Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains...Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.展开更多
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
Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by ...Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by the ancient mortise-and-tenon joint,we herein report a series of crystalline nanocluster superstructures(MTC-1 and MTC-2)that were exclusively assembled by such molecular joints,representing the first paradigm of its kind.Despite alterations in functional groups(methyl and ethyl),the supramolecular packing motif remains invariant,underscoring the robustness of this directed assembly strategy.Notably,the ethyl groups in MTC-2 serve as“locking pins”,resulting in MTC-2 a fascinating Luban lock-like construction.This ingenious design endows MTC-2 with enhanced photogenerated charge migration and superior O2 adsorption capability,achieving a record-high photocatalytic H_(2)O_(2) production rate(19,978μmol·g^(-1)·h^(-1))among all isolated crystalline cluster-based materials,an order-of-magnitude enhancement over existing benchmarks.This work not only presents a record-breaking photocatalyst but also establishes a general assembly strategy,the mortise-and-tenon joint,which is expected to guide the rational design of functional superstructures across diverse nanocluster systems.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
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
Sodium-ion batteries(SIBs) hold great promise to be the next-generation large-scale energy storage system due to their costeffectiveness and resource availability.More importantly,sodium-ion batteries have energy dens...Sodium-ion batteries(SIBs) hold great promise to be the next-generation large-scale energy storage system due to their costeffectiveness and resource availability.More importantly,sodium-ion batteries have energy density approaching that of lithiumion batteries,outperforming most of their counterparts.Further improvement of their energy density depends on the innovation of high-capacity layered sodium-ion cathodes,which entails the participation of anionic redox whose origin and reversibility are closely associated with the superstructures in the transition metal layer.Recently,various superstructures were found in layered sodium-ion cathodes and were tightly correlated with their anionic redox activity and electrochemistry.Given its high importance in tailoring the performance of sodium-ion cathodes,in this minireview,we systematically summarize the recent progress of superstructure in SIBs,assisting in understanding the underlying mechanism of anionic redox that is coupled with transition metal migration,O-O dimer formation,and consequently,the voltage hysteresis.We start with the structurerelationship between anionic redox and superstructures(mainly honeycomb,ribbon and mesh superstructures) by delving into the band structure of these Na-based cathodes.The different properties of the three main superstructures are then compared and discussed,followed by a revisit of recent progress on varying the honeycomb superstructures.Finally,we present our perspectives on how to utilize such superstructure-related anionic redox via stabilizing and tuning the structural units with various strategies.We hope this minireview can clarify the various characteristics of different superstructures and offer a unique insight toward high-energy-density sodium-ion batteries with anionic redox.展开更多
“Chiral-induced spin selectivity(CISS)”and its device applications are predominantly at the experimental stage,with mechanisms not fully understood.There is a need for new chiral materials with simple structures and...“Chiral-induced spin selectivity(CISS)”and its device applications are predominantly at the experimental stage,with mechanisms not fully understood.There is a need for new chiral materials with simple structures and high room-temperature electron spin polarization rates,crucial for theoretical studies and low-power spin optoelectronic devices.This study examines the CISS effect in carbon nanotubes,graphene chiral rolls,and graphene chiral stacks.While all three exhibit chirality,only the one-side follow curved surface of the graphene rolls demonstrates the CISS effect.Using true and false chirality analysis from Professor Barron,we found that only the charge motion(current)on the chiral surface is true chiral,leading to spin polarization.Thus,the CISS phenomenon occurs when charge motion on the chiral surface is chiral.Both chiral surface structures and chiral charge motion are necessary for electron spin polarization.Further theoretical validation of these conditions will enhance CISS theory.展开更多
Metal-organic framework(MOF)nanoparticles are successfully confined in the hollow mesoporous carbon spheres(HMCSs)through space-confined synthesis methods.The prepared ZIF-67@HMCSs nanocomposites act as effective sacr...Metal-organic framework(MOF)nanoparticles are successfully confined in the hollow mesoporous carbon spheres(HMCSs)through space-confined synthesis methods.The prepared ZIF-67@HMCSs nanocomposites act as effective sacrificial templates,which can afford Co^(2+)sources.After a facile solvothermal reaction and sequential cation etching,yolk-shell-structured layered double hydroxide@HMCSs(LDH@HMCSs)have been synthesized.The LDH@HMCSs nanocomposite possesses a three-dimensional(3D)hollow nanocage superstructure that effectively blocks the self-stacking of LDH nanosheets and promotes ion transport.Compared to CoFe-LDH@HMCSs,and Co-LDH@HMCSs,CoNi-LDH@HMCSs exhibit superior electrochemical performance and desalination performance due to the remarkable synergistic effect between the CoNi-LDH nanosheets and mesoporous N-doped carbon shells.The resultant CoNi-LDH@HMCSs-0.4-based capacitive deionization(CDI)device exhibits excellent salt adsorption capacity(SAC,36.41 mg·g^(-1))and good cycle stability.This work will confirm the significance of constructing superstructure and open new avenues for the practical application of CDI technology in water treatment.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
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111,and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300,and 19DZ2271500)+2 种基金the China Postdoctoral Science Foundation(2022M712402),the Shanghai Rising-Star Program(23YF1449200)the Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(2023-3-YB-07)。
文摘Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.
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supported by the National Natural Science Foundation of China(Nos.22575048,22101048,22271046,and 22373015)the National Science Fund for Distinguished Young Scholars of China(No.22425102)+1 种基金the Natural Science Foundation of Fujian Province(No.2025J01628)the Open Project of the National Key Laboratory of Structural Chemistry(No.20250002).
文摘Precise control over the isomorphic selfassembly of nanocluster superstructures via weak interactions remains a fundamental challenge in materials science,primarily due to the lack of directional guidance.Inspired by the ancient mortise-and-tenon joint,we herein report a series of crystalline nanocluster superstructures(MTC-1 and MTC-2)that were exclusively assembled by such molecular joints,representing the first paradigm of its kind.Despite alterations in functional groups(methyl and ethyl),the supramolecular packing motif remains invariant,underscoring the robustness of this directed assembly strategy.Notably,the ethyl groups in MTC-2 serve as“locking pins”,resulting in MTC-2 a fascinating Luban lock-like construction.This ingenious design endows MTC-2 with enhanced photogenerated charge migration and superior O2 adsorption capability,achieving a record-high photocatalytic H_(2)O_(2) production rate(19,978μmol·g^(-1)·h^(-1))among all isolated crystalline cluster-based materials,an order-of-magnitude enhancement over existing benchmarks.This work not only presents a record-breaking photocatalyst but also establishes a general assembly strategy,the mortise-and-tenon joint,which is expected to guide the rational design of functional superstructures across diverse nanocluster systems.
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 National Natural Science Foundation of China (52372166,92472103)the support of China Postdoctoral Science Foundation(GZB20250006)。
文摘Sodium-ion batteries(SIBs) hold great promise to be the next-generation large-scale energy storage system due to their costeffectiveness and resource availability.More importantly,sodium-ion batteries have energy density approaching that of lithiumion batteries,outperforming most of their counterparts.Further improvement of their energy density depends on the innovation of high-capacity layered sodium-ion cathodes,which entails the participation of anionic redox whose origin and reversibility are closely associated with the superstructures in the transition metal layer.Recently,various superstructures were found in layered sodium-ion cathodes and were tightly correlated with their anionic redox activity and electrochemistry.Given its high importance in tailoring the performance of sodium-ion cathodes,in this minireview,we systematically summarize the recent progress of superstructure in SIBs,assisting in understanding the underlying mechanism of anionic redox that is coupled with transition metal migration,O-O dimer formation,and consequently,the voltage hysteresis.We start with the structurerelationship between anionic redox and superstructures(mainly honeycomb,ribbon and mesh superstructures) by delving into the band structure of these Na-based cathodes.The different properties of the three main superstructures are then compared and discussed,followed by a revisit of recent progress on varying the honeycomb superstructures.Finally,we present our perspectives on how to utilize such superstructure-related anionic redox via stabilizing and tuning the structural units with various strategies.We hope this minireview can clarify the various characteristics of different superstructures and offer a unique insight toward high-energy-density sodium-ion batteries with anionic redox.
基金support of this research,we gratefully acknowledge the National Natural Science Foundation of China(No.22375141).
文摘“Chiral-induced spin selectivity(CISS)”and its device applications are predominantly at the experimental stage,with mechanisms not fully understood.There is a need for new chiral materials with simple structures and high room-temperature electron spin polarization rates,crucial for theoretical studies and low-power spin optoelectronic devices.This study examines the CISS effect in carbon nanotubes,graphene chiral rolls,and graphene chiral stacks.While all three exhibit chirality,only the one-side follow curved surface of the graphene rolls demonstrates the CISS effect.Using true and false chirality analysis from Professor Barron,we found that only the charge motion(current)on the chiral surface is true chiral,leading to spin polarization.Thus,the CISS phenomenon occurs when charge motion on the chiral surface is chiral.Both chiral surface structures and chiral charge motion are necessary for electron spin polarization.Further theoretical validation of these conditions will enhance CISS theory.
基金supported by the National Natural Science Foundation of China(No.52371240).
文摘Metal-organic framework(MOF)nanoparticles are successfully confined in the hollow mesoporous carbon spheres(HMCSs)through space-confined synthesis methods.The prepared ZIF-67@HMCSs nanocomposites act as effective sacrificial templates,which can afford Co^(2+)sources.After a facile solvothermal reaction and sequential cation etching,yolk-shell-structured layered double hydroxide@HMCSs(LDH@HMCSs)have been synthesized.The LDH@HMCSs nanocomposite possesses a three-dimensional(3D)hollow nanocage superstructure that effectively blocks the self-stacking of LDH nanosheets and promotes ion transport.Compared to CoFe-LDH@HMCSs,and Co-LDH@HMCSs,CoNi-LDH@HMCSs exhibit superior electrochemical performance and desalination performance due to the remarkable synergistic effect between the CoNi-LDH nanosheets and mesoporous N-doped carbon shells.The resultant CoNi-LDH@HMCSs-0.4-based capacitive deionization(CDI)device exhibits excellent salt adsorption capacity(SAC,36.41 mg·g^(-1))and good cycle stability.This work will confirm the significance of constructing superstructure and open new avenues for the practical application of CDI technology in water treatment.
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.
