Designing carbon materials with ideal stable hierarchical porous structures and fiexible functional properties for efficient and sustainable Zn2+ion storage still faces great challenges. Herein, the threedimensional c...Designing carbon materials with ideal stable hierarchical porous structures and fiexible functional properties for efficient and sustainable Zn2+ion storage still faces great challenges. Herein, the threedimensional carbon superstructures with spherical nanofiower-like structures were tailor-made by the self-assembly strategy. Specifically, organic polymer units(i.e., organic motifs) were formed by tetrachloro-p-benzoquinone(TBQ) and 2,6-diamino anthraquinone(DAQ) via a noble-metal-free catalyzed coupling reaction. Subsequently, the organic motifs assemble into spherical nanofiower-like superstructures induced by intermolecular hydrogen bonding and aromatic π-π stacking interactions. Welldesigned carbon superstructures can provide a stable backbone that effectively blocks structural stacking and collapse. Meanwhile, the hierarchical porous structures in 3D carbon superstructures provide continuous charge transport pathways to greatly shorten the ion diffusion distance, and as a result, the carbon superstructures-based zinc-ion hybrid capacitors(ZIHCs) provide a capacity of 245 m Ah/g at 0.5 A/g, a high energy density of 152 Wh/kg and an ultra-long life of 300,000 cycles at 20 A/g. The excellent electrochemical performance is also attributed to the corresponding charge storage mechanism, i.e., the alternate binding of Zn^(2+)/CF_(3)SO_(3)^(-) ions. Besides, the high-level N/O motifs improve the surface properties of the carbon superstructures and reduce the ion migration barriers for more efficient charge storage. This paper provides insights into the design of advanced carbon-based cathodes and presents a fundamental understanding of their charge storage mechanisms.展开更多
Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and ...Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and quantifying these superstructures hinder the optimization of pyrrhotite depression in flotation processes.To address this critical issue,synchrotron X-ray powder diffraction(S-XRPD)with Rietveld refinement was employed to quantify the distribution of superstructures in the feed and flotation concentrates of a copper–gold ore.To elucidate the mechanisms influencing depression,density functional theory(DFT)calculations were conducted to explore the electronic structures and surface reactivity of the pyrrhotite superstructures toward the adsorption of water,oxygen and hydroxyl ions(OH-)as dominant species present in the flotation process.S-XRPD analysis revealed that flotation recovery rates of pyrrhotite followed the order of 4C<6C<5C.DFT calculations indicated that the Fe 3d and S 3p orbital band centers exhibited a similar trend relative to the Fermi level with 4C being the closest.The Fe3d band center suggested that the 4C structure possessed a more reactive surface toward the oxygen reduction reaction,promoting the formation of hydrophilic Fe-OH sites.The S 3p band center order also implied that xanthate on the non-magnetic 5C and 6C surfaces could oxidize to dixanthogen,increasing hydrophobicity and floatability,while 4C formed less hydrophobic metal-xanthate complexes.Adsorption energy and charge transfer analyses of water,hydroxyl ions and molecular oxygen further supported the high reactivity and hydrophilic nature of 4C pyrrhotite.The strong bonding with hydroxyl ions indicated enhanced surface passivation by hydrophilic Fe–OOH complexes,aligning with the experimentally observed flotation order(4C<6C<5C).These findings provide a compelling correlation between experimental flotation results and electronic structure calculations,delivering crucial insights for optimizing flotation processes and improving pyrrhotite depression.This breakthrough opens up new opportunities to enhance the efficiency of flotation processes in the mining industry.展开更多
Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds o...Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.展开更多
Hydrogen evolution electrocatalysts derived from metal-organic crystalline frameworks can inherit the merits of ordered and adjustable structures with high surface area.In this paper,organic-octamolybdate crystalline ...Hydrogen evolution electrocatalysts derived from metal-organic crystalline frameworks can inherit the merits of ordered and adjustable structures with high surface area.In this paper,organic-octamolybdate crystalline superstructures(OOCS)with a fixed stoichiometric ratio of Mo_(8)(L)_(2) and high Mo content(>40 wt%)were synthesized using flexible ligands with controllable lengths(named as OOCS-1-3).Then,molybdenum carbides coated with carbon layers as electrocatalysts(Mo_(2)C@C-1-3)can be obtained directly from a one-step high-temperature carbonization process using OOCS-1-3 as precursors.As a typical example,Mo_(2)C@C-3 exhibits satisfactory hydrogen evolution activity with a low overpotential of 151 m V(1.0 mol/L KOH)at 10 m A/cm^(2) and stability for 24 h.The electrocatalytic activity is mainly from the synergistic interactions between the carbon layers and molybdenum carbide species.Furthermore,compared with the initial content of C,N,Mo in OOCS and Mo_(2)C@C,the catalytic activity increases with the N amount.This work makes organic-octamolybdate crystalline superstructures used as general precursors to product high Mo content electrocatalysts applied in energy storage and conversion fields.展开更多
Glioblastoma(GBM) remains a formidable challenge in oncology.Chemodynamic therapy(CDT) that triggers tumor cell death by reactive oxygen species(ROS) could open up a new door for GBM treatment.Herein,we report a novel...Glioblastoma(GBM) remains a formidable challenge in oncology.Chemodynamic therapy(CDT) that triggers tumor cell death by reactive oxygen species(ROS) could open up a new door for GBM treatment.Herein,we report a novel CDT nanoagent.Hemoglobin(Hb)and glucose oxidase(GOx) were employed as powerful CDT catalysts.Instead of encapsulating the proteins in drug delivery nanocarriers,we formulate multimeric superstructures as self-delivery entities by crosslinking techniques.Red blood cell(RBC) membranes are camouflaged on the protein superstructures to promote the delivery across blood-brain barrier.The as-prepared RBC@Hb@GOx nanoparticles(NPs) offer superior biocompatibility,simplified structure,and high accumulation at the tumor site.We successfully demonstrated that the NPs could efficiently produce toxic ROS to kill U87 MG cancer cells in vitro and inhibit the growth of GBM tumor in vivo,suggesting that the new CDT nanoagent holds great promise for treating GBM.展开更多
Urchin-like Ni O superstructures have been prepared via a thermal decomposition reaction of Ni C_2O_4 at 400 for 1h. The morphology and structure of the synthesized urchin-like superstructures have been characterized ...Urchin-like Ni O superstructures have been prepared via a thermal decomposition reaction of Ni C_2O_4 at 400 for 1h. The morphology and structure of the synthesized urchin-like superstructures have been characterized by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The results show that urchin-like Ni O superstructures were a polycrystal with cubic structure and typical diameters of 200 to 500 nm and the self-assembly nanoparticles average diameter is 14 nm. The as-prepared Ni O superstructures have a high Brunauer-Emmett-Teller surface area of about 60.32 m^2/g. The UV-vis spectrum of urchin-like Ni O consists of one peak at 357 nm(3.47 e V).展开更多
Mitochondria, usually ovoid structures no larger than 0.5 microns can fuse into structures that are 5 microns and larger such as nebenkern, spheroidal or cup-shaped mitochondria, and even mega-mitochondria. In studyin...Mitochondria, usually ovoid structures no larger than 0.5 microns can fuse into structures that are 5 microns and larger such as nebenkern, spheroidal or cup-shaped mitochondria, and even mega-mitochondria. In studying differentiation of human endometrial epithelial cells, it became clear that formation of mitochondrial superstructures was an essential part of the process. In this paper, the origins, function, and demise of these superstructures called mitonucleons are described. In the course of reading papers about mitochondrial superstructures, it became obvious that there are important similarities, particularly with regard to function, between the mitonucleon and the nebenkern, a superstructure essential for dramatic tail elongation during spermatogenesis in grasshoppers, drosophila, and other insects. Close inspection of photomicrographs of differentiating mitonucleons during the first 12 hours suggests that gases build up in vacuoles within the mitochondrial superstructure creating pressure that elevates syncytial membranes and compresses nuclear aggregates contained within the mitonucleon.展开更多
The ultrathinβ-Sn(001)films have attracted tremendous attention owing to its topological superconductivity(TSC),which hosts Majorana bound state(MBSs)for quantum computation.Recently,β-Sn(001)thin films have been su...The ultrathinβ-Sn(001)films have attracted tremendous attention owing to its topological superconductivity(TSC),which hosts Majorana bound state(MBSs)for quantum computation.Recently,β-Sn(001)thin films have been successfully fabricated via phase transition engineering.However,the understanding of structural phase transition ofβ-Sn(001)thin films is still elusive.Here,we report the direct growth of ultrathinβ-Sn(001)films epitaxially on the highly oriented pyrolytic graphite(HOPG)substrate and the characterization of intricate structural-transition-induced superstructures.The morphology was obtained by using atomic force microscopy(AFM)and low-temperature scanning tunneling microscopy(STM),indicating a structure-related bilayer-by-bilayer growth mode.The ultrathinβ-Sn film was made of multiple domains with various superstructures.Both high-symmetric and distorted superstructures were observed in the atomic-resolution STM images of these domains.The formation mechanism of these superstructures was further discussed based on the structural phase transition ofβtoα-Sn at the atomic-scale thickness.Our work not only brings a deep understanding of the structural phase transition of Sn film at the two-dimensional limit,but also paves a way to investigate their structure-sensitive topological properties.展开更多
Using scanning tunneling microscopy we observe a stripe phase smoothly interfacing with a triangular 2 ×2 super- structure on the surface of 2H-NbSe2 single crystM. Proximity-induced superconductivity is demonstr...Using scanning tunneling microscopy we observe a stripe phase smoothly interfacing with a triangular 2 ×2 super- structure on the surface of 2H-NbSe2 single crystM. Proximity-induced superconductivity is demonstrated in these new ordered structures by measurements of low-temperature tunneling spectra. The modulation of superconduc- tivity by the reconstruction provides an opportunity to understand the interplay between superconductivity and charge orders.展开更多
Hierarchical superstructures assembled by nanosheets can effectively prevent aggregation of nanosheets and improve performance in energy storage.Therefore,we proposed a facile hydrothermal method to obtain three-dimen...Hierarchical superstructures assembled by nanosheets can effectively prevent aggregation of nanosheets and improve performance in energy storage.Therefore,we proposed a facile hydrothermal method to obtain three-dimensional(3D)superstructure assembled by nanosheets.We found that the ratio of Co^(2+)/HMTA affected the morphology of the samples,and the 3D hierarchical structures of are obtained while the ratio of Co^(2+)/HMTA is 12:25.The hierarchical structures with sufficient interior space preserves the original sheet-like dimensional components and results in sufficient active sites and efficient mass diffusion.Hence,the 3D Co_(2)V_(2)O_(7)·nH_(2)O hierarchical structure exhibits good rate capability and high stability while as electrode materials.Meanwhile,when power density is 745.13 W/kg,the assembled CVO-2//AC shows an energy density of 47.7 Wh/kg.The work displays a facile method for fabrication of 3D superstructure assembled by 2D nanosheets that can be applied in energy storage.展开更多
Since there may exist dark matter particles ν and δ with mass - 10^-1 e V in the universe, the superstructures with a scale of 10^19 solar masses （large number A - 10^19） appeared during the era near and before th...Since there may exist dark matter particles ν and δ with mass - 10^-1 e V in the universe, the superstructures with a scale of 10^19 solar masses （large number A - 10^19） appeared during the era near and before the hydrogen recombination. Since there are superstructures in the universe, there may be no necessity for the existence of dark energy. For checking the superstructure in the universe by CMB anisotropy, we need to measure CMB angular power spectrum especially around ten degrees across the sky- in more details, While neutrino u is related to electroweak unification, the fourth stable elementary particle 6 may be related to strong-gravity unification, which suggests p ＋ p^- → n ＋ δ^- and that some new baryons appeared in the TeV region.展开更多
Planar assemblies of plasmonic nanoparticles have provided opportunities in various fields.This study exploits the self-assembly of gold nanorods(AuNRs)into planar,layered chiral superstructures(dodecamer)using DNA or...Planar assemblies of plasmonic nanoparticles have provided opportunities in various fields.This study exploits the self-assembly of gold nanorods(AuNRs)into planar,layered chiral superstructures(dodecamer)using DNA origami technology.Due to the collective plasmonic coupling modes,the dodecamers exhibit g-factors of up to+0.06,which is 4-5 times higher than those of the dextrodimers.The chiroptical property of the superstructures proved to be strongly size-dependent,exhibiting enhanced g-factors with increasing the size of AuNRs.Moreover,by excluding the averaging and close-to-racemic effects in the ensemble colloids,circular differential scattering(CDS)and circularly polarized luminescence(CPL)were studied at the single-particle level,revealing the essential role of the structural chirality of superstructure in correlating single-particle scattering with nearby dye emission.The observed correlated CDS and CPL show g-factors up to−0.17 and−0.6,respectively.These results highlight the potential of DNA origami-directed plasmonic assemblies for nanoscale chirality engineering,with applications in biosensing,chiral photonics,and metamaterials.展开更多
The novel fabrication of multiple components and unique heterostructure can inject infinite vitality into the electromagnetic wave(EMW)attenuation field.Herein,through the self-assembly of polyimide com-plexes and cat...The novel fabrication of multiple components and unique heterostructure can inject infinite vitality into the electromagnetic wave(EMW)attenuation field.Herein,through the self-assembly of polyimide com-plexes and catalytic chemical vapor deposition,porous carbon microflowers were synthesized accompa-nied by carbon nanotubes(CNTs).By regulating the metal ions,the composition and structure of the as-obtained hybrids are modified correspondingly,and thus the adjustable thermal management and EMW absorption capabilities are obtained.In detail,the rich pores and huge specific surface area endow the hierarchical structures with distinguished thermal insulation ability(λ<0.07).The carbon framework and CNTs are beneficial for consuming EMWs via conductive loss and defect polarization loss while reduc-ing the filling ratio and thickness.The doped heteroatoms and abundant heterointerfaces generate ample dipole polarization and interface polarization losses(supported by DFT calculation).The metal nanopar-ticles uniformly embedded in the carbon framework offer optimized impedance matching,proper de-fect polarization,and suitable magnetic loss.Accordingly,the synergy of magnetic-dielectric balance and flower-like superstructure enables FNCFN2 and NNCFN2 to accomplish remarkable microwave absorbing capacity with thin thickness(14 wt.%).Therefore,respectable specific reflection loss and specific effec-tive absorption bandwidth are acquired(215.39 dB mm^(-1) and 22.10 GHz mm^(-1),257.23 dB mm^(-1) and 22.12 GHz mm^(-1) respectively),superior to those of certain renowned carbon-based absorbers.The simu-lation results of electric field intensity distributions,power loss density,and radar cross section reduction(maximum value of 36.02 dBm2)also verify the prominent radar stealth capability.Moreover,the cus-tomizable approach can be applied to other metals to obtain fulfilling behaviors.Henceforth,this work provides profound insights into the relationship between structure and performance,and proposes an efficient path for mass-producing multifunctional and high-performance EMW absorbers with excellent thermal properties.展开更多
The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of an...The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of anthraquinone-based COFs(i.e.,AAn-COF and OH-AAn-COF)with tunable 1D superstructures(e.g.,nanofibers(NF)and hollow tubes(HT))have been produced via Schiff-base condensation reaction.Interestingly,a rarely reported nanosheet-based self-template mechanism and a nanosheet-crimping mechanism have been demonstrated for the production of COF-based nanofibers and hollow tubes,respectively.Besides,the obtained COF-based superstructures can be post-modified with transition metals for efficient CO_(2)RR.Specifically,AAn-COF-Cu(NF)and OH-AAn-COF-Cu(HT)exhibit superior faradaic-efficiency with CH_(4)(FECH_(4))of 77%(-128.1 mA cm^(-2),-0.9 V)and 61%(-99.5 mA cm^(-2),-1.0 V)in a flow-cell,respectively.Noteworthy,the achieved FECH_(4) of AAn-COF-Cu(NF)(77%)is the highest one among reported crystalline COFs.This work provides a general methodology in exploring morphology-controlled COFs for electrocatalytic CO_(2)RR.展开更多
Mesocrystals, the non-classical crystals with highly ordered nanoparticle superstructures, have shown great potential in many applications because of their newly collective properties. However, there is still a lack o...Mesocrystals, the non-classical crystals with highly ordered nanoparticle superstructures, have shown great potential in many applications because of their newly collective properties. However, there is still a lack of a facile and general synthesis strategy to organize and integrate distinct components into complex mesocrystals, and of reported application for them in industrial catalytic reactions. Herein we report a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals (denoted as CuO-M1Ox-M2Oy, where M1 and M2 = Zn, In, Fe, Ni, Mn, and Co) using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination. When these mesocrystals were used as the catalyst to produce trichlorosilane (TCS) via Si hydrochlorination reaction, they exhibited excellent catalytic performance with much increased Si conversion and TCS selectivity. In particular, the TCS yield was increased 19-fold than that of the catalyst-free process. The latter is the current industrial process. The efficiently catalytic property of these mesocrystals is attributed to the formation of well-defined nanoscale heterointerfaces that can effectively facilitate the charge transfer, and the generation of the compressive and tensile strain on CuO near the interfaces among different metal oxides. The synthetic approach developed here could be applicable to fabricate versatile complicated metal oxide mesocrystals as novel catalysts for various industrial chemical reactions.展开更多
The vibration response and noise caused by subway trains can affect the safety and comfort of superstructures.To study the dynamic response characteristics of subway stations and superstructures under train loads with...The vibration response and noise caused by subway trains can affect the safety and comfort of superstructures.To study the dynamic response characteristics of subway stations and superstructures under train loads with a hard combination,a numerical model is developed in this study.The indoor model test verified the accuracy of the numerical model.The influence laws of different hard combinations,train operating speeds and modes were studied and evaluated accordingly.The results show that the frequency corresponding to the peak vibration acceleration level of each floor of the superstructure property is concentrated at 10–20 Hz.The vibration response decreases in the high-frequency parts and increases in the lowfrequency parts with increasing distance from the source.Furthermore,the factors,such as train operating speed,operating mode,and hard combination type,will affect the vibration of the superstructure.The vibration response under the reversible operation of the train is greater than that of the unidirectional operation.The operating speed of the train is proportional to its vibration response.The vibration amplification area appears between the middle and the top of the superstructure at a higher train speed.Its vibration acceleration level will exceed the limit value of relevant regulations,and vibration-damping measures are required.Within the scope of application,this study provides some suggestions for constructing subway stations and superstructures.展开更多
Low-dimensional materials have attracted increasing attention due to their guiding significance for material preparation and potential wide-ranging applications.Through the controllable synthesis and suitably designed...Low-dimensional materials have attracted increasing attention due to their guiding significance for material preparation and potential wide-ranging applications.Through the controllable synthesis and suitably designed fusion of lowdimensional materials into ordered complex superstructures,it has become an effective way to explore new properties of materials and construct structures meeting new application needs.Based on low-dimensional materials such as metal oxides,copolymers,metal-organic complexes,and organic crystals,great efforts have been devoted to the design and construction of complex superstructures with regular repeatability.A series of unique cases including multi-block,core/multi-shell,hyperbranched and network structures have been reported,which has promoted the development of the field of material preparation.Herein,we summarize representative progress of low-dimensional complex superstructures in a reasonable structure classification manner.Ultimately,the existing challenges are discussed,and an outlook is given for future study of precise construction of superstructures as well as exploitation of potential applications.展开更多
Fullerene assembling with specific donor molecules would yield multi-functional metamaterials via the collective behavior,wherein linear acenes are widely used as donor molecules to construct the charge‐transfer hete...Fullerene assembling with specific donor molecules would yield multi-functional metamaterials via the collective behavior,wherein linear acenes are widely used as donor molecules to construct the charge‐transfer heterojunction structure with fullerene.However,they are generally prepared by vacuum deposition due to the insoluble property of high‐performance linear acenes molecules in common solvents,which makes the construction of fullerene with insoluble donor molecules still be a big challenge in the solution‐processed method.To this end,chemical modification provides an effective solution‐processed strategy to construct donor and acceptor systems.Here,the C60‐pentacene is assembled into controllable flower‐like superstructures by the surface grafting method.It is found that the nanofeatures of the microflowers could be regulated by temperature,resulting in dense‐flakes morphology at room temperature and loose flakes at high temperatures.Furthermore,the dense‐flakes microflowers structures with less mass but better crystalline structure exhibit better optoelectronic properties.Our results reveal an effective control on the nanofeatures of the self‐assembled fullerenes complex super-structures and their role for the optoelectronic performance,which may promote the exploring of fullerene superstructures as photodetectors.展开更多
Carbon materials are a key component in energy storage and conversion devices and their microstructure plays a crucial role in determining device performance.However,traditional carbon materials are unable to meet the...Carbon materials are a key component in energy storage and conversion devices and their microstructure plays a crucial role in determining device performance.However,traditional carbon materials are unable to meet the requirements for applications in emerging fields such as renewable energy and electric vehicles due to limitations including a disordered structure and uncontrolled defects.With an aim of realizing devisable structures,adjustable functions,and performance breakthroughs,superstructured carbons is proposed and represent a category of carbon-based materials,characterized by precisely-built pores,networks,and interfaces.Superstructured carbons can overcome the limitations of traditional carbon materials and improve the performance of energy storage and conversion devices.We review the structure-activity relationships of superstructured carbons and recent research advances from three aspects including a precisely customized pore structure,a dense carbon network framework,and a multi-component highly coupled interface between the different components.Finally,we provide an outlook on the future development of and practical challenges in energy storage and conversion devices.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 22272118, 22172111, 21905207, and 22309134)the Science and Technology Commission of Shanghai Municipality (Nos. 22ZR1464100, 20ZR1460300, and 19DZ2271500)+2 种基金China Postdoctoral Science Foundation (No. 2022M712402), Shanghai Rising-Star Program (No. 23YF1449200)Zhejiang Provincial Science and Technology Project (No. 2022C01182)the Fundamental Research Funds for the Central Universities (Nos. 22120210529 and 2023–3-YB-07)。
文摘Designing carbon materials with ideal stable hierarchical porous structures and fiexible functional properties for efficient and sustainable Zn2+ion storage still faces great challenges. Herein, the threedimensional carbon superstructures with spherical nanofiower-like structures were tailor-made by the self-assembly strategy. Specifically, organic polymer units(i.e., organic motifs) were formed by tetrachloro-p-benzoquinone(TBQ) and 2,6-diamino anthraquinone(DAQ) via a noble-metal-free catalyzed coupling reaction. Subsequently, the organic motifs assemble into spherical nanofiower-like superstructures induced by intermolecular hydrogen bonding and aromatic π-π stacking interactions. Welldesigned carbon superstructures can provide a stable backbone that effectively blocks structural stacking and collapse. Meanwhile, the hierarchical porous structures in 3D carbon superstructures provide continuous charge transport pathways to greatly shorten the ion diffusion distance, and as a result, the carbon superstructures-based zinc-ion hybrid capacitors(ZIHCs) provide a capacity of 245 m Ah/g at 0.5 A/g, a high energy density of 152 Wh/kg and an ultra-long life of 300,000 cycles at 20 A/g. The excellent electrochemical performance is also attributed to the corresponding charge storage mechanism, i.e., the alternate binding of Zn^(2+)/CF_(3)SO_(3)^(-) ions. Besides, the high-level N/O motifs improve the surface properties of the carbon superstructures and reduce the ion migration barriers for more efficient charge storage. This paper provides insights into the design of advanced carbon-based cathodes and presents a fundamental understanding of their charge storage mechanisms.
基金supported by the Australian Research Council Linkage Project(No.LP200200717)co sponsored by Newmont Corporation(United States)and Vega Industries(India)+1 种基金the Powder Diffraction Beamline at the Australia’s Nuclear Science and Technology Organisation(No.PDR19870),Australiathe Centre for Microscopy and Microanalysis at the University of Queensland(No.1366),Australia。
文摘Pyrrhotite naturally occurs in various superstructures including magnetic(4C)and non-magnetic(5C,6C)types,each with distinct physicochemical properties and flotation behaviors.Challenges in accurately identifying and quantifying these superstructures hinder the optimization of pyrrhotite depression in flotation processes.To address this critical issue,synchrotron X-ray powder diffraction(S-XRPD)with Rietveld refinement was employed to quantify the distribution of superstructures in the feed and flotation concentrates of a copper–gold ore.To elucidate the mechanisms influencing depression,density functional theory(DFT)calculations were conducted to explore the electronic structures and surface reactivity of the pyrrhotite superstructures toward the adsorption of water,oxygen and hydroxyl ions(OH-)as dominant species present in the flotation process.S-XRPD analysis revealed that flotation recovery rates of pyrrhotite followed the order of 4C<6C<5C.DFT calculations indicated that the Fe 3d and S 3p orbital band centers exhibited a similar trend relative to the Fermi level with 4C being the closest.The Fe3d band center suggested that the 4C structure possessed a more reactive surface toward the oxygen reduction reaction,promoting the formation of hydrophilic Fe-OH sites.The S 3p band center order also implied that xanthate on the non-magnetic 5C and 6C surfaces could oxidize to dixanthogen,increasing hydrophobicity and floatability,while 4C formed less hydrophobic metal-xanthate complexes.Adsorption energy and charge transfer analyses of water,hydroxyl ions and molecular oxygen further supported the high reactivity and hydrophilic nature of 4C pyrrhotite.The strong bonding with hydroxyl ions indicated enhanced surface passivation by hydrophilic Fe–OOH complexes,aligning with the experimentally observed flotation order(4C<6C<5C).These findings provide a compelling correlation between experimental flotation results and electronic structure calculations,delivering crucial insights for optimizing flotation processes and improving pyrrhotite depression.This breakthrough opens up new opportunities to enhance the efficiency of flotation processes in the mining industry.
基金financially supported by the Program for the Development of Science and Technology of Jilin Province(Nos.YDZJ202201ZYTS313,YDZJ202201ZYTS395,20240402072GH,and 20240101004JJ)the National Natural Science Foundation of China(Nos.22201097 and 52171210)。
文摘Improving the surface atoms utilization efficiency of catalysts is extremely important for large-scale H_(2)production by electrochemical water splitting,but it remains a great challenge.Herein,we reported two kinds of Mo O_(3)-polyoxometalate hybrid nanobelt superstructures(MoO_(3)-POM HNSs,POM=PW_(12)O_(40)and Si W_(12)O_(40))using a simple hydrothermal method.Such superstructure with highly uniform nanoparticles as building blocks can expose more surface atoms and emanate increased specific surface area.The incorporated POMs generated abundant oxygen vacancies,improved the electronic mobility,and modulated the surface electronic structure of MoO_(3),allowing to optimize the H^(*)adsorption/desorption and dehydrogenation kinetics of catalyst.Notably,the as-prepared MoO_(3)-PW_(12)O_(40)HNSs electrodes not only displayed the low overpotentials of 108 mV at 10 mA/cm^(2)current density in 0.5 mol/L H_(2)SO_(4)electrolyte but also displayed excellent long-term stability.The hydrogen evolution reaction(HER)performance of MoO_(3)-POM superstructures is significantly better than that of corresponding bulk materials MoO_(3)@PW_(12)O_(40)and Mo O_(3)@Si W_(12)O_(40),and the overpotentials are about 8.3 and 4.9 times lower than that of single Mo O_(3).This work opens an avenue for designing highly surface-exposed catalysts for electrocatalytic H_(2)production and other electrochemical applications.
基金financially supported by Joint Fund Project of the Natural Science Foundation of Jilin Province(No.YDZJ202301ZYTS290)。
文摘Hydrogen evolution electrocatalysts derived from metal-organic crystalline frameworks can inherit the merits of ordered and adjustable structures with high surface area.In this paper,organic-octamolybdate crystalline superstructures(OOCS)with a fixed stoichiometric ratio of Mo_(8)(L)_(2) and high Mo content(>40 wt%)were synthesized using flexible ligands with controllable lengths(named as OOCS-1-3).Then,molybdenum carbides coated with carbon layers as electrocatalysts(Mo_(2)C@C-1-3)can be obtained directly from a one-step high-temperature carbonization process using OOCS-1-3 as precursors.As a typical example,Mo_(2)C@C-3 exhibits satisfactory hydrogen evolution activity with a low overpotential of 151 m V(1.0 mol/L KOH)at 10 m A/cm^(2) and stability for 24 h.The electrocatalytic activity is mainly from the synergistic interactions between the carbon layers and molybdenum carbide species.Furthermore,compared with the initial content of C,N,Mo in OOCS and Mo_(2)C@C,the catalytic activity increases with the N amount.This work makes organic-octamolybdate crystalline superstructures used as general precursors to product high Mo content electrocatalysts applied in energy storage and conversion fields.
基金supported by the Villum Fonden, Denmark, Project No. 13153the China Scholarship Council (CSC) for its generous support。
文摘Glioblastoma(GBM) remains a formidable challenge in oncology.Chemodynamic therapy(CDT) that triggers tumor cell death by reactive oxygen species(ROS) could open up a new door for GBM treatment.Herein,we report a novel CDT nanoagent.Hemoglobin(Hb)and glucose oxidase(GOx) were employed as powerful CDT catalysts.Instead of encapsulating the proteins in drug delivery nanocarriers,we formulate multimeric superstructures as self-delivery entities by crosslinking techniques.Red blood cell(RBC) membranes are camouflaged on the protein superstructures to promote the delivery across blood-brain barrier.The as-prepared RBC@Hb@GOx nanoparticles(NPs) offer superior biocompatibility,simplified structure,and high accumulation at the tumor site.We successfully demonstrated that the NPs could efficiently produce toxic ROS to kill U87 MG cancer cells in vitro and inhibit the growth of GBM tumor in vivo,suggesting that the new CDT nanoagent holds great promise for treating GBM.
基金supported by Fund of Weinan Teachers University(10YKF014)
文摘Urchin-like Ni O superstructures have been prepared via a thermal decomposition reaction of Ni C_2O_4 at 400 for 1h. The morphology and structure of the synthesized urchin-like superstructures have been characterized by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The results show that urchin-like Ni O superstructures were a polycrystal with cubic structure and typical diameters of 200 to 500 nm and the self-assembly nanoparticles average diameter is 14 nm. The as-prepared Ni O superstructures have a high Brunauer-Emmett-Teller surface area of about 60.32 m^2/g. The UV-vis spectrum of urchin-like Ni O consists of one peak at 357 nm(3.47 e V).
文摘Mitochondria, usually ovoid structures no larger than 0.5 microns can fuse into structures that are 5 microns and larger such as nebenkern, spheroidal or cup-shaped mitochondria, and even mega-mitochondria. In studying differentiation of human endometrial epithelial cells, it became clear that formation of mitochondrial superstructures was an essential part of the process. In this paper, the origins, function, and demise of these superstructures called mitonucleons are described. In the course of reading papers about mitochondrial superstructures, it became obvious that there are important similarities, particularly with regard to function, between the mitonucleon and the nebenkern, a superstructure essential for dramatic tail elongation during spermatogenesis in grasshoppers, drosophila, and other insects. Close inspection of photomicrographs of differentiating mitonucleons during the first 12 hours suggests that gases build up in vacuoles within the mitochondrial superstructure creating pressure that elevates syncytial membranes and compresses nuclear aggregates contained within the mitonucleon.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61674045,61911540074,and 21622304)the Fund from the Ministry of Science and Technology of China(Grant No.2016YFA0200700)+1 种基金the Strategic Priority Research Program and Key Research Program of Frontier Sciences(Chinese Academy of Sciences)(Grant Nos.XDB30000000 and QYZDB-SSW-SYS031)Zhihai Cheng was supported by the Fundamental Research Funds for the Central Universities and the Research Funds of Renmin University of China(Grant No.21XNLG27).
文摘The ultrathinβ-Sn(001)films have attracted tremendous attention owing to its topological superconductivity(TSC),which hosts Majorana bound state(MBSs)for quantum computation.Recently,β-Sn(001)thin films have been successfully fabricated via phase transition engineering.However,the understanding of structural phase transition ofβ-Sn(001)thin films is still elusive.Here,we report the direct growth of ultrathinβ-Sn(001)films epitaxially on the highly oriented pyrolytic graphite(HOPG)substrate and the characterization of intricate structural-transition-induced superstructures.The morphology was obtained by using atomic force microscopy(AFM)and low-temperature scanning tunneling microscopy(STM),indicating a structure-related bilayer-by-bilayer growth mode.The ultrathinβ-Sn film was made of multiple domains with various superstructures.Both high-symmetric and distorted superstructures were observed in the atomic-resolution STM images of these domains.The formation mechanism of these superstructures was further discussed based on the structural phase transition ofβtoα-Sn at the atomic-scale thickness.Our work not only brings a deep understanding of the structural phase transition of Sn film at the two-dimensional limit,but also paves a way to investigate their structure-sensitive topological properties.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11574372 and 11322432the 'Strategic Priority Research Program(B)' of the Chinese Academy of Sciences under Grant No XDB07020300
文摘Using scanning tunneling microscopy we observe a stripe phase smoothly interfacing with a triangular 2 ×2 super- structure on the surface of 2H-NbSe2 single crystM. Proximity-induced superconductivity is demonstrated in these new ordered structures by measurements of low-temperature tunneling spectra. The modulation of superconduc- tivity by the reconstruction provides an opportunity to understand the interplay between superconductivity and charge orders.
基金supported by the National Natural Science Foundation of China(Nos.NSFC-U1904215 and 21671170)the Topnotch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+1 种基金Program for Young Changjiang Scholars of the Ministry of Education,China(No.Q2018270)the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Hierarchical superstructures assembled by nanosheets can effectively prevent aggregation of nanosheets and improve performance in energy storage.Therefore,we proposed a facile hydrothermal method to obtain three-dimensional(3D)superstructure assembled by nanosheets.We found that the ratio of Co^(2+)/HMTA affected the morphology of the samples,and the 3D hierarchical structures of are obtained while the ratio of Co^(2+)/HMTA is 12:25.The hierarchical structures with sufficient interior space preserves the original sheet-like dimensional components and results in sufficient active sites and efficient mass diffusion.Hence,the 3D Co_(2)V_(2)O_(7)·nH_(2)O hierarchical structure exhibits good rate capability and high stability while as electrode materials.Meanwhile,when power density is 745.13 W/kg,the assembled CVO-2//AC shows an energy density of 47.7 Wh/kg.The work displays a facile method for fabrication of 3D superstructure assembled by 2D nanosheets that can be applied in energy storage.
文摘Since there may exist dark matter particles ν and δ with mass - 10^-1 e V in the universe, the superstructures with a scale of 10^19 solar masses （large number A - 10^19） appeared during the era near and before the hydrogen recombination. Since there are superstructures in the universe, there may be no necessity for the existence of dark energy. For checking the superstructure in the universe by CMB anisotropy, we need to measure CMB angular power spectrum especially around ten degrees across the sky- in more details, While neutrino u is related to electroweak unification, the fourth stable elementary particle 6 may be related to strong-gravity unification, which suggests p ＋ p^- → n ＋ δ^- and that some new baryons appeared in the TeV region.
基金the financial support from the National Key Research and Development Program of China(No.2021YFA1200300)the National Natural Science Foundation of China(Nos.22372031 and 22074102).
文摘Planar assemblies of plasmonic nanoparticles have provided opportunities in various fields.This study exploits the self-assembly of gold nanorods(AuNRs)into planar,layered chiral superstructures(dodecamer)using DNA origami technology.Due to the collective plasmonic coupling modes,the dodecamers exhibit g-factors of up to+0.06,which is 4-5 times higher than those of the dextrodimers.The chiroptical property of the superstructures proved to be strongly size-dependent,exhibiting enhanced g-factors with increasing the size of AuNRs.Moreover,by excluding the averaging and close-to-racemic effects in the ensemble colloids,circular differential scattering(CDS)and circularly polarized luminescence(CPL)were studied at the single-particle level,revealing the essential role of the structural chirality of superstructure in correlating single-particle scattering with nearby dye emission.The observed correlated CDS and CPL show g-factors up to−0.17 and−0.6,respectively.These results highlight the potential of DNA origami-directed plasmonic assemblies for nanoscale chirality engineering,with applications in biosensing,chiral photonics,and metamaterials.
基金supported by the Natural Science Foundation of Shandong Province(Nos.ZR2021ME194,2022TSGC2448,and 2023TSGC0545)the Key Technology Research and Development Program of Shandong Province(No.2021ZLGX01).
文摘The novel fabrication of multiple components and unique heterostructure can inject infinite vitality into the electromagnetic wave(EMW)attenuation field.Herein,through the self-assembly of polyimide com-plexes and catalytic chemical vapor deposition,porous carbon microflowers were synthesized accompa-nied by carbon nanotubes(CNTs).By regulating the metal ions,the composition and structure of the as-obtained hybrids are modified correspondingly,and thus the adjustable thermal management and EMW absorption capabilities are obtained.In detail,the rich pores and huge specific surface area endow the hierarchical structures with distinguished thermal insulation ability(λ<0.07).The carbon framework and CNTs are beneficial for consuming EMWs via conductive loss and defect polarization loss while reduc-ing the filling ratio and thickness.The doped heteroatoms and abundant heterointerfaces generate ample dipole polarization and interface polarization losses(supported by DFT calculation).The metal nanopar-ticles uniformly embedded in the carbon framework offer optimized impedance matching,proper de-fect polarization,and suitable magnetic loss.Accordingly,the synergy of magnetic-dielectric balance and flower-like superstructure enables FNCFN2 and NNCFN2 to accomplish remarkable microwave absorbing capacity with thin thickness(14 wt.%).Therefore,respectable specific reflection loss and specific effec-tive absorption bandwidth are acquired(215.39 dB mm^(-1) and 22.10 GHz mm^(-1),257.23 dB mm^(-1) and 22.12 GHz mm^(-1) respectively),superior to those of certain renowned carbon-based absorbers.The simu-lation results of electric field intensity distributions,power loss density,and radar cross section reduction(maximum value of 36.02 dBm2)also verify the prominent radar stealth capability.Moreover,the cus-tomizable approach can be applied to other metals to obtain fulfilling behaviors.Henceforth,this work provides profound insights into the relationship between structure and performance,and proposes an efficient path for mass-producing multifunctional and high-performance EMW absorbers with excellent thermal properties.
基金supported by the National Natural Science Foundation of China(21871141,21871142,21901122,22071109 and 92061101)the Natural Science Research of Jiangsu Higher Education Institutions of China(19KJB150011)+3 种基金China Postdoctoral Science Foundation(2018M630572 and 2019M651873)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX201171)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘The design of selective and efficient covalent organic frameworks(COFs)based electrocatalysts with tunable morphology for efficient CO_(2) reduction reaction(CO_(2)RR)to CH_(4) is highly desirable.Here,two kinds of anthraquinone-based COFs(i.e.,AAn-COF and OH-AAn-COF)with tunable 1D superstructures(e.g.,nanofibers(NF)and hollow tubes(HT))have been produced via Schiff-base condensation reaction.Interestingly,a rarely reported nanosheet-based self-template mechanism and a nanosheet-crimping mechanism have been demonstrated for the production of COF-based nanofibers and hollow tubes,respectively.Besides,the obtained COF-based superstructures can be post-modified with transition metals for efficient CO_(2)RR.Specifically,AAn-COF-Cu(NF)and OH-AAn-COF-Cu(HT)exhibit superior faradaic-efficiency with CH_(4)(FECH_(4))of 77%(-128.1 mA cm^(-2),-0.9 V)and 61%(-99.5 mA cm^(-2),-1.0 V)in a flow-cell,respectively.Noteworthy,the achieved FECH_(4) of AAn-COF-Cu(NF)(77%)is the highest one among reported crystalline COFs.This work provides a general methodology in exploring morphology-controlled COFs for electrocatalytic CO_(2)RR.
基金the National Natural Science Foundation of China(Nos.21878301,21978299,and 21908224)Z.Z.thanks the kind support of Guangdong Technion Israel Institute of Technology(GTTIT)for the collaboration.
文摘Mesocrystals, the non-classical crystals with highly ordered nanoparticle superstructures, have shown great potential in many applications because of their newly collective properties. However, there is still a lack of a facile and general synthesis strategy to organize and integrate distinct components into complex mesocrystals, and of reported application for them in industrial catalytic reactions. Herein we report a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals (denoted as CuO-M1Ox-M2Oy, where M1 and M2 = Zn, In, Fe, Ni, Mn, and Co) using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination. When these mesocrystals were used as the catalyst to produce trichlorosilane (TCS) via Si hydrochlorination reaction, they exhibited excellent catalytic performance with much increased Si conversion and TCS selectivity. In particular, the TCS yield was increased 19-fold than that of the catalyst-free process. The latter is the current industrial process. The efficiently catalytic property of these mesocrystals is attributed to the formation of well-defined nanoscale heterointerfaces that can effectively facilitate the charge transfer, and the generation of the compressive and tensile strain on CuO near the interfaces among different metal oxides. The synthetic approach developed here could be applicable to fabricate versatile complicated metal oxide mesocrystals as novel catalysts for various industrial chemical reactions.
基金National Natural Science Foundation of China under Grant No.51578463。
文摘The vibration response and noise caused by subway trains can affect the safety and comfort of superstructures.To study the dynamic response characteristics of subway stations and superstructures under train loads with a hard combination,a numerical model is developed in this study.The indoor model test verified the accuracy of the numerical model.The influence laws of different hard combinations,train operating speeds and modes were studied and evaluated accordingly.The results show that the frequency corresponding to the peak vibration acceleration level of each floor of the superstructure property is concentrated at 10–20 Hz.The vibration response decreases in the high-frequency parts and increases in the lowfrequency parts with increasing distance from the source.Furthermore,the factors,such as train operating speed,operating mode,and hard combination type,will affect the vibration of the superstructure.The vibration response under the reversible operation of the train is greater than that of the unidirectional operation.The operating speed of the train is proportional to its vibration response.The vibration amplification area appears between the middle and the top of the superstructure at a higher train speed.Its vibration acceleration level will exceed the limit value of relevant regulations,and vibration-damping measures are required.Within the scope of application,this study provides some suggestions for constructing subway stations and superstructures.
基金supported by the National Natural Science Foundation of China(52173177,21971185 and 51821002)the Collaborative Innovation Center of Suzhou Nano Science and Technology(CIC-Nano)the“111”Project of the State Administration of Foreign Experts Affairs of China
文摘Low-dimensional materials have attracted increasing attention due to their guiding significance for material preparation and potential wide-ranging applications.Through the controllable synthesis and suitably designed fusion of lowdimensional materials into ordered complex superstructures,it has become an effective way to explore new properties of materials and construct structures meeting new application needs.Based on low-dimensional materials such as metal oxides,copolymers,metal-organic complexes,and organic crystals,great efforts have been devoted to the design and construction of complex superstructures with regular repeatability.A series of unique cases including multi-block,core/multi-shell,hyperbranched and network structures have been reported,which has promoted the development of the field of material preparation.Herein,we summarize representative progress of low-dimensional complex superstructures in a reasonable structure classification manner.Ultimately,the existing challenges are discussed,and an outlook is given for future study of precise construction of superstructures as well as exploitation of potential applications.
基金Beijing National Laboratory for Molecular Sciences,Grant/Award Number:BNLMS202006National Natural Science Foundation of China,Grant/Award Numbers:21875108,62004138+1 种基金Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20191289Instrument&Equipment Open Funding of Nanjing University of Science and Technology。
文摘Fullerene assembling with specific donor molecules would yield multi-functional metamaterials via the collective behavior,wherein linear acenes are widely used as donor molecules to construct the charge‐transfer heterojunction structure with fullerene.However,they are generally prepared by vacuum deposition due to the insoluble property of high‐performance linear acenes molecules in common solvents,which makes the construction of fullerene with insoluble donor molecules still be a big challenge in the solution‐processed method.To this end,chemical modification provides an effective solution‐processed strategy to construct donor and acceptor systems.Here,the C60‐pentacene is assembled into controllable flower‐like superstructures by the surface grafting method.It is found that the nanofeatures of the microflowers could be regulated by temperature,resulting in dense‐flakes morphology at room temperature and loose flakes at high temperatures.Furthermore,the dense‐flakes microflowers structures with less mass but better crystalline structure exhibit better optoelectronic properties.Our results reveal an effective control on the nanofeatures of the self‐assembled fullerenes complex super-structures and their role for the optoelectronic performance,which may promote the exploring of fullerene superstructures as photodetectors.
文摘Carbon materials are a key component in energy storage and conversion devices and their microstructure plays a crucial role in determining device performance.However,traditional carbon materials are unable to meet the requirements for applications in emerging fields such as renewable energy and electric vehicles due to limitations including a disordered structure and uncontrolled defects.With an aim of realizing devisable structures,adjustable functions,and performance breakthroughs,superstructured carbons is proposed and represent a category of carbon-based materials,characterized by precisely-built pores,networks,and interfaces.Superstructured carbons can overcome the limitations of traditional carbon materials and improve the performance of energy storage and conversion devices.We review the structure-activity relationships of superstructured carbons and recent research advances from three aspects including a precisely customized pore structure,a dense carbon network framework,and a multi-component highly coupled interface between the different components.Finally,we provide an outlook on the future development of and practical challenges in energy storage and conversion devices.
