Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transpo...Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transport in topological devices.The presence of these carriers in real materials strongly depends on the Fermi-level position.2M-WSe_(2),with its topological and van der Waals nature,serves as an ideal platform for studying quantum transport in two-dimensional systems,despite the fact that interlayer coupling suppresses the formation of light carriers.In this study,we solvothermally intercalate 1,3-diaminopropane molecules into the interlayer space of 2M-WSe_(2);these molecules effectively adapt to the electronic structure by eliminating interlayer coupling.Simultaneously,slight electron doping via charge transfer results in a small Fermi pocket with an extremely light effective mass,0.04–0.06 me,as revealed by quantum oscillation measurements.This study demonstrates that molecular intercalation is an effective approach for engineering van der Waals topological materials to achieve specific quantum transport properties.展开更多
The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNT...The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).展开更多
Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs ...Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs their functionality by reducing active sites and obstructing ionic transport.This study presents a facile synthesis approach for nickel-intercalated MXene,designed to enhance surface reactivity,avoid restacking,and achieve improved electrochemical performance.Electrochemical studies revealed that the nickel-MXene hybrid showed better cycling stability,retaining 83.7%of its capacity after 10000 cycles and attaining an energy density of 26 Wh kg^(-1) at a power density of 1872Wkg^(-1).It also exhibited overpotentials of 109 and 482 mV at 10 and 100 mA cm^(-2),respectively,in the hydrogen evolution reaction.To predict the structural and electrical alterations caused by nickel inclusion,as well as to understand the intercalation mechanism,spin-polarized density functional theory calculations were carried out.The theoretical results showed an improved carrier concentration for nickel-MXene.Nickel-MXene possessed superior electronic characteristics and surplus active sites with hexagonal closed-packed(hcp)edge sites,which enhanced electrochemical properties.Our results demonstrate that nickel intercalation prevents the restacking of MXene but also significantly improves their electrochemical characteristics,making them ideal for energy storage and catalytic applications.展开更多
The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of ...The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.展开更多
Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existen...Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.展开更多
The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from ...The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from their highly tunable properties.In this article,the influence of Fe intercalation in NbSe_(2)was elaborately investigated using a combination of techniques.Magnetic studies have shown that the insertion of Fe atoms induces an antiferromagnetic state in which the easy axis aligns out of the plane.The sign reversal of the magnetoresistance across the Neel temperature can be satisfactorily explained by the moderate interaction between electrons and local spins.The Hall and Seebeck measurements reveal a multi-band nature,and the contribution of various phonon scattering processes is discussed based on the thermal conductivity and specific heat data.展开更多
Naproxen （Nap）, a non-steroidal anti-inflammatory drug （NSAIDs）, was intercalated into the gallery of Mg-A1 layered double hydroxides （LDHs） by ion exchange and co-precipitation with different location of magnes...Naproxen （Nap）, a non-steroidal anti-inflammatory drug （NSAIDs）, was intercalated into the gallery of Mg-A1 layered double hydroxides （LDHs） by ion exchange and co-precipitation with different location of magnesium ion and aluminum ion solutions, respectively. The product was characterized with powder X-ray diffraction （XRD）, Fourier Transform Infrared spectral （FT-IR） and Thermogravimetry （TG）. The results showed an expanded LDH structure, indicating that the drug was successfully intercalated into LDH with the monolayer perpendicular to （along the short axis orientation in proper angle） Nap anion. As compared to the pure form of Nap, the thermal stability of the intercalated Nap was significantly enhanced due to the host-vip interaction involving hydrogen bond and electrostatic attraction. We further investigated the drug release characteristics of the pillared LDH materials by a dissolution test in simulation gastrointestinal and intestinal fluids under different pH values. The results indicated that the release percentages decrease upon increasing pH from 4.60 to 7.43, likely due to the dependence of release mechanism on pH. We have carded out a kinetic simulation to the release data and found that the dissolution mechanism was mainly responsible for the release behavior of Nap-LDHs at pH 4.60, while the ion-exchange mechanism was responsible for that at pH 7.43. In addition, the initial release rates and equilibrium percent releases of the nanohybrids depended significantly on the synthesis methods, from which we have proposed a schematic model. The current study clearly showed that this drug-inorganic layered material has prospective applications in drug delivery system.展开更多
Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabl...Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.展开更多
Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion ...Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.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
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
Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herei...Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herein,we engineer tetraethylammonium(TEA)cation intercalation as a dual-function strategy that concurrently enables interlayer distance enlargement and electrostatic shielding effects,resolving Al^(3+) polarization-induced sluggish kinetics and cathode degradation in RABs.TEA intercalation triggers exceptional V2O5 interlayer expansion from 4.37 to 13.10Å,while the modulated charge distribution generates an electrostatic shielding effect that significantly weakens the Coulombic interactions between Al^(3+) and V2O5 frameworks.This dual mechanism collectively enhances ion diffusion kinetics and suppresses lattice stress accumulation.Ex situ X-ray diffraction and transmission electron microscopy analyses confirm that the“molecular pillar effect”of TEA enables minimal and highly reversible structural deformation of the cathode(<2.0%volume change after 200 cycles),demonstrating zero-strain aluminum-storage behavior.The optimized cathode delivers a high reversible capacity of 258 mAh g^(−1) at 0.5 A g^(−1),maintains 99%capacity retention at 5.0 A g^(−1),and exhibits an ultralow capacity decay rate of 0.01%per cycle over 6000 cycles.This work opens new pathways for designing stable high-performance RAB cathodes through synergistic modulation of electronic and lattice structures.展开更多
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
As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode mate...As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode materials undergo complex ion intercalation and deintercalation processes,accompanied by defect formation and structural evolution.However,the microscopic mechanisms underlying processes such as cation disordering,lattice oxygen loss,and stage structure formation are still not fully understood.To address these challenges,we have developed the Electrode Dynamic Ion Intercalation/Deintercalation Simulator(EDIS),a software platform designed to simulate the dynamic processes of ion intercalation and deintercalation in electrode materials.Leveraging high-precision machine learning potentials,EDIS can efficiently model structural evolution and lithium-ion diffusion behavior under various states of charge and discharge,achieving accuracy approaching that of quantum mechanical methods in relevant chemical spaces.The software supports quantitative analysis of how variations in lithium-ion concentration and distribution affect lithium-ion transport properties,enables evaluation of the impact of structural defects,and allows for tracking of both structural evolution and transport characteristics during continuous cycling.EDIS is versatile and can be extended to sodium-ion batteries and related systems.By enabling in-depth analysis of these microscopic processes,EDIS provides a robust theoretical tool for mechanistic studies and the rational design of high-performance electrode materials for next-generation lithium-ion batteries.展开更多
Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge t...Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge towards efficient DCBs.Here,we introduce a heteroatom-doped sp^(3) /sp^(2) hybridized carbon fiber membrane(cPAN-Gr)as a universal binder-free active electrode that effectively overcomes this trade-off,enabling efficient Li-ion intercalation chemistry for advanced DCBs.By strategically tuning the sp^(3) and sp^(2) carbon hybridization,the interlayer interaction,geometric and electronic structures of c PANGr are simultaneously optimized,which facilitates rapid Li-ion adsorption,smooth interlayer transport,and efficient electron transport by maximizing the synergy between sp^(2) -and sp^(3) -hybridized carbon.This,coupled with a 3D porous network structure,endows the c PAN-Gr with superior Li-ion storage capability and fast reaction kinetics.Therefore,the c PAN-Gr electrode delivers a high reversible capacity of 345 m A h g^(-1),excellent rate capability(50 C),and an ultralong cycle life over 10,000 cycles,outperforming other reported carbon-based electrodes.Moreover,the constructed DCB exhibits a large specific capacity of 135 m A h g^(-1),long-term cyclability over 500 cycles,and a remarkable energy density of 524.4 Wh kg^(-1).The c PAN-Gr electrode can also be expanded to construct a LiFePO_(4)//cPAN-Gr full battery.Combined theoretical and experimental studies reveal the crucial role of an optimized sp^(3) /sp^(2) ratio(79%)with topological defects and pyridine/pyrrolic N sites on the performance enhancement.This work offers new insights into the design of advanced carbon materials for DCBs and beyond.展开更多
基金supported by the National Key Research and Development Program of China (Grant No.2023YFA1406301)the National Natural Science Foundation of China (Grant Nos.52250308 and 52525205)。
文摘Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transport in topological devices.The presence of these carriers in real materials strongly depends on the Fermi-level position.2M-WSe_(2),with its topological and van der Waals nature,serves as an ideal platform for studying quantum transport in two-dimensional systems,despite the fact that interlayer coupling suppresses the formation of light carriers.In this study,we solvothermally intercalate 1,3-diaminopropane molecules into the interlayer space of 2M-WSe_(2);these molecules effectively adapt to the electronic structure by eliminating interlayer coupling.Simultaneously,slight electron doping via charge transfer results in a small Fermi pocket with an extremely light effective mass,0.04–0.06 me,as revealed by quantum oscillation measurements.This study demonstrates that molecular intercalation is an effective approach for engineering van der Waals topological materials to achieve specific quantum transport properties.
基金the financial support from the National Natural Science Foundation of China(No.22178307)China Southern Power Grid(Grant Nos.0470002022030103HX00002-01).
文摘The poor electronic conductivity of metal-organic framework(MOF)materials hinders their direct application in the field of electrocatalysis in fuel cells.Herein,we proposed a strategy of embedding carbon nanotubes(CNTs)during the growth process of MOF crystals,synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure.Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin.Simultaneously,the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency.X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT changed the electron cloud density on the catalytic active center Co,optimizing the electronic structure.Consequently,the E_(1/2) of the TCPPCo-MOF-CNT catalyst under neutral conditions reached 0.77 V(vs.RHE),outperforming the catalyst without CNTs.When the TCPPCo-MOF-CNT was employed as the cathode catalyst in assembling microbial fuel cells(MFCs)with Nafion-117 as the proton exchange membrane,the maxi-mum power density of MFCs reached approximately 500 mW·m^(-2).
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF-2020R1A6A1A03043435 and NRF-2021R1A2C1008798).
文摘Two-dimensional MXenes are renowned for their remarkable electrical conductivity and electrochemical activity making them highly promising for electrode applications.However,the restacking of MXene nanosheets impairs their functionality by reducing active sites and obstructing ionic transport.This study presents a facile synthesis approach for nickel-intercalated MXene,designed to enhance surface reactivity,avoid restacking,and achieve improved electrochemical performance.Electrochemical studies revealed that the nickel-MXene hybrid showed better cycling stability,retaining 83.7%of its capacity after 10000 cycles and attaining an energy density of 26 Wh kg^(-1) at a power density of 1872Wkg^(-1).It also exhibited overpotentials of 109 and 482 mV at 10 and 100 mA cm^(-2),respectively,in the hydrogen evolution reaction.To predict the structural and electrical alterations caused by nickel inclusion,as well as to understand the intercalation mechanism,spin-polarized density functional theory calculations were carried out.The theoretical results showed an improved carrier concentration for nickel-MXene.Nickel-MXene possessed superior electronic characteristics and surplus active sites with hexagonal closed-packed(hcp)edge sites,which enhanced electrochemical properties.Our results demonstrate that nickel intercalation prevents the restacking of MXene but also significantly improves their electrochemical characteristics,making them ideal for energy storage and catalytic applications.
基金financially supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJQN202300759)the Vanadium Titanium Materials Engineering Technology Research Center Foundation Project of Sichuan(No.2022FTGC07)+5 种基金the National Key R&D Program of China(No.2023YFC3009500)the National Natural Science Foundation of China(No.22379103)the Science and Technology Projects of Suzhou City(No.SYC2022043)the Campus Science Fund Project of Chongqing Jiaotong University(Nos.2020020086 and 2020023032)the Graduate Tutor Team Construction Project of Chongqing(No.JDDSTD2022006)the Graduate Student Research Innovation Project of Chongqing(No.2024S0110)
文摘The issue of water molecule activity in aqueous zinc-ion batteries presents a significant challenge.During the charging and discharging process,the strong polarity of water molecules tends to cause the dissolution of cathode materials,which reduces the cycle stability and specific capacity,consequently limiting the practical application of zinc-ion batteries.In this work,hydroxypropylβ-cyclodextrin(HP-β-CD),a special stereo cyclic organic molecule with hydrophobic inner cavity and hydrophilic outer cavity,is used as the intercalator for hydrated vanadium oxide(VOH)to enlarge the layer spacing and enhance the hydrophobicity of the cathode material.The larger interlayer spacing(13.9Å)of HP-β-CD-VOH is beneficial for improving ion mobility and the intrinsic electrochemical reaction kinetics.HP-β-CD-VOH delivers a discharge capacity of 336.7 mAh g^(-1)at 0.2 A g^(-1)and high-rate capability(242 mAh g^(-1)at 5 A g^(-1)).Due to the hydrophobic property of HP-β-CD in the interlayer pillar,the vanadium dissolution effect of polar water molecules can be reduced during charge and discharge;HP-β-CDVOH demonstrates sustained high efficiency and extended cycle longevity,maintaining a remarkable durability of 6000 cycles at a current density of 10 A g^(-1).This study presents an effective strategy for developing high-performance aqueous zinc-ion battery cathode materials.
基金supported by the National Natural Science Foundation of China(22075196,U22A20418,21878204)the Research Project Supported by Shanxi Scholarship Council of China(2022-050).
文摘Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction(OER)electrocatalysts in the form of oxyhydroxides through electrochemical activation.However,the role and existence form of leached oxygen anions are still controversial.Herein,we selected iron selenite-wrapped hydrated nickel molybdate(denoted as NiMoO/FeSeO)as a pre-catalyst to study the oxyanion effect.It is surprising to find that SeO_(2)-exists in the catalyst in the form of intercalation,which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation,or adsorbed on the catalyst surface.The experiment and theoretical calculations show that the existence of SeO_(4)^(2-)intercalation effectively adjusts the electronic structure of NiFeOOH,promotes intramolecular electron transfer and O-O release,and thus lowers the reaction energy barrier.As expected,the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm^(-2)in 1 M KOH.Further,the anion exchange membrane water electrolyzer(AEMWE)consisting of NiFeOOHSeO anode and Pt/C cathode can reach 1 A cm^(-2)at 1.70 V and no significant attenuation within 300 h.Our findings provide insights into the mechanism,by which the intercalated oxyanions enhance the OER performance of NiFeOOH,thereby facilitating large-scale hydrogen production through AEMWE.
基金Project supported by the National Natural Science Foundation of China(Grant No.12274440)the National Key R&D Program of China(Grant No.2022YFA1403903)+1 种基金the Strategic Priority Research Program(B)of the Chinese Academy of Sciences(Grant No.XDB33010100)the Fund of the Synergetic Extreme Condition User Facility(SECUF)。
文摘The interaction between charge and spin degrees of freedom has always been the central issue of condensed matter physics,and transition metal dichalcogenides(TMDs)provide an ideal platform to study it benefiting from their highly tunable properties.In this article,the influence of Fe intercalation in NbSe_(2)was elaborately investigated using a combination of techniques.Magnetic studies have shown that the insertion of Fe atoms induces an antiferromagnetic state in which the easy axis aligns out of the plane.The sign reversal of the magnetoresistance across the Neel temperature can be satisfactorily explained by the moderate interaction between electrons and local spins.The Hall and Seebeck measurements reveal a multi-band nature,and the contribution of various phonon scattering processes is discussed based on the thermal conductivity and specific heat data.
基金Science and Technique Foundation of Xi'an City (Grant No.YF07058)
文摘Naproxen （Nap）, a non-steroidal anti-inflammatory drug （NSAIDs）, was intercalated into the gallery of Mg-A1 layered double hydroxides （LDHs） by ion exchange and co-precipitation with different location of magnesium ion and aluminum ion solutions, respectively. The product was characterized with powder X-ray diffraction （XRD）, Fourier Transform Infrared spectral （FT-IR） and Thermogravimetry （TG）. The results showed an expanded LDH structure, indicating that the drug was successfully intercalated into LDH with the monolayer perpendicular to （along the short axis orientation in proper angle） Nap anion. As compared to the pure form of Nap, the thermal stability of the intercalated Nap was significantly enhanced due to the host-vip interaction involving hydrogen bond and electrostatic attraction. We further investigated the drug release characteristics of the pillared LDH materials by a dissolution test in simulation gastrointestinal and intestinal fluids under different pH values. The results indicated that the release percentages decrease upon increasing pH from 4.60 to 7.43, likely due to the dependence of release mechanism on pH. We have carded out a kinetic simulation to the release data and found that the dissolution mechanism was mainly responsible for the release behavior of Nap-LDHs at pH 4.60, while the ion-exchange mechanism was responsible for that at pH 7.43. In addition, the initial release rates and equilibrium percent releases of the nanohybrids depended significantly on the synthesis methods, from which we have proposed a schematic model. The current study clearly showed that this drug-inorganic layered material has prospective applications in drug delivery system.
基金supported by the National KeyR&D Program of China(Grant No.2024YFB3817400)the National Natural Science Foundation of China(Grants No.12274276 and No.U24A6002)+1 种基金the Natural Science Foundation of Shanxi Province(China)(Grant No.202403021223008)Supported by Scientific and Technology Innovation Programs of Higher Education Institutions in Shanxi(Grant No.2024Q017 and No.2025L043).
文摘Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.
基金support from the National Natural Science Foundation of China(NSFC 21905092,22475072 and 22075085)the Fundamental Research Funds for the Central Universities+1 种基金supported by the Shanghai Frontiers Science Center of Molecule Intelligent SynthesesEast China Normal University Multifunctional Platform for Innovation(004)。
文摘Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.
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.
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.
基金supported by the Key R&D Program of Zaozhuang city,China(2024GH12)the Zaozhuang Gathering of Talents Program。
文摘Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herein,we engineer tetraethylammonium(TEA)cation intercalation as a dual-function strategy that concurrently enables interlayer distance enlargement and electrostatic shielding effects,resolving Al^(3+) polarization-induced sluggish kinetics and cathode degradation in RABs.TEA intercalation triggers exceptional V2O5 interlayer expansion from 4.37 to 13.10Å,while the modulated charge distribution generates an electrostatic shielding effect that significantly weakens the Coulombic interactions between Al^(3+) and V2O5 frameworks.This dual mechanism collectively enhances ion diffusion kinetics and suppresses lattice stress accumulation.Ex situ X-ray diffraction and transmission electron microscopy analyses confirm that the“molecular pillar effect”of TEA enables minimal and highly reversible structural deformation of the cathode(<2.0%volume change after 200 cycles),demonstrating zero-strain aluminum-storage behavior.The optimized cathode delivers a high reversible capacity of 258 mAh g^(−1) at 0.5 A g^(−1),maintains 99%capacity retention at 5.0 A g^(−1),and exhibits an ultralow capacity decay rate of 0.01%per cycle over 6000 cycles.This work opens new pathways for designing stable high-performance RAB cathodes through synergistic modulation of electronic and lattice structures.
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supported by the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB1040300)the National Natural Science Foundation of China(Grant No.52172258)。
文摘As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode materials undergo complex ion intercalation and deintercalation processes,accompanied by defect formation and structural evolution.However,the microscopic mechanisms underlying processes such as cation disordering,lattice oxygen loss,and stage structure formation are still not fully understood.To address these challenges,we have developed the Electrode Dynamic Ion Intercalation/Deintercalation Simulator(EDIS),a software platform designed to simulate the dynamic processes of ion intercalation and deintercalation in electrode materials.Leveraging high-precision machine learning potentials,EDIS can efficiently model structural evolution and lithium-ion diffusion behavior under various states of charge and discharge,achieving accuracy approaching that of quantum mechanical methods in relevant chemical spaces.The software supports quantitative analysis of how variations in lithium-ion concentration and distribution affect lithium-ion transport properties,enables evaluation of the impact of structural defects,and allows for tracking of both structural evolution and transport characteristics during continuous cycling.EDIS is versatile and can be extended to sodium-ion batteries and related systems.By enabling in-depth analysis of these microscopic processes,EDIS provides a robust theoretical tool for mechanistic studies and the rational design of high-performance electrode materials for next-generation lithium-ion batteries.
基金financial support from Guangdong Basic and Applied Basic Research Foundation(2020B1515420001and 2023B1515040027)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(23yxqntd002)the Postdoctoral Fellowship Program of CPSF(GZC20242066)。
文摘Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge towards efficient DCBs.Here,we introduce a heteroatom-doped sp^(3) /sp^(2) hybridized carbon fiber membrane(cPAN-Gr)as a universal binder-free active electrode that effectively overcomes this trade-off,enabling efficient Li-ion intercalation chemistry for advanced DCBs.By strategically tuning the sp^(3) and sp^(2) carbon hybridization,the interlayer interaction,geometric and electronic structures of c PANGr are simultaneously optimized,which facilitates rapid Li-ion adsorption,smooth interlayer transport,and efficient electron transport by maximizing the synergy between sp^(2) -and sp^(3) -hybridized carbon.This,coupled with a 3D porous network structure,endows the c PAN-Gr with superior Li-ion storage capability and fast reaction kinetics.Therefore,the c PAN-Gr electrode delivers a high reversible capacity of 345 m A h g^(-1),excellent rate capability(50 C),and an ultralong cycle life over 10,000 cycles,outperforming other reported carbon-based electrodes.Moreover,the constructed DCB exhibits a large specific capacity of 135 m A h g^(-1),long-term cyclability over 500 cycles,and a remarkable energy density of 524.4 Wh kg^(-1).The c PAN-Gr electrode can also be expanded to construct a LiFePO_(4)//cPAN-Gr full battery.Combined theoretical and experimental studies reveal the crucial role of an optimized sp^(3) /sp^(2) ratio(79%)with topological defects and pyridine/pyrrolic N sites on the performance enhancement.This work offers new insights into the design of advanced carbon materials for DCBs and beyond.
