Radio frequency capacitively coupled plasma source(RF-CCP)with a hollow electrode can increase the electron density through the hollow cathode effect(HCE),which offers a method to modify the spatial profiles of the pl...Radio frequency capacitively coupled plasma source(RF-CCP)with a hollow electrode can increase the electron density through the hollow cathode effect(HCE),which offers a method to modify the spatial profiles of the plasma density.In this work,the variations of the HCE in one RF period are investigated by using a two-dimensional particle-in-cell/Monte-Carlo collision(PIC/MCC)model.The results show that the sheath electric field,the sheath potential drop,the sheath thickness,the radial plasma bulk width,the electron energy distribution function(EEDF),and the average electron energy in the cavity vary in one RF period.During the hollow electrode sheath's expansion phase,the secondary electron heating and sheath oscillation heating in the cavity are gradually enhanced,and the frequency of the electron pendular motion in the cavity gradually increases,hence the HCE is gradually enhanced.However,during the hollow electrode sheath's collapse phase,the secondary electron heating is gradually attenuated.In addition,when interacting with the gradually collapsed hollow electrode sheaths,high-energy plasma bulk electrons in the cavity will lose some energy.Furthermore,the frequency of the electron pendular motion in the cavity gradually decreases.Therefore,during the hollow electrode sheath's collapse phase,the HCE is gradually attenuated.展开更多
Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology r...Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.展开更多
The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named...The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.展开更多
Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult...Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.展开更多
Introduction: The management of fractures of the tibia shaft is an important aspect of orthopaedic care, and the selection of the surgical method for fixation can substantially impact patient outcomes. The current rev...Introduction: The management of fractures of the tibia shaft is an important aspect of orthopaedic care, and the selection of the surgical method for fixation can substantially impact patient outcomes. The current review aims to compare the outcomes of adult tibia fractures treated with solid nails to those treated with hollow nails. Methods: A search on Scopus, PubMed, and Cochrane Library, using three keywords (Outcome, Tibia shaft fractures, Nail) was conducted in April 2023. Results were compiled and two independent reviewers screened and selected eligible articles After removing duplicates, titles and abstracts were read to exclude ineligible studies. Full-text articles of the remaining papers were read to select eligible studies which were further critically appraised to ascertain their methodological quality. The data extracted from the selected papers were synthesized using a combination of pooling of results, tests of statistical difference (t-test and chi-square) and narrative synthesis methods. Results: A total of 2295 articles were obtained from the databases and citation searching. A total of 9 papers were identified as eligible and included in the review. Findings revealed that there is no statistical difference in the outcomes of tibia fractures treated with either solid or hollow nail groups such as duration of surgery (p = 0.541), rate of delayed and non-union (p = 0.342), and rate of surgical site infections (p = 0.395). Conclusion: Intramedullary nailing of tibia shaft fractures with either solid or hollow nails have similar functional outcomes.展开更多
Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membra...Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.展开更多
Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heter...Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heterostructure as a model and multifunctional catalyst modified on separators to induce interfacial charge modulation and expose more active sites for promoting the adsorption and catalytic conversion ability of sulfur species.Theoretical and experimental findings verify that the in-situ formed core-shell hetero-interface induces the formation of P-Co-O binding and charge redistribution to activate surface O active sites for binding lithium polysulfides(LiPSs)via strong Li-O bonding,thus strongly adsorbing with Li PSs.Meanwhile,the strong Li-O bonding weakens the competing Li-S bonding in LiPSs or Li2S adsorbed on CoO/CoP-Box surface,plus the hollow heterostructure provides abundant active sites and fast electron/Li+transfer,so reducing Li2S nucleation/dissolution activation energy.As expected,LSBs with CoO/CoP-Box modified separator and traditional sulfur/carbon black cathode display a large initial capacity of 1240 mA h g^(-1)and a long cycling stability with 300 cycles(~60.1%capacity retention)at 0.5C.Impressively,the thick sulfur cathode(sulfur loading:5.2 mg cm^(-2))displays a high initial areal capacity of 6.9 mA h cm^(-2).This work verifies a deep mechanism understanding and an effective strategy to induce interfacial charge modulation and enhance active sites for designing efficient dual-directional Li-S catalysts via engineering hollow core-shell hetero-structure.展开更多
The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow...The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow nanofibers using a simple electrospinning and thermal treatment method.The hierarchical hollow nanofiber is composed of a nitrogen-doped carbon-coated NiS_(1.03) tube wall,in which pea-like uniformly discrete MoS_(2) nanoparticles are enclosed.As a sodium-ion battery electrode material,the MoS_(2)@NiS_(1.03)-carbon hollow nanofibers have abundant diphasic heterointerfaces,a conductive network,and appropriate volume variation-buffering spaces,which can facilitate ion diffusion kinetics,shorten the diffusion path of electrons/ion,and buffer volume expansion during Na^(+)insertion/extraction.It shows outstanding rate capacity and long-cycle performance in a sodium-ion battery.This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long-life stability of sodium storage performance of electrode materials.展开更多
Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in seconda...Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.展开更多
The development of efficient metal-zeolite bifunctional catalysts for catalytic fast pyrolysis(CFP) of biomass waste is highly desirable for bioenergy and renewable biofuel production.However,conventional metal-loaded...The development of efficient metal-zeolite bifunctional catalysts for catalytic fast pyrolysis(CFP) of biomass waste is highly desirable for bioenergy and renewable biofuel production.However,conventional metal-loaded zeolites often suffer from metal sintering during pyrolysis and are thus inactivated.In this study,single-site Ga-functionalized hollow ZSM-5(GaO_x@HS-Z5) was synthesized via an impregnationdissolution-recrystallization strategy without H_(2) reduction.The Ga atom was coordinated to four oxygen atoms in HS-Z5 frameworks.Benefitting from the highly dispersed single-Ga atoms and hollow zeolite framework,3GaO_x@HS-Z5 performed the best in producing hydrocarbon-rich bio-oil compared to impregnated 3GaO_x/HS-Z5 and H_(2)-reduced 3Ga@HS-Z5 in the maize straw CFP.In particular,3GaO_x@HS-Z5 delivered the highest bio-oil yield(23.6 wt%) and hydrocarbon selectivity(49.4 area%).3GaO_x@HS-Z5 also retained its structural integrity and catalytic activity after five pyrolysis-regeneration cycles,demonstrating its advantage in practical biomass CFP.The elimination of H_(2) reduction during the synthesis of catalyst provides an additional advantage for simplifying the CFP process and reducing operating costs.The retained Ga micro-environment and anti-sintering properties were unique for 3GaO_x@HS-Z5,as severe metal sintering occurred during pyrolysis for other metals(e.g.,NiO_x,ZnO_x,FeO_x,and CoO_x) that encapsulated HS-Z5.展开更多
Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid p...Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.展开更多
Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane cont...Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.展开更多
The hollow strontium carbonate pompons was synthesized for the first time by a controlled reaction precipitation method with sodium dodecyl benzene sulfonate(SDBS)and polyvinyl pyrrolidone(PVP)work together as templat...The hollow strontium carbonate pompons was synthesized for the first time by a controlled reaction precipitation method with sodium dodecyl benzene sulfonate(SDBS)and polyvinyl pyrrolidone(PVP)work together as template.The sampled particles were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption measurement,X-ray diffraction(XRD),Energy dispersive X-Ray spectroscopy(EDX),Fourier transform infrared spectroscopy(FTIR),Thermogravimetric analysis and differential scanning calorimetry(TGA-DSC),etc.It is shown that the assynthesized hollow strontium carbonate pompons with the size of about 2μm consist of flake-like particles under the optimal reaction conditions.The formation mechanism of hollow strontium carbonate pompons was preliminarily explored.展开更多
Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are li...Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are limited by the excessive expansion rate and low intrinsic conductivity.Herein,heterogeneous hollow sphere NiS-Cu_(9)S_(5)/NC(labeled as(NiCu)S/NC)based on Oswald ripening mechanism was prepared through a simple and feasible methodology.From a structural perspective,the hollow structure provides an expansion buffer and raises the electrochemical active area.In terms of electron/ion during the cycles,Na^(+)storage mechanism is optimized by NiS/Cu_(9)S_(5)heterogeneous interface,which increases the storage sites and shortens the migration path of Na^(+).The formation of built-in electric field strengthens the electron/ion mobility.Based on the first principle calculations,it is further proved the formation of heterogeneous interfaces and the direction of electron flow.As the anode for SIBs,the synthesized(NiCu)S/NC delivers high reverse capacity(559.2 mA h g^(-1)at 0.5 A g^(-1)),outstanding rate performance(185.3 mA h g^(-1)at 15 A g^(-1)),long-durable stability(342.6 mA h g^(-1)at 4 A g^(-1)after 1500cycles,150.0 m A h g^(-1)at 10 A g^(-1)after 20,000 cycles with 0.0025%average attenuation rate).The matching cathode electrode Na_(3)V_(2)(PO_(4))_(3)/C is assembled with(NiCu)S/NC for the full-battery that achieves high energy density(253.7 W h kg^(-1))and reverse capacity(288.7 mA h g^(-1)).The present work provides a distinctive strategy for constructing electrodes with excellent capacity and stability for SIBs.展开更多
Achieving high-efficiency sodium storage in metal selenides is still severely constrained in consideration of their inferior electronic conductivity and inadequate Na^(+)insertion pathways and active sites.Heteroatom ...Achieving high-efficiency sodium storage in metal selenides is still severely constrained in consideration of their inferior electronic conductivity and inadequate Na^(+)insertion pathways and active sites.Heteroatom doping accompanied by spontaneously developed lattice defects can effectively tune electronic structure of metal selenides,which give a strong effect to motivate fast charge transfer and Na^(+)accessibility.Herein,we finely designed and successfully constructed a fascinating phosphorus-doped Cu_(2)Se@C hollow nanosphere with abundant vacancy defects(Cu_(2)P_(x)Se_(1-x)@C)through a combination strategy of selenization of Cu_(2)O nanosphere template,self-polymerization of dopamine,and subsequent phosphorization treatment.Such exquisite composite possesses enriched active sites,superior conductivity,and sufficient Na^(+)insertion channel,which enable much faster Na^(+)diffusion rates and more remarkable pseudocapacitive features,Satisfyingly,the Cu_(2)P_(x)Se_(1-x)@C composites manifest the supernormal sodium-storage capabilities,that is,a reversible capacity of 403.7 mA h g^(-1) at 1.0 A g^(-1) over 100 cycles,and an ultrastable cyclic lifespan over 1000 cycles at 20.0 A g^(-1) with a high capacity-retention of about249.7 mA h g^(-1).The phase transformation of the Cu_(2)P_(x)Se_(1-x)@C involving the intercalation of Na^(+)into Cu_(2)Se and the following conversion of NaCuSe to Cu and Na2Se were further demonstrated through a series of ex-situ characterization methods.DFT results demonstrate that the coexistence of phosphorusdoping and vacancy defects within Cu_(2)Se results in the reduction of Na^(+)adsorption energy from-1.47to-1.56 eV improving the conductivity of Cu_(2)Se to further accelerate fast Na^(+)mobility.展开更多
The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of ...The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.展开更多
The loading strategy of cocatalysts affects its activity exerting and atom utilization.Here,a novel strategy for loading precious metal(Pt)cocatalysts by means of ultrathin N-doped carbon layer is reported.The strateg...The loading strategy of cocatalysts affects its activity exerting and atom utilization.Here,a novel strategy for loading precious metal(Pt)cocatalysts by means of ultrathin N-doped carbon layer is reported.The strategy is based on a pyrolysis process of predesigned N-containing polymers and Pt complexes on hard-template surface,during which Pt can be reduced by carbon from pyrolysis at high temperatures.Finally,the hollow TiO_(2)composite with stable and dispersed Pt on its inner surface was prepared.It shows an ultrahigh photocatalytic H_(2)production activity as high as 25.7 mmol h^(-1)g^(-1)with methanol as sacrificial regent,and displays an apparent quantum yield as 13.2%.The improved photocatalytic activity and stability can be attributed to the highly dispersed and ultrafine Pt nanoparticles,enhanced interaction between Pt-species and carbon support,fast photo-excited electron transport from the high graphitization degree of NC layers,ample oxygen vacancies/defects,as well as the manipulated local charge distribution of Pt/NC-layer configuration.Additionally,the universality of the proposed strategy was demonstrated by replacing metal sources(such as,Ru and Pd).This work presented a promising strategy for the design and development of novel photocatalysts,which shows a broad application prospect.展开更多
Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed...Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.展开更多
Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selecti...Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.展开更多
Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ord...Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ordered structure and toxic superacid that dissolves or destabilizes the metal nodes.To solve this problem,herein,we report a straightforward two-step pathway for the covalent hybridization of disordered CTF(d–CTF)–ZIF composites via preincorporation of an imidazole(IM)linker into ordered CTFs,followed by the imidazole-site-specific covalent growth of ZIFs.Direct carbonization of these synthesized d–CTF−IM−ZIF hybrids results in unique hollow carbon super-heterostructures with ultrahigh nitrogen content(>18.6%),high specific surface area(1663m^(2)g^(−1)),and beneficial trace metal(Co/Zn NPs)contents for promoting the redox pseudocapacitance.As proof of concept,the obtained carbon super-heterostructure(Co–Zn–NC_(SNH)–800)is used as a positive electrode in an asymmetric supercapacitor,demonstrating a remarkable energy density of 61Wh kg^(−1)and extraordinary cyclic stability of 97%retention after 30,000 cycles at the cell level.Our presynthetic modifications of CTF and their covalent hybridization with ZIF crystals pave the way toward new design strategies for synthesizing functional porous carbon materials for promising energy applications.展开更多
文摘Radio frequency capacitively coupled plasma source(RF-CCP)with a hollow electrode can increase the electron density through the hollow cathode effect(HCE),which offers a method to modify the spatial profiles of the plasma density.In this work,the variations of the HCE in one RF period are investigated by using a two-dimensional particle-in-cell/Monte-Carlo collision(PIC/MCC)model.The results show that the sheath electric field,the sheath potential drop,the sheath thickness,the radial plasma bulk width,the electron energy distribution function(EEDF),and the average electron energy in the cavity vary in one RF period.During the hollow electrode sheath's expansion phase,the secondary electron heating and sheath oscillation heating in the cavity are gradually enhanced,and the frequency of the electron pendular motion in the cavity gradually increases,hence the HCE is gradually enhanced.However,during the hollow electrode sheath's collapse phase,the secondary electron heating is gradually attenuated.In addition,when interacting with the gradually collapsed hollow electrode sheaths,high-energy plasma bulk electrons in the cavity will lose some energy.Furthermore,the frequency of the electron pendular motion in the cavity gradually decreases.Therefore,during the hollow electrode sheath's collapse phase,the HCE is gradually attenuated.
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212,52102058,52204414,52204413,and 52204412)the National Key R&D Program of China (Nos.2021YFC1910504,2019YFC1907101,2019YFC1907103,and 2017YFB0702304)+7 种基金the Key R&D Program of Ningxia Hui Autonomous Region,China (Nos.2021BEG01003 and2020BCE01001)the Xijiang Innovation and Entrepreneurship Team,China (No.2017A0109004)the Macao Young Scholars Program (No.AM2022024),Chinathe Beijing Natural Science Foundation (Nos.L212020 and 2214073),Chinathe Guangdong Basic and Applied Basic Research Foundation,China (Nos.2021A1515110998 and 2020A1515110408)the China Postdoctoral Science Foundation (No.2022M710349)the Fundamental Research Funds for the Central Universities,China (Nos.FRF-BD-20-24A,FRF-TP-20-031A1,FRF-IC-19-017Z,and 06500141)the Integration of Green Key Process Systems MIIT and Scientific and Technological Innovation Foundation of Foshan,China(Nos.BK22BE001 and BK21BE002)。
文摘Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.
基金the National Key Research and Development Program(2021YFC3001103)the National Natural Science Foundation(22278209,22178165,21921006,22208149)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20211262,BK20220354)a project funded by the priority academic program development of Jiangsu higher education institutions(PAPD)of China。
文摘The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.
基金This work was supported by National Key R&D Program of China(2021YFF0500503)National Natural Science Foundation of China(21925202,U22B2071)International Joint Mission on Climate Change and Carbon Neutrality.
文摘Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.
文摘Introduction: The management of fractures of the tibia shaft is an important aspect of orthopaedic care, and the selection of the surgical method for fixation can substantially impact patient outcomes. The current review aims to compare the outcomes of adult tibia fractures treated with solid nails to those treated with hollow nails. Methods: A search on Scopus, PubMed, and Cochrane Library, using three keywords (Outcome, Tibia shaft fractures, Nail) was conducted in April 2023. Results were compiled and two independent reviewers screened and selected eligible articles After removing duplicates, titles and abstracts were read to exclude ineligible studies. Full-text articles of the remaining papers were read to select eligible studies which were further critically appraised to ascertain their methodological quality. The data extracted from the selected papers were synthesized using a combination of pooling of results, tests of statistical difference (t-test and chi-square) and narrative synthesis methods. Results: A total of 2295 articles were obtained from the databases and citation searching. A total of 9 papers were identified as eligible and included in the review. Findings revealed that there is no statistical difference in the outcomes of tibia fractures treated with either solid or hollow nail groups such as duration of surgery (p = 0.541), rate of delayed and non-union (p = 0.342), and rate of surgical site infections (p = 0.395). Conclusion: Intramedullary nailing of tibia shaft fractures with either solid or hollow nails have similar functional outcomes.
基金supported by the National Natural Science Foundation of China (21978253)the Fundamental Research Funds for the Central Universities (226-2022-00020, 226-2022-00055)。
文摘Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.
基金supported by the National Natural Science Foundation of China(51972066)the Natural Science Foundation of Guangdong Province of China(2021A1515011718)the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme 2017。
文摘Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heterostructure as a model and multifunctional catalyst modified on separators to induce interfacial charge modulation and expose more active sites for promoting the adsorption and catalytic conversion ability of sulfur species.Theoretical and experimental findings verify that the in-situ formed core-shell hetero-interface induces the formation of P-Co-O binding and charge redistribution to activate surface O active sites for binding lithium polysulfides(LiPSs)via strong Li-O bonding,thus strongly adsorbing with Li PSs.Meanwhile,the strong Li-O bonding weakens the competing Li-S bonding in LiPSs or Li2S adsorbed on CoO/CoP-Box surface,plus the hollow heterostructure provides abundant active sites and fast electron/Li+transfer,so reducing Li2S nucleation/dissolution activation energy.As expected,LSBs with CoO/CoP-Box modified separator and traditional sulfur/carbon black cathode display a large initial capacity of 1240 mA h g^(-1)and a long cycling stability with 300 cycles(~60.1%capacity retention)at 0.5C.Impressively,the thick sulfur cathode(sulfur loading:5.2 mg cm^(-2))displays a high initial areal capacity of 6.9 mA h cm^(-2).This work verifies a deep mechanism understanding and an effective strategy to induce interfacial charge modulation and enhance active sites for designing efficient dual-directional Li-S catalysts via engineering hollow core-shell hetero-structure.
基金financially supported by the National Natural Science Foundation of China(NSFC)(Grant Nos.22175007,21975007,52172080,and 22005012)the National Natural Science Foundation for Outstanding Youth Foundation,the Fundamental Research Funds for the Central Universities,the National Program for Support of Top-notch Young Professionalsthe 111 project(Grant No.B14009).
文摘The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high-performance energy storage devices.Here,we designed pea-like MoS_(2)@NiS_(1.03)-carbon hollow nanofibers using a simple electrospinning and thermal treatment method.The hierarchical hollow nanofiber is composed of a nitrogen-doped carbon-coated NiS_(1.03) tube wall,in which pea-like uniformly discrete MoS_(2) nanoparticles are enclosed.As a sodium-ion battery electrode material,the MoS_(2)@NiS_(1.03)-carbon hollow nanofibers have abundant diphasic heterointerfaces,a conductive network,and appropriate volume variation-buffering spaces,which can facilitate ion diffusion kinetics,shorten the diffusion path of electrons/ion,and buffer volume expansion during Na^(+)insertion/extraction.It shows outstanding rate capacity and long-cycle performance in a sodium-ion battery.This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long-life stability of sodium storage performance of electrode materials.
基金financially supported by the Shenzhen Science and Technology Program(JCYJ20220530141012028),ChinaThe National Natural Science Foundation of China(22005178),China+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01),ChianThe fellowship of China Postdoctoral Science Foundation(2022M722333),Chianthe Jiangsu Funding Program for Excellent Postdoctoral Talent,Chian。
文摘Hollow nanostructures with external shells and inner voids have been proved to greatly shorten the transport distance of ions/electrons and buffer volume change,especially for the large-sized potassium-ions in secondary batteries.In this work,hollow carbon(HC) nanospheres embedded with S,P co-doped NiSe_(2)nanoparticles are fabricated by "drop and dry" and "dissolving and precipitation" processes to form Ni(OH)2nanocrystals followed by annealing with S and P dopants to form nanoparticles.The resultant S,P-NiSe_(2)/HC composite exhibits excellent cyclic performance with 131.6 mA h g^(-1)at1000 mA g^(-1)after 3000 cycles for K^(+)storage and a capacity of 417.1 mA h g^(-1)at 1000 mA g^(-1)after1000 cycles for Li^(+)storage.K-ion full cells are assembled and deliver superior cycling stability with a ca pacity of 72.5 mA h g^(-1)at 200 mA g^(-1)after 500 cycles.The hollow carbon shell with excellent electrical conductivity effectively promotes the transporta tion and tolerates large volume variation for both K^(+)and Li^(+).Density functional theory calculations confirm that the S and P co-doping NiSe_(2) enables stronger adsorption of K^(+)ions and higher electrical conductivity that contributes to the improved electrochemical performance.
基金supported by the National Natural Science Foundation of China (2217600921906005)+3 种基金the Beijing Natural Science Foundation (8222064)the Bingtuan Science and Technology Program (2023CB008-21)the CNPC Innovation Foundation (2022DQ02-0406)the financial support from Beihang University。
文摘The development of efficient metal-zeolite bifunctional catalysts for catalytic fast pyrolysis(CFP) of biomass waste is highly desirable for bioenergy and renewable biofuel production.However,conventional metal-loaded zeolites often suffer from metal sintering during pyrolysis and are thus inactivated.In this study,single-site Ga-functionalized hollow ZSM-5(GaO_x@HS-Z5) was synthesized via an impregnationdissolution-recrystallization strategy without H_(2) reduction.The Ga atom was coordinated to four oxygen atoms in HS-Z5 frameworks.Benefitting from the highly dispersed single-Ga atoms and hollow zeolite framework,3GaO_x@HS-Z5 performed the best in producing hydrocarbon-rich bio-oil compared to impregnated 3GaO_x/HS-Z5 and H_(2)-reduced 3Ga@HS-Z5 in the maize straw CFP.In particular,3GaO_x@HS-Z5 delivered the highest bio-oil yield(23.6 wt%) and hydrocarbon selectivity(49.4 area%).3GaO_x@HS-Z5 also retained its structural integrity and catalytic activity after five pyrolysis-regeneration cycles,demonstrating its advantage in practical biomass CFP.The elimination of H_(2) reduction during the synthesis of catalyst provides an additional advantage for simplifying the CFP process and reducing operating costs.The retained Ga micro-environment and anti-sintering properties were unique for 3GaO_x@HS-Z5,as severe metal sintering occurred during pyrolysis for other metals(e.g.,NiO_x,ZnO_x,FeO_x,and CoO_x) that encapsulated HS-Z5.
基金financially supported by the Natural Science Foundation of Shandong Province,China(ZR2021QE192)the National Natural Science Foundation of China(21975154,22179078)+1 种基金the Postdoctoral Science Foundation of China(2018M63074)Qingdao Post-doctoral Applied Research Project(QDBSH20220202040)。
文摘Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.
基金the financial support from Dalian Institute of Chemical Physics (DMTO201604)Focus Area Innovation Team Support Plan of Dalian (2021RT03)+1 种基金National Natural Science Foundation of China (21878284)Regional Development Young Scholars of the Chinese Academy of Sciences。
文摘Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.
基金Funded by the National Natural Science Foundation of China(No.22002143)the Natural Science Foundation of Shanxi Province of China(No.201901D211223)the Postgraduate Students Scientific Research Project of North University of China(No.20201766)。
文摘The hollow strontium carbonate pompons was synthesized for the first time by a controlled reaction precipitation method with sodium dodecyl benzene sulfonate(SDBS)and polyvinyl pyrrolidone(PVP)work together as template.The sampled particles were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption measurement,X-ray diffraction(XRD),Energy dispersive X-Ray spectroscopy(EDX),Fourier transform infrared spectroscopy(FTIR),Thermogravimetric analysis and differential scanning calorimetry(TGA-DSC),etc.It is shown that the assynthesized hollow strontium carbonate pompons with the size of about 2μm consist of flake-like particles under the optimal reaction conditions.The formation mechanism of hollow strontium carbonate pompons was preliminarily explored.
基金financial supported by the National Natural Science Foundation of China(51572202)the National Nature Science Foundation of Jiangsu Province(BK20221259)Duozhu Technology(Wuhan)Co.,Ltd.
文摘Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are limited by the excessive expansion rate and low intrinsic conductivity.Herein,heterogeneous hollow sphere NiS-Cu_(9)S_(5)/NC(labeled as(NiCu)S/NC)based on Oswald ripening mechanism was prepared through a simple and feasible methodology.From a structural perspective,the hollow structure provides an expansion buffer and raises the electrochemical active area.In terms of electron/ion during the cycles,Na^(+)storage mechanism is optimized by NiS/Cu_(9)S_(5)heterogeneous interface,which increases the storage sites and shortens the migration path of Na^(+).The formation of built-in electric field strengthens the electron/ion mobility.Based on the first principle calculations,it is further proved the formation of heterogeneous interfaces and the direction of electron flow.As the anode for SIBs,the synthesized(NiCu)S/NC delivers high reverse capacity(559.2 mA h g^(-1)at 0.5 A g^(-1)),outstanding rate performance(185.3 mA h g^(-1)at 15 A g^(-1)),long-durable stability(342.6 mA h g^(-1)at 4 A g^(-1)after 1500cycles,150.0 m A h g^(-1)at 10 A g^(-1)after 20,000 cycles with 0.0025%average attenuation rate).The matching cathode electrode Na_(3)V_(2)(PO_(4))_(3)/C is assembled with(NiCu)S/NC for the full-battery that achieves high energy density(253.7 W h kg^(-1))and reverse capacity(288.7 mA h g^(-1)).The present work provides a distinctive strategy for constructing electrodes with excellent capacity and stability for SIBs.
基金supported by the China Postdoctoral Science Foundation(Nos.2021M690534 and 2020M673650)the Science and Technology Research Program of Chongqing Municipal Education Commission(Nos.KJQN202101439 and KJQN202101441)+1 种基金the Innovation Research Team at Institutions of Higher Education in Chongqing(No.CXQT20027)the Program for Vanadium and Titanium Resource Comprehensive Utilization Key Laboratory of Sichuan Province(No.2022FTSZ02)。
文摘Achieving high-efficiency sodium storage in metal selenides is still severely constrained in consideration of their inferior electronic conductivity and inadequate Na^(+)insertion pathways and active sites.Heteroatom doping accompanied by spontaneously developed lattice defects can effectively tune electronic structure of metal selenides,which give a strong effect to motivate fast charge transfer and Na^(+)accessibility.Herein,we finely designed and successfully constructed a fascinating phosphorus-doped Cu_(2)Se@C hollow nanosphere with abundant vacancy defects(Cu_(2)P_(x)Se_(1-x)@C)through a combination strategy of selenization of Cu_(2)O nanosphere template,self-polymerization of dopamine,and subsequent phosphorization treatment.Such exquisite composite possesses enriched active sites,superior conductivity,and sufficient Na^(+)insertion channel,which enable much faster Na^(+)diffusion rates and more remarkable pseudocapacitive features,Satisfyingly,the Cu_(2)P_(x)Se_(1-x)@C composites manifest the supernormal sodium-storage capabilities,that is,a reversible capacity of 403.7 mA h g^(-1) at 1.0 A g^(-1) over 100 cycles,and an ultrastable cyclic lifespan over 1000 cycles at 20.0 A g^(-1) with a high capacity-retention of about249.7 mA h g^(-1).The phase transformation of the Cu_(2)P_(x)Se_(1-x)@C involving the intercalation of Na^(+)into Cu_(2)Se and the following conversion of NaCuSe to Cu and Na2Se were further demonstrated through a series of ex-situ characterization methods.DFT results demonstrate that the coexistence of phosphorusdoping and vacancy defects within Cu_(2)Se results in the reduction of Na^(+)adsorption energy from-1.47to-1.56 eV improving the conductivity of Cu_(2)Se to further accelerate fast Na^(+)mobility.
基金supported by the National Natural Science Foundation of China (21972124, 22272148)the Priority Academic Program Development of Jiangsu Higher Education Institution。
文摘The strong metal-support interaction inducing combined effect plays a crucial role in the catalysis reaction. Herein, we revealed that the combined advantages of MoSe_(2), Ru, and hollow carbon spheres in the form of Ru nanoparticles(NPs) anchored on a two-dimensionally ordered MoSe_(2) nanosheet-embedded mesoporous hollow carbon spheres surface(Ru/MoSe_(2)@MHCS) for the largely boosted hydrogen evolution reaction(HER) performance. The combined advantages from the conductive support, oxyphilic MoSe_(2), and Ru active sites imparted a strong synergistic effect and charge redistribution in the Ru periphery which induced high catalytic activity, stability, and kinetics for HER. Specifically, the obtained Ru/MoSe_(2)@MHCS required a small overpotential of 25.5 and 38.4 mV to drive the kinetic current density of 10 mA cm^(-2)both in acid and alkaline media, respectively, which was comparable to that of the Pt/C catalyst. Experimental and theoretical results demonstrated that the charge transfer from MoSe_(2) to Ru NPs enriched the electronic density of Ru sites and thus facilitated hydrogen adsorption and water dissociation. The current work showed the significant interfacial engineering in Ru-based catalysts development and catalysis promotion effect understanding via the metal-support interaction.
基金supported by the Natural Science Foundation of the Shanxi Province of China(No.201801D121069)Graduate Education Innovation Foundation of Province Shanxi of China(No.2020SY359)。
文摘The loading strategy of cocatalysts affects its activity exerting and atom utilization.Here,a novel strategy for loading precious metal(Pt)cocatalysts by means of ultrathin N-doped carbon layer is reported.The strategy is based on a pyrolysis process of predesigned N-containing polymers and Pt complexes on hard-template surface,during which Pt can be reduced by carbon from pyrolysis at high temperatures.Finally,the hollow TiO_(2)composite with stable and dispersed Pt on its inner surface was prepared.It shows an ultrahigh photocatalytic H_(2)production activity as high as 25.7 mmol h^(-1)g^(-1)with methanol as sacrificial regent,and displays an apparent quantum yield as 13.2%.The improved photocatalytic activity and stability can be attributed to the highly dispersed and ultrafine Pt nanoparticles,enhanced interaction between Pt-species and carbon support,fast photo-excited electron transport from the high graphitization degree of NC layers,ample oxygen vacancies/defects,as well as the manipulated local charge distribution of Pt/NC-layer configuration.Additionally,the universality of the proposed strategy was demonstrated by replacing metal sources(such as,Ru and Pd).This work presented a promising strategy for the design and development of novel photocatalysts,which shows a broad application prospect.
基金Funded by the Project of Sanya Yazhou Bay Science and Technology City (No.SCKJ-JYRC-2022-44)the Opening Funding of the State Key Laboratory of Silicate Materials for Architecture (SySJJ2018-06)+1 种基金the Fundamental Research Funds for the Central Universities (WUT:2016VA096),Chinathe Research Program (No.S2634339)through a Grant Provided by the Ministry of SMEs and Startups。
文摘Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.
基金the support from the National Key Research and Development Program of China(2021YFB3801301)the National Natural Science Foundation of China(22075076,21908098,and 21908054)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.
基金Ministry of Trade,Industry&Energy of Korea,Grant/Award Number:RS‐2022‐00155717National Research Foundation of Korea,Grant/Award Numbers:2020H1D3A1A04081472,2022M3J1A1054323。
文摘Carbon super-heterostructures with high nitrogen contents from the covalent hybrid precursors of covalent triazine frameworks(CTFs)and zeolitic imidazolic frameworks(ZIFs)are scarcely explored because of CTF's ordered structure and toxic superacid that dissolves or destabilizes the metal nodes.To solve this problem,herein,we report a straightforward two-step pathway for the covalent hybridization of disordered CTF(d–CTF)–ZIF composites via preincorporation of an imidazole(IM)linker into ordered CTFs,followed by the imidazole-site-specific covalent growth of ZIFs.Direct carbonization of these synthesized d–CTF−IM−ZIF hybrids results in unique hollow carbon super-heterostructures with ultrahigh nitrogen content(>18.6%),high specific surface area(1663m^(2)g^(−1)),and beneficial trace metal(Co/Zn NPs)contents for promoting the redox pseudocapacitance.As proof of concept,the obtained carbon super-heterostructure(Co–Zn–NC_(SNH)–800)is used as a positive electrode in an asymmetric supercapacitor,demonstrating a remarkable energy density of 61Wh kg^(−1)and extraordinary cyclic stability of 97%retention after 30,000 cycles at the cell level.Our presynthetic modifications of CTF and their covalent hybridization with ZIF crystals pave the way toward new design strategies for synthesizing functional porous carbon materials for promising energy applications.
