designed.The system was then used to generate multienzyme complexes of D-allulose 3-epimerase(DAE),ribitol dehydrogenase(RDH),and formate dehydrogenase(FDH)for rare sugar production.This scaffolded multienzymatic assembly achieves a 10.4-fold enhancement in the catalytic performance compared to its unassembled counterparts,obtaining allitol yield of more than 95%.Molecular dynamics simulations revealed that shorter distances between neighboring enzymes in scaffold-mounted complexes facilitated the transfer of reaction intermediates.A dual-module catalytic system incorporating(1)scaffold-bound complexes of DAE,RDH,and FDH and(2)scaffold-bound complexes of alcohol dehydrogenase and NADH oxidase expressed intracellularly in E.coli was used to synthesize D-allulose from D-fructose.This system synthesized 90.6%D-allulose from 300 g L^(−1)D-fructose,with a space-time yield of 13.6 g L^(−1)h^(−1).Our work demonstrates the programmability and versatility of scaffold-based strategies for the advancement of multienzyme cascades.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
The synthesis of metal catalysts confined in porous materials is still a great challenge.Here,a framework sustained by bulky rigid polyoxometalate(POM)blocks[Mo_(36)O_(112)(H_(2)O)_(16)]^(8-)({Mo_(36)})is used to rest...The synthesis of metal catalysts confined in porous materials is still a great challenge.Here,a framework sustained by bulky rigid polyoxometalate(POM)blocks[Mo_(36)O_(112)(H_(2)O)_(16)]^(8-)({Mo_(36)})is used to restrict the size of Ag particles to obtain a novel composite of well-sized silver nanoparticles encapsulated in a POM framework.展开更多
In the present work,Au@Pd nanoparticles,which serve as catalytic active centers,were first implanted in amphiphilic hollow vinyl-pyridyl group-doped periodic mesoporous organosilica(PMO)shells,and yolk-shell smart Pic...In the present work,Au@Pd nanoparticles,which serve as catalytic active centers,were first implanted in amphiphilic hollow vinyl-pyridyl group-doped periodic mesoporous organosilica(PMO)shells,and yolk-shell smart Pickering Au@Pd@Py-PMO nanoreactors were obtained.Herein,two smart aspects of the novel nanoreactor are demonstrated:one is the adsorption and the other is the catalytic process.Interestingly,it was found that the obtained vinyl-pyridyl group-doped nanoreactors can easily adsorb hydrophobic molecules containing nitro-groups or vinyl-groups into their interior rather than simply indiscriminately adsorb organic substances.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
Recently emerged cancer immunochemotherapy has provided enormous new possibilities to replace traditional chemotherapy in fighting tumor.However,the treatment efficacy is hampered by tumor hypoxiainduced immunosuppres...Recently emerged cancer immunochemotherapy has provided enormous new possibilities to replace traditional chemotherapy in fighting tumor.However,the treatment efficacy is hampered by tumor hypoxiainduced immunosuppression in tumor microenvironment(TME).Herein,we fabricated a self-oxygenation/degradable inorganic nanozyme with a core-shell structure to relieve tumor hypoxia in cancer immunochemotherapy.By integrating the biocompatible CaO2 as the oxygen-storing component,this strategy is more effective than the earlier designed nanocarriers for delivering oxygen or H2O2,and thus provides remarkable oxygenation and long-term capability in relieving hypoxia throughout the tumor tissue.Consequently,in vivo tests validate that the delivery system can successfully relieve hypoxia and reverse the immunosuppressive TME to favor antitumor immune responses,leading to enhanced chemoimmunotherapy with cytotoxic T lymphocyte-associated antigen 4 blockade.Overall,a facile,robust and effective strategy is proposed to improve tumor oxygenation by using self-decomposable and biocompatible inorganic nanozyme reactor,which will not only provide an innovative pathway to relieve intratumoral hypoxia,but also present potential applications in other oxygen-favored cancer therapies or oxygen deficiency-originated diseases.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
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
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 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
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 Co_(3)O_(4)@SiO_(2)as precursor,core-shell structured CoP@SiO_(2)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 NaH_(2)PO_(2)was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm^(2)and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO_(2)with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.
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.
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@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_(4))into nanoreactors(SiO_(2)).ZIF-67 crystals provide a cobalt species;SiO_(2)was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co_(3)O_(4)@SiO_(2)with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co_(3)(OH)4Si_(2)O_(5).Subsequently,CoSx and CoP-SiO_(2)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National Natural Science Foundation of China(Nos.22101267,21672192,21803059,U2004191,U1904212 and 21801063)for financial support.
文摘Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence spectroscopy.Owing to the determined cavity size and excellent optical performance of cages,the resulting supramolecular cages were confirmed to be the light-harvesting system based on Foster resonance energy-transfer(FRET).The developed cages display good water solubilities and can act as nanoreactors and light-harvesting systems to catalyze the difluoromethylation of quinoxalin-2(1H)-ones with sodium difluoromethanesulfinate under the irradiation of sunlight.Compared with eosin Y alone,this system displayed enhanced catalytic activity in catalyzing the difluoromethylation,which realizes the simulation of the photosynthesis process.
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This work was financially supported by National Natural Science Foundation of China(Grant Nos.51702095,51702362,51722503,and 51621004)Natural Science Foundation of Hunan Province,China(Grant No.2018JJ3041)the scientific research project of National University of Defense Technology(Grant Nos.ZK19-27 and ZK17-03-61).
文摘Despite great progress of lithium-sulfur(Li-S)battery performance at the laboratory-level,both key parameters and challenges at cell scales to achieve practical high energy density require high-sulfur-loading cathodes and lean electrolytes.Herein,a novel carbon foam integrated by hollow carbon bubble nanoreactors with ultrahigh pore volume of 6.9 cm3·g−1 is meticulously designed for ultrahigh sulfur content up to 96 wt.%.Tailoring polysulfide trapping and ion/electron transport kinetics during the charge-discharge process can be achieved by adjusting the wall thickness of hollow carbon bubbles.And a further in-depth understanding of electrochemical reaction mechanism for the cathode is impelled by the in-situ Raman spectroscopy.As a result,the as-prepared cathode delivers high specific capacitances of 1,269 and 695 mAh·g−1 at 0.1 and 5 C,respectively.Furthermore,Li-S pouch cells with high areal sulfur loading of 6.9 mg·cm−2 yield exceptional practical energy density of 382 Wh·kg−1 under lean electrolyte of 3.5µL·mg−1,which demonstrates the great potential for realistic high-energy Li-S batteries.
基金Acknowledgements This work was financially supported by the National Natural Science Foundation of China （Nos. 21373208, 91545204, 21688102, and 21621063）, and Ministry of Science and Technology of China （Nos. 2016YFA0200200, 2013CB834603, and 2013CB933100）, and the Strategic Priority Research Program of the Chinese Academy of Sciences （No. XDB17020200）.
文摘Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the shells. In this study, we show that Pt nanoparticles （NPs） can be embedded into few-layer hexagonal boron nitride （h-BN） overlayers, forming Pt@h-BN core-shell nanocatalysts. The h-BN shells not only protect the Pt NPs under harsh conditions but also allow gaseous molecules such as CO and 02 to access a large part of the Pt surfaces through a facile intercalation process. As a result, the Pt@h-BN nanostructures act as nanoreactors, and CO oxidation reactions with improved activity, selectivity, and stability occur at the core-shell interfaces. The confinement effect exerted by the h-BN shells promotes the Pt-catalyzed reactions. Our work suggests that two-dimensional shells can function as robust but flexible covers on nanocatalyst surfaces and tune the surface reactivity.
基金This work was financially supported by the Natural Science Foundation of China(21975042)the Project of Six Talents Climax Foundation of Jiangsu(XCL-082)+3 种基金Innovation Platform Project Supported by Jiangsu Province(6907041203)the Young Talent Lifting Project of Jiangsu Science and Technology Associate,the Fundamental Research Funds for the Central Universities,the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_0261)the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe open project of State Key Laboratory of Physical Chemistry of Solid Surfaces in Xiamen University.
文摘One-dimensional(1D)oxide nanofibers have attracted much attention in recent years but are still hampered by the difficulty in the expansion to 2D or 3D dimensions.Herein,ultrathin CeO_(2)/SiO_(2)nanofibers with intriguing core-sheath structures were simply fabricated by a facile single-spinneret electrospinning method and were subsequently integrated as 2D nanofi-brous mats and 3D sponges.Introducing secondary oxide(i.e.,SiO_(2))could induce a unique fine structure and further inhibit the sintering of CeO_(2)nanocrystals,endowing the resultant dual-oxide nanofibers with high porosity,good flexibility,and enriched oxygen defects.Benefiting from the core-sheath structure and dual-oxide component,the CeO_(2)/SiO_(2)nanofibers could stabilize 2.59 nm-Pt clusters against sintering at 600℃.Once assembled into a 2D mat,the nanofibers could efficiently decrease the soot oxidation temperature by 63℃.Moreover,the core-sheath CeO_(2)/SiO_(2)nanofibers can be readily integrated with graphene nanosheets into a 3D sponge via a gas foaming protocol,showing 218.5 mg/g of adsorption capacity toward Rhodamine B molecules.This work shed lights on the versatile applications of oxide nanofibers toward clean energy ultili-zation and low-carbon development.
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.
文摘Multienzyme cascades enable the sequential synthesis of complex chemicals by combining multiple catalytic processes in one pot,offering considerable time and cost savings compared to a series of separate batch reactions.However,challenges related to coordination and regulatory interplay among multiple enzymes reduce the catalytic efficiency of such cascades.Herein,we genetically programmed a scaffold framework that selectively and orthogonally recruits enzymes as designed.The system was then used to generate multienzyme complexes of D-allulose 3-epimerase(DAE),ribitol dehydrogenase(RDH),and formate dehydrogenase(FDH)for rare sugar production.This scaffolded multienzymatic assembly achieves a 10.4-fold enhancement in the catalytic performance compared to its unassembled counterparts,obtaining allitol yield of more than 95%.Molecular dynamics simulations revealed that shorter distances between neighboring enzymes in scaffold-mounted complexes facilitated the transfer of reaction intermediates.A dual-module catalytic system incorporating(1)scaffold-bound complexes of DAE,RDH,and FDH and(2)scaffold-bound complexes of alcohol dehydrogenase and NADH oxidase expressed intracellularly in E.coli was used to synthesize D-allulose from D-fructose.This system synthesized 90.6%D-allulose from 300 g L^(−1)D-fructose,with a space-time yield of 13.6 g L^(−1)h^(−1).Our work demonstrates the programmability and versatility of scaffold-based strategies for the advancement of multienzyme cascades.
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(NSFC 21801226)the Natural Science Foundation of Zhejiang Province(LY20B010002 and LQ22B010002)the Zhejiang Normal University Fund.
文摘The synthesis of metal catalysts confined in porous materials is still a great challenge.Here,a framework sustained by bulky rigid polyoxometalate(POM)blocks[Mo_(36)O_(112)(H_(2)O)_(16)]^(8-)({Mo_(36)})is used to restrict the size of Ag particles to obtain a novel composite of well-sized silver nanoparticles encapsulated in a POM framework.
基金supported by the National Natural Science Foundation of China(21390394,21771082,21771081,and 21703128)“111”project(BP0719036)the Natural Science Foundation of Jilin Province(no.20190201207JC).
文摘In the present work,Au@Pd nanoparticles,which serve as catalytic active centers,were first implanted in amphiphilic hollow vinyl-pyridyl group-doped periodic mesoporous organosilica(PMO)shells,and yolk-shell smart Pickering Au@Pd@Py-PMO nanoreactors were obtained.Herein,two smart aspects of the novel nanoreactor are demonstrated:one is the adsorption and the other is the catalytic process.Interestingly,it was found that the obtained vinyl-pyridyl group-doped nanoreactors can easily adsorb hydrophobic molecules containing nitro-groups or vinyl-groups into their interior rather than simply indiscriminately adsorb organic substances.
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(Nos.81371627 and 81727804)the Jiangsu Provincial Natural Science Fund for Distinguished Young Scholars(BK201900)the“Double First-Class”University project(Nos.CPU2018GY24 and CPU2018GY20).
文摘Recently emerged cancer immunochemotherapy has provided enormous new possibilities to replace traditional chemotherapy in fighting tumor.However,the treatment efficacy is hampered by tumor hypoxiainduced immunosuppression in tumor microenvironment(TME).Herein,we fabricated a self-oxygenation/degradable inorganic nanozyme with a core-shell structure to relieve tumor hypoxia in cancer immunochemotherapy.By integrating the biocompatible CaO2 as the oxygen-storing component,this strategy is more effective than the earlier designed nanocarriers for delivering oxygen or H2O2,and thus provides remarkable oxygenation and long-term capability in relieving hypoxia throughout the tumor tissue.Consequently,in vivo tests validate that the delivery system can successfully relieve hypoxia and reverse the immunosuppressive TME to favor antitumor immune responses,leading to enhanced chemoimmunotherapy with cytotoxic T lymphocyte-associated antigen 4 blockade.Overall,a facile,robust and effective strategy is proposed to improve tumor oxygenation by using self-decomposable and biocompatible inorganic nanozyme reactor,which will not only provide an innovative pathway to relieve intratumoral hypoxia,but also present potential applications in other oxygen-favored cancer therapies or oxygen deficiency-originated diseases.
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.
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.
