Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typical...Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typically evaluated by a dimensionless figure of merit (ZT = S2σT/(κe+ κl)), which depends on the delicate interplay among the electrical conductivity (σ), Seebeck coefficient (S), lattice thermal conductivity (κl), and electronic thermal conductivity (κe) [4].展开更多
Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible s...Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.展开更多
V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve th...V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.展开更多
Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalyti...Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].展开更多
Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chlori...Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an imp...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.展开更多
Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performa...Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.展开更多
Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In...Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.展开更多
MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties en...MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.展开更多
We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an...We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.展开更多
Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The met...Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.展开更多
Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pell...Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pellets.Addressing the gap in the application of organically-intercalated modified bentonite in the pelletizing field,this study introduces an innovative modification process for bentonite that employs the synergistic effect of mechanical force and dimethyl sulfoxide to enhance the intercalation of organic compounds within bentonite,thus significantly enhancing its binding performance.The colloid value and swell capacity of modified bentonite(98.5 m L/3g and 55.0 m L/g)were much higher than the original bentonite(90.5 m L/3g and 17.5 m L/g).With the decrease of bentonite dosage from1.5wt%to 1.0wt%,the drop number of green pellets from a height of 0.5 m and the compressive strengths of roasted pellets using the modified bentonite(6.0 times and 2916 N per pellet)were significantly higher than those of the original bentonite(4.0 times and 2739 N per pellet).This study provides a comprehensive analysis of the intercalation modification mechanism of bentonite,offering crucial technical insights for the development of high-performance modified bentonite as iron ore pellet binders.展开更多
Sodium bis[N-2-oxyphenyl-5-substituted-salicylideneiminato-ONO]ruthenate（Ⅲ） hemitriethylamine compounds of general formula Na[Ru（N-R-5-X-salim）2]＇0.5Et3N, where, R = C6H40, X = El, Br, NO2, salim = salicylidenei...Sodium bis[N-2-oxyphenyl-5-substituted-salicylideneiminato-ONO]ruthenate（Ⅲ） hemitriethylamine compounds of general formula Na[Ru（N-R-5-X-salim）2]＇0.5Et3N, where, R = C6H40, X = El, Br, NO2, salim = salicylideneiminato, Et3N triethylamine, were synthesized and characterized on the basis of elemental analysis, MALDI-TOF （matrix-assisted laser desorption/ionization/time-of-flight） mass spectra, IH NMR （nuclear magnetic resonance）, electronic spectra and cyclic voltammograms. Ru（Ⅲ） is chelated with two O2N anionic tridentate Schiff bases derived from 5-X-salicyladehyde and 2-aminophenol. Spectroscopic titrations of the Ru（Ⅲ） compounds with CT DNA （calf thymus DNA） in the LMCT （ligand metal charge transfer） region have shown moderate intercalation properties of compounds with binding constants KD = 2.06-3.85 × 104 Ml. Electrochemical evidence of intercalative mode of binding is based on the decrease of current and shift of anodic and cathodic peaks towards higher values of potential with IxL-increment of CT DNA in Ru（Ⅲ） compound solution.展开更多
A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of allo...A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.展开更多
Neural tube defects （NTDs） are severe congenital malformation diseases, which occur in 1 out of 1000 births in human. In Xenopus, several tissue movements are involved in the neural tube closure process. Immediately...Neural tube defects （NTDs） are severe congenital malformation diseases, which occur in 1 out of 1000 births in human. In Xenopus, several tissue movements are involved in the neural tube closure process. Immediately after the neural tube fusion, the neural crest cells get monopolar protrusion toward dorsal midline and migrate to form the roof of the neural tube. At the same time, radial intercalation takes place from the ventral neural tube and forces it to be single-layered. Here, we physically block the neural tube closure to test the cell movements and the following patterning in Xenopus laevis explants. The results show that the single-layered neural tube fails to form and the neural crest cells remain at the lateral regions in the explants with NTDs. However, the patterning of the neural tube is not affected as indicated by the normal expression of the preneural genes. These results indicate a requirement of the neural tube fusion for the radial intercalation and the dorsal midline directed neural crest migration, but not for the dorsal-ventral patterning of the neural tube.展开更多
Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG ...Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.展开更多
Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Here...Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.展开更多
A gelatin/MMT nanocomposite was prepared in an aqueous solution and investigated by XRD,FTIR and 13 C NMR,and then the intercalation mechanism was discussed.The result of XRD indicated that the gelatin molecule...A gelatin/MMT nanocomposite was prepared in an aqueous solution and investigated by XRD,FTIR and 13 C NMR,and then the intercalation mechanism was discussed.The result of XRD indicated that the gelatin molecule had already inserted into the interlayer of MMT,and the intercalation or exfoliation structure had been achieved.The result of 13 C NMR demonstrated that the ions interaction between gelatin and MMT was attributed to the driving force for intercalation.In order to confirm the role of -COO - of gelatin in the combination with MMT,lauric sodium was brought in as a model to react with MMT,and was characterized by XRD and FTIR,the result proved that there existed a kind of strong interaction between -COO - and ions of MMT.展开更多
基金supports from the Department of Education of Liaoning Province (LJ242510147006)
文摘Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typically evaluated by a dimensionless figure of merit (ZT = S2σT/(κe+ κl)), which depends on the delicate interplay among the electrical conductivity (σ), Seebeck coefficient (S), lattice thermal conductivity (κl), and electronic thermal conductivity (κe) [4].
基金financially supported by the supported by Shandong Provincial Natural Science Foundation(ZR2024MB108)Taishan Young Scholar Program(tsqn202312312)Excellent Young Scholars of the Shandong Provincial Natural Science Foundation(Overseas)(2023HWYQ-112)。
文摘Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.
文摘V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.
文摘Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].
基金financial support from the National Natural Science Foundation of China(52372173,52072034)。
文摘Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.
基金financially supported by the National Natural Science Foundation of China(Nos.22435005,22193042,21921001,52202194,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBSLY-SLH024)。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.
基金supported by the National Key R&D Program of China(2022YFA1203400)the National Natural Science Foundation of China(W2441009)。
文摘Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.
基金funded by the National Natural Science Foundation of China(Nos.22179098 and 22209153).
文摘Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.
基金supported by the National Key Research and Development Program of China(Grant Nos.2022YFA1402404 and 2023YFA1406304)the National Natural Science Foundation of China(Grant Nos.92161201,T2221003,12104221,12104220,12274208,12025404,12004174,91961101,T2394473,62274085,12374043,and U2032208)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20230079,BK20243013,and BK20233001)the Fundamental Research Funds for the Central Universities(Grant Nos.020414380192 and 2024300432).
文摘MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.
基金supported by the National Natural Science Foundation of China(Grant Nos.22090042 and 22175018).
文摘We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.
基金supported by the International Science & Technology Cooperation Program of China(2010DFB63680)the National Natural Science Foundation of China(21376220)Zhejiang Provincial Natural Science Foundation of China(LY16B060009,LY12B03008)~~
文摘Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.
基金financial support by the National Key Research and Development Program of China(No.2023YFC2907801)the Hunan Provincial Natural Science Foundation of China(No.2023JJ40760)the Scientific and Technological Project of Yunnan Precious Metals Laboratory,China(No.YPML-2023050276)。
文摘Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pellets.Addressing the gap in the application of organically-intercalated modified bentonite in the pelletizing field,this study introduces an innovative modification process for bentonite that employs the synergistic effect of mechanical force and dimethyl sulfoxide to enhance the intercalation of organic compounds within bentonite,thus significantly enhancing its binding performance.The colloid value and swell capacity of modified bentonite(98.5 m L/3g and 55.0 m L/g)were much higher than the original bentonite(90.5 m L/3g and 17.5 m L/g).With the decrease of bentonite dosage from1.5wt%to 1.0wt%,the drop number of green pellets from a height of 0.5 m and the compressive strengths of roasted pellets using the modified bentonite(6.0 times and 2916 N per pellet)were significantly higher than those of the original bentonite(4.0 times and 2739 N per pellet).This study provides a comprehensive analysis of the intercalation modification mechanism of bentonite,offering crucial technical insights for the development of high-performance modified bentonite as iron ore pellet binders.
文摘Sodium bis[N-2-oxyphenyl-5-substituted-salicylideneiminato-ONO]ruthenate（Ⅲ） hemitriethylamine compounds of general formula Na[Ru（N-R-5-X-salim）2]＇0.5Et3N, where, R = C6H40, X = El, Br, NO2, salim = salicylideneiminato, Et3N triethylamine, were synthesized and characterized on the basis of elemental analysis, MALDI-TOF （matrix-assisted laser desorption/ionization/time-of-flight） mass spectra, IH NMR （nuclear magnetic resonance）, electronic spectra and cyclic voltammograms. Ru（Ⅲ） is chelated with two O2N anionic tridentate Schiff bases derived from 5-X-salicyladehyde and 2-aminophenol. Spectroscopic titrations of the Ru（Ⅲ） compounds with CT DNA （calf thymus DNA） in the LMCT （ligand metal charge transfer） region have shown moderate intercalation properties of compounds with binding constants KD = 2.06-3.85 × 104 Ml. Electrochemical evidence of intercalative mode of binding is based on the decrease of current and shift of anodic and cathodic peaks towards higher values of potential with IxL-increment of CT DNA in Ru（Ⅲ） compound solution.
基金the National Nature Science Foundation of China (Nos. 50771046 and 20373016) the Natural Science Foundation of Guangdong Province (No. 05200534)the Key Projects of Guangdong Province and Guangzhou City, China (Nos. 2006A10704003 and 2006Z3-D2031)
文摘A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.
基金supported by grants from the National Natural Science Foundation of China (30425011 30530380)the Innovation Project of the Chinese Academy of Sciences (KSCX2-YW-R-090)~~
文摘Neural tube defects （NTDs） are severe congenital malformation diseases, which occur in 1 out of 1000 births in human. In Xenopus, several tissue movements are involved in the neural tube closure process. Immediately after the neural tube fusion, the neural crest cells get monopolar protrusion toward dorsal midline and migrate to form the roof of the neural tube. At the same time, radial intercalation takes place from the ventral neural tube and forces it to be single-layered. Here, we physically block the neural tube closure to test the cell movements and the following patterning in Xenopus laevis explants. The results show that the single-layered neural tube fails to form and the neural crest cells remain at the lateral regions in the explants with NTDs. However, the patterning of the neural tube is not affected as indicated by the normal expression of the preneural genes. These results indicate a requirement of the neural tube fusion for the radial intercalation and the dorsal midline directed neural crest migration, but not for the dorsal-ventral patterning of the neural tube.
文摘Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.
基金financial support provided by the National Natural Science Foundation of China(No.51932005)Liao Ning Revitalization Talents Program(XLYC1807175)+4 种基金the Joint Research Fund Liaoning Shenyang National Laboratory for Materials Science(SYNL)(20180510047)the Research Fund of SYNL(L2019F38)the Youth Innovation Promotion Association CAS(2015152)the Program for the Development of Science and Technology of Jilin Province(No.20190201309JC)the Project of Development and Reform Commission of Jilin Province(No.2019C042-1)。
文摘Although MXenes is highly attractive as anode materials of lithium ion batteries,it sets a bottleneck for higher capacity of the V2CTxMXene due to the limited interlayer space and the derived surface terminations.Herein,the cation intercalation and ion-exchange were well employed to achieve a K+and Ca2+intercalated V2CTxMXene.A larger interlayer distance and low F surface terminations were thereof obtained,which accelerates the ion transport and promotes the delicate surface of V2CTx MXene.As a result,a package of enhanced capacity,rate performance and cyclability can be achieved.Furthermore,the ion exchange approach can be extended to other 2 D layered materials,and both the interlayer control and the surface modification will be achieved.
文摘A gelatin/MMT nanocomposite was prepared in an aqueous solution and investigated by XRD,FTIR and 13 C NMR,and then the intercalation mechanism was discussed.The result of XRD indicated that the gelatin molecule had already inserted into the interlayer of MMT,and the intercalation or exfoliation structure had been achieved.The result of 13 C NMR demonstrated that the ions interaction between gelatin and MMT was attributed to the driving force for intercalation.In order to confirm the role of -COO - of gelatin in the combination with MMT,lauric sodium was brought in as a model to react with MMT,and was characterized by XRD and FTIR,the result proved that there existed a kind of strong interaction between -COO - and ions of MMT.
