Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge....Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.展开更多
In comparison with traditional anthraquinone methods or electrocatalytic approaches,piezocatalysis for H_(2)O_(2)generation has garnered extensive attention as an environmentally friendly strategy.It is highly anticip...In comparison with traditional anthraquinone methods or electrocatalytic approaches,piezocatalysis for H_(2)O_(2)generation has garnered extensive attention as an environmentally friendly strategy.It is highly anticipated to develop piezocatalysts with strong piezoresponse,high stress sensitivity and high catalytic activity.Here,we present few-layer Bi_(2)O_(2)(OH)NO_(3)(BON)nanosheets(~3-4 unit-cell layers)with oxygen vacancies,synthesized via a one-step method,as an efficient piezoelectric catalyst for dual-channel H_(2)O_(2)production from H_(2)O and air.The few-layer structure endows BON with exceptional mechanical energy harvesting capabilities,while the larger specific surface area facilitates amplifying the modification effects induced by oxygen vacancies.The introduced vacancies boost surface structure asymmetry,creating localized polarization fields and strengthening piezoelectric potential.Simultaneously,the intrinsic effect of oxygen vacancies efficiently facilitates the adsorption and activation of O_(2),H_(2)O,and intermediates,thereby enhancing the piezoelectric catalytic activity.Thus,the optimized BON exhibits a H_(2)O_(2)yield of 1345.24μmol·g^(-1)from pure water and air via two-electron oxygen reduction and two-electron water oxidation reactions,approximately five times higher than the original BON and surpassing the majority of reported piezoelectric catalysts.This work highlights the importance of microstructure control and defect engineering,and emphasizes the crucial role of structure and oxygen vacancy concentration regulation in enhancing the performance of piezoelectric catalysis for H_(2)O_(2)production.It provides valuable guidance for designing high-performance catalysts tailored for sustainable environmental remediation.展开更多
Carbon and few-layer MoS2 nanosheets co- modified TiO2 nanocomposites （defined as MoS2-C@TiO2） were prepared through a facile one-step pyrolysis reaction technique. In this unique nanostructure, the TiO2 nanosh- eet...Carbon and few-layer MoS2 nanosheets co- modified TiO2 nanocomposites （defined as MoS2-C@TiO2） were prepared through a facile one-step pyrolysis reaction technique. In this unique nanostructure, the TiO2 nanosh- eets with stable structure serve as the backbones, and carbon coating and few-layer MoS2 tightly adhere onto the surface of the TiO2. It needs to be pointed out that the carbon coating improves the overall electronic conductivity and the few-layer MoS2 facilitates the diffusion of lithium ions and offers more active sites for lithium-ion storage. As a result, when evaluated as lithium-ion battery anodes, the MoS2-C@TiO2 nanocomposites exhibit markedly enhanced lithium storage capability compared with pure TiO2. A high specific capacity of 180 mA.h.g-1 has been achieved during the preliminary cycles, and the specific capacity can maintain 160 mA.h.g-1 at a high current density of 1C （1C=167 mA.g-1） even after 300 discharge/ charge cycles, indicating the great potential of the MoS2- C@TiO2 on energy storage.展开更多
MXenes have attracted great interest in various fields,and pillared MXenes open a new path with larger interlayer spacing.However,the further study of pillared MXenes is blocked at multilayered state due to serious re...MXenes have attracted great interest in various fields,and pillared MXenes open a new path with larger interlayer spacing.However,the further study of pillared MXenes is blocked at multilayered state due to serious restacking phenomenon of few-layered MXene nanosheets.In this work,for the first time,we designed a facile NH4+method to fundamentally solve the restacking issues of MXene nanosheets and succeeded in achieving pillared few-layered MXene.Sn nanocomplex pillared few-layered Ti3C2Tx(STCT)composites were synthesized by introducing atomic Sn nanocomplex into interlayer of pillared few-layered Ti3C2Tx MXenes via pillaring technique.The MXene matrix can inhibit Sn nanocomplex particles agglomeration and serve as conductive network.Meanwhile,the Sn nanocomplex particles can further open the interlayer spacing of Ti3C2Tx during lithiation/delithiation processes and therefore generate extra capacity.Benefiting from the“pillar effect,”the STCT composites can maintain 1016 mAh g^?1 after 1200 cycles at 2000 mA g^?1 and deliver a stable capacity of 680 mAh g^?1 at 5 A g^?1,showing one of the best performances among MXene-based composites.This work will provide a new way for the development of pillared MXenes and their energy storage due to significant breakthrough from multilayered state to few-layered one.展开更多
Both MXene and zeolitic imidazolate framework(ZIF)derivatives are tend to agglomerate during the compound process,which adversely affects their electrochemical properties.To alleviate this phenomenon,fewlayer MXene wa...Both MXene and zeolitic imidazolate framework(ZIF)derivatives are tend to agglomerate during the compound process,which adversely affects their electrochemical properties.To alleviate this phenomenon,fewlayer MXene was stripped by mechanical method,and electrostatic self-assembly with ZIF-67 in the presence of cationic surfactants.Furthermore,CoNi_(2)S_(4)/MXene composite was synthesized by the facile hydrothermal reaction.CoNi_(2)S_(4)well retained the cube frame structure of the ZIF-67 with the sagging outer frame and rough surface.In the composite,CoNi_(2)S_(4)nanocubes were interlinked by MXene nanosheets,which can effectively improve the structural stability and make full use of the active surface.CoNi_(2)S_(4)/MXene composite electrode exhibits an outperforming specific capacitance(751 C·g^(-1)at 1 A·g^(-1)),far higher than that of pure CoNi2S4(600 C·g^(-1)at 1 A·g^(-1)).An asymmetric supercapacitor(CoNi_(2)S_(4)/MXene//reduced graphene oxide(RGO))assembling delivers high energy density of 33.8 Wh·kg^(-1)and excellent cycling performance.This study indicates the potential of MXene/ZIF derivatives in the application of supercapacitor.展开更多
Currently,developing supercapacitors with robust cycle stability and suitability for wide-temperature-range operations is still a huge challenge.In the present work,few-layer hexagonal boron nitride nanosheets(h-BNNSs...Currently,developing supercapacitors with robust cycle stability and suitability for wide-temperature-range operations is still a huge challenge.In the present work,few-layer hexagonal boron nitride nanosheets(h-BNNSs)with a thickness of 2−4 atomic layers were fabricated via vacuum freeze-drying and nitridation.Then,the h-BNNSs/reduced graphene oxide(rGO)composite were further prepared using a hydrothermal method.Due to the combination of two two-dimensional(2D)van der Waals-bonded materials,the as-prepared h-BNNSs/rGO electrode exhibited robustness to wide-temperature-range operations from−10 to 50℃.When the electrodes worked in a neutral aqueous electrolyte(1 M Na2SO4),they showed a great stable cycling performance with almost 107%reservation of the initial capacitance at 0℃ and 111% at 50℃ for 5000 charge−discharge cycles.展开更多
High-performance and low-cost gas sensors are highly desirable and involved in industrial production and environmental detection.The combination of highly conductive MXene and metal oxide materials is a promising stra...High-performance and low-cost gas sensors are highly desirable and involved in industrial production and environmental detection.The combination of highly conductive MXene and metal oxide materials is a promising strategy to further improve the sensing performances.In this study,the hollow SnO_(2)nanospheres and few-layer MXene are assembled rationally via facile electrostatic synthesis processes,then the SnO_(2)/Ti_(3)C_(2)T_(x)nanocomposites were obtained.Compared with that based on either pure SnO_(2)nanoparticles or hollow nanospheres of SnO_(2),the SnO_(2)/Ti_(3)C_(2)T_(x)composite-based sensor exhibits much better sensing performances such as higher response(36.979),faster response time(5 s),and much improved selectivity as well as stability(15 days)to 100ppm C2H5OH at low working temperature(200°C).The improved sensing performances are mainly attributed to the large specific surface area and significantly increased oxygen vacancy concentration,which provides a large number of active sites for gas adsorption and surface catalytic reaction.In addition,the heterostructure interfaces between SnO_(2)hollow spheres and MXene layers are beneficial to gas sensing behaviors due to the synergistic effect.展开更多
Transition metal nitrides have become the focus of research in sodium ion batteries(SIBs)due to their unique metal properties and high theoretical capacity.However,the low actual capacity is still the main bottleneck ...Transition metal nitrides have become the focus of research in sodium ion batteries(SIBs)due to their unique metal properties and high theoretical capacity.However,the low actual capacity is still the main bottleneck for their application.Herein,using Mo-aniline frameworks as precursors,the carbon encapsulated nitrogen-rich Mo_(x)N is decorated by few-layered MoSe_(2) nanosheets(MoSe_(2)@Mo_(x)N/C-I)after the facile calcinating,selenizing,and nitriding.The carbon encapsulation can effectively strengthen the structural stability of Mo_(x)N.The nitrogen-rich Mo_(x)N and decoration of few-layered MoSe_(2) can create rich heterointerfaces and extra active sites for rapid sodium-ion storage,thus promoting reaction kinetics and improving actual capacity.The MoSe_(2)@Mo_(x)N/C-I as an anode achieves a large reversible capacity of 522.8 mAh g^(-1)at 0.1 A g^(-1),and 254.3 mAh g^(-1)capacity is obtained after 6000 cycles at 5.0 A g^(-1),showing signally improved sodium-ion storage properties.The storage mechanisms and kinetic behaviors are described systematically via the advanced testing techniques and density functional theory(DFT)calculations.It is found that the nitrogen-rich Mo_(x)N as the substrate is the basis of long cycling stability,and the few-layered MoSe_(2) are the key to improving actual capacity.This work indicates that the decoration of few-layered selenides has a broad application prospect in high-performance metal-ion batteries.展开更多
Few-layer graphene grown on Ni thin films has been studied by scanning tunneling microscopy. In most areas on the surfaces, moir6 patterns resulted from rotational stacking faults were observed. At a bias lower than 2...Few-layer graphene grown on Ni thin films has been studied by scanning tunneling microscopy. In most areas on the surfaces, moir6 patterns resulted from rotational stacking faults were observed. At a bias lower than 200 mV, only one sublattice shows up in regions without moir6 patterns while both sublattices are seen in regions with moir6 pattens. This phenomenon can be used to identify AB stacked regions. The scattering characteristics at various types of step edges are different from those of monolayer graphene edges, either armchair or zigzag.展开更多
In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-r...In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-ray absorption spectroscopy to determine the electronic structure and coordination geometry of the Fe species and in situ high angle annular dark field scanning transmission electron microscopy combined with atomic resolved electron energy loss spectroscopy to localize these,identify their chemical configuration and monitor their dynamics during thermal annealing.We show the high mobility of peripheral Fe atoms,first diffusing rapidly at the trims of the graphene layers and at temperatures as high as 573 K,diffusing from the edge planes towards in-plane locations of the graphene layers forming three-,four-coordinated metal sites and more complexes polynuclear Fe species.This process occurs via bond C-C breaking which partially reduces the extension of the graphene domains.However,the vast majority of Fe is segregated as a metal phase.This dynamic interconversion depends on the structural details of the surrounding graphitic environment in which these are formed as well as the Fe loading.N species appear stabilizing isolated and polynuclear Fe species even at temperatures as high as 873 K.The significance of our results lies on the fact that single Fe atoms in graphene are highly mobile and therefore a structural description of the electroactive sites as such is insufficient and more complex species might be more relevant,especially in the case of multielectron transfer reactions.Here we provide the experimental evidence of the formation of these polynuclear Fe-N sites and their structural characteristics.展开更多
Assembly of the top-down graphene units mostly results in 3D porous structure with randomly organized pores.The direct bottom-up synthesis of macroscopic 2D graphene sheets with organized pores are long sought in mate...Assembly of the top-down graphene units mostly results in 3D porous structure with randomly organized pores.The direct bottom-up synthesis of macroscopic 2D graphene sheets with organized pores are long sought in materials chemistry field,but rarely achieved.Herein,we present a self-catalysisassisted bottom-up route usingL-glutamic acid and iron chloride as starting materials for the fabrication of the millimeter-sized few-layer graphene sheets with aligned porous channels parallel to the 2D direction.The amino-and carboxyl-functional groups inL-glutamic acid can coordinate with iron cations,thus allowing an atomic dispersion of iron cations.The pyrolysis thus initiated the growth of graphene catalyzed by in-situ generated iron nanoparticles,and a dynamic flow of iron nanoparticles eventually led to the formation of millimeter-sized few-layer graphene sheets with aligned channels(60-85 nm in diameter).Used as anodes in lithium-ion batteries,these graphene sheets showed a good rate capability(142 m A h g^(-1) at 2 A g^(-1))and high capacity retention of 93%at 2 A g^(-1) after 1200 cycles.Kinetic analysis revealed that lithium ions storage was dominated by diffusion behavior and capacitive behavior together,in that graphene sheets with aligned channels could accelerate electron transfer and shorten lithium ions transport pathway.This work provides a novel approach to prepare unique porous graphene materials with specific structure for energy storage.展开更多
A capping layer for black phosphorus（BP） field-effect transistors（FETs） can provide effective isolation from the ambient air; however, this also brings inconvenience to the post-treatment for optimizing devices. W...A capping layer for black phosphorus（BP） field-effect transistors（FETs） can provide effective isolation from the ambient air; however, this also brings inconvenience to the post-treatment for optimizing devices. We perform low-temperature hydrogenation on Al2 O3 capped BP FETs. The hydrogenated BP devices exhibit a pronounced improvement of mobility from 69.6 to 107.7 cm2 v-1 s-1, and a dramatic decrease of subthreshold swing from8.4 to 2.6 V/dec. Furthermore, high/low frequency capacitance-voltage measurements suggest reduced interface defects in hydrogenated BP FETs. This could be due to the passivation of interface traps at both Al2 O3/BP and BP/SiO2 interfaces with hydrogen revealed by secondary ion mass spectroscopy.展开更多
To develop anode materials with superior volumetric storage is crucial for practical application of lithium/sodium-ion batteries.Here,we have developed a micro/nanostructured Sn S/few-layer graphene(Sn S/FLG)composite...To develop anode materials with superior volumetric storage is crucial for practical application of lithium/sodium-ion batteries.Here,we have developed a micro/nanostructured Sn S/few-layer graphene(Sn S/FLG)composite by facile scalable plasma milling.Inside the hybrid,SnS nanoparticles are tightly supported by FLG,forming nanosized primary particles as building blocks and assembling to microsized secondary granules.With this unique micro/nanostructure,the Sn S/FLG composite possesses a high tap density of 1.98 g cm^(-3)and thus ensures a high volumetric storage.The combination of Sn S nanoparticles and FLG nanosheets can not only enhance the overall electrical conductivity and facilitate the ion diffusion greatly,but alleviate the large volume expansion of Sn S effectively and maintain the electrode integrity during cycling.Thus,the densely compacted Sn S/FLG composite exhibits superior volumetric lithium and sodium storage,including high volumetric capacities of 1926.5/1051.4 m Ah cm^(-3)at 0.2 A g^(-1),and high retained capacities of 1754.3/760.3 m Ah cm^(-3)after 500cycles at 1.0 A g^(-1).With superior volumetric storage performance and facile scalable synthesis,the Sn S/FLG composite can be a promising anode for practical batteries application.展开更多
The hexagonal boron nitrides （BNs） with different morphologies are synthesized on a large scale by a simple route using a two-step synthetic process. The morphology of h-BN can be easily controlled by changing the h...The hexagonal boron nitrides （BNs） with different morphologies are synthesized on a large scale by a simple route using a two-step synthetic process. The morphology of h-BN can be easily controlled by changing the heat-treatment atmosphere. The whiskers with 0.5-10 μm in diameter and 50-100 μm in length consist of few-layers nanosheets in the NH3 gas. The BN nanosheets can be dissociated from the whiskers by ultrasonic treatment, which are less than 5 nm in thickness and even only two layers thick. The concentration and activity of N play an important rule, and abundant N and higher activity are conducive for refining grain in reaction. The H3BO3 and C3N6H6 molecules form a layer-like morphology with the interlinked planar triangle by a hydrogen-bonded structure.展开更多
High-quality graphene flakes have long been desirable for numerous applications including energy stor- age, printable electronics, and catalysis. In this contribution, we report a green, efficient, facile gas-driven e...High-quality graphene flakes have long been desirable for numerous applications including energy stor- age, printable electronics, and catalysis. In this contribution, we report a green, efficient, facile gas-driven exfoliation process for the preparation of high-quality graphene in large scale. The gas exfoliation process was realized by the interplay between the expansion of interlayer at high temperature and the gasifi- cation of liquid nitrogen within the interlayer. Detailed experiments demonstrated that the higher tem- perature was critical to the formation of fewer layers. The exfoliated graphene was proved to be of high quality. We further investigated the electrochemical behavior of this exfoliated graphene. As a result, this few-layered graphene demonstrated an enhanced capability as a supercapacitor, much higher than its counterpart parent material.展开更多
Graphene materials like turbostratic graphene exhibit remarkable promise for an array of applications,spanning from electronic devices to aerospace technologies.It is essential to develop a fabrication method that is ...Graphene materials like turbostratic graphene exhibit remarkable promise for an array of applications,spanning from electronic devices to aerospace technologies.It is essential to develop a fabrication method that is not only economical and efficient,but also environmentally sustainable.In this study,the molten salt-assisted magnesiothermic reduction(MSAMR)method is proposed for the synthesis of few-layer turbostratic graphene.K_(2)CO_(3)serves as both the carbon source and the catalyst for graphitization,facilitating the formation of the graphene structure,while in-situ generated MgO nanoparticles exert confinement and templating effects on the growth of graphene.The molten salts used effectively prevent the aggregation and the Bernal stacking of graphene sheets,ensuring the few-layer and turbostratic structure.The synergistic effects of K 2CO 3,in-situ generated MgO,and molten salts guarantee the formation of few-layer turbostratic graphene at a relatively low temperature,characterized with 4–8 stacking layers,a mesopore-dominated microstructure,and a high degree of graphitization.展开更多
The Pt-free photocatalytic hydrogen evolution(PHE)has been the focus in the photocatalytic field.The catalytic system with the large accessible surface and good mass-transfer ability,as well as the intimate combinatio...The Pt-free photocatalytic hydrogen evolution(PHE)has been the focus in the photocatalytic field.The catalytic system with the large accessible surface and good mass-transfer ability,as well as the intimate combination of co-catalyst with semiconductor is promising for the promotion of the application.Here,we have reported the design of the two-dimensional(2D)porous C_(3)N_(4)nanosheets(PCN NS)intimately combined with few-layered MoS_(2)for the high-effective Pt-free PHE.The PCN NS were synthesized based on peeling the melamine–cyanuric acid precursor(MC precursor)by the triphenylphosphine(TP)molecular followed by the calcination,mainly due to the matched size of the(100)plane distance of the precursor(0.8 nm)and the height of TP molecular.The porous structure is favorable for the mass-transfer and the 2D structure having large accessible surface,both of which are positive to promote the photocatalytic ability.The few-layered MoS_(2)are grown on PCN to give 2D MoS_(2)/PCN composites based on anchoring phosphomolybdic acid(PMo_(12))cluster on polyetherimide(PEI)-modified PCN followed by the vulcanization.The few-layered MoS_(2)have abundant edge active sites,and its intimate combination with porous PCN NS is favorable for the faster transfer and separation of the electrons.The characterization together with the advantage of 2D porous structure can largely promote the photocatalytic ability.The MoS_(2)/PCN showed good PHE activity with the high hydrogen production activity of 4,270.8μmol·h^(−1)·g^(−1)under the simulated sunlight condition(AM1.5),which was 7.9 times of the corresponding MoS_(2)/bulk C_(3)N_(4)and 12.7 times of the 1 wt.%Pt/bulk C_(3)N_(4).The study is potentially meaningful for the synthesis of PCN-based catalytic systems.展开更多
Optical modulation is significant and ubiquitous to telecommunication technologies,smart windows,and military devices.However,due to the limited tunability of traditional doping,achieving broadband optical property ch...Optical modulation is significant and ubiquitous to telecommunication technologies,smart windows,and military devices.However,due to the limited tunability of traditional doping,achieving broadband optical property change is a tough problem.Here,we demonstrate a remarkable transformation of optical transmittance in few-layer graphene(FLG)covering the electromagnetic spectra from the visible to the terahertz wave after lithium(Li)intercalation.It results in the transmittance being higher than 90%from the wavelengths of 480 to 1040 nm,and it increases most from 86.4%to 94.1%at 600 nm,reduces from∼80%to∼68%in the wavelength range from 2.5 to 11μm,has∼20%reduction over a wavelength range from 0.4 to 1.2 THz,and reduces from 97.2%to 68.2%at the wavelength of 1.2 THz.The optical modification of lithiated FLG is attributed to the increase of Fermi energy(E_(f))due to the charge transfer from Li to graphene layers.Our results may provide a new strategy for the design of broadband optical modulation devices.展开更多
Considering the high safety,low-cost and high capacity,aqueous zinc ion batteries have been a potential candidate for energy storage ensuring smooth electricity supply.Herein,we have synthesized inverse opal manganese...Considering the high safety,low-cost and high capacity,aqueous zinc ion batteries have been a potential candidate for energy storage ensuring smooth electricity supply.Herein,we have synthesized inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets by a solution template method at mild temperature.The ultrathin nanosheets with the thickness as small as 1 nm are well separated without obvious aggregation.Used as cathode material for aqueous zinc ion batteries,the few-layered ultrathin nanosheets combined with the inverse opal structure guarantee excellent performance.A high specific discharge capacity of 262.9 mAh·g^-1 is retained for the 100th cycle at a current density of 300 mA·g^-1 with a high capacity retention of 95.6%.A high specific discharge capacity of 121 mAh·g^-1 at a high current density of 2,000 mA·g^-1 is achieved even after 5,000 long-term cycles.The ex-situ X-ray diffraction (XRD) patterns,selected-area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM) results demonstrate that the discharge/charge processes involve the reversible formation of zinc sulfate hydroxide hydrate on the cathode while in-plane crystal structure of the layered bimessite MnO2 could be maintained.This unique structured MnO2 is a promising candidate as cathode material for high capacity,high rate capability and long-term aqueous zinc-ion batteries.展开更多
基金supported by National Natural Science Foundation of China(52302034,52402060,52202201,52021006)Beijing National Laboratory for Molecular Sciences(BNLMS-CXTD202001)+1 种基金Shenzhen Science and Technology Innovation Commission(KQTD20221101115627004)China Postdoctoral Science Foundation(2024T170972)。
文摘Graphdiyne(GDY)is a two-dimensional carbon allotrope with exceptional physical and chemical properties that is gaining increasing attention.However,its efficient and scalable synthesis remains a significant challenge.We present a microwave-assisted approach for its continuous,large-scale production which enables synthesis at a rate of 0.6 g/h,with a yield of up to 90%.The synthesized GDY nanosheets have an average diameter of 246 nm and a thickness of 4 nm.We used GDY as a stable coating for potassium(K)metal anodes(K@GDY),taking advantage of its unique molecular structure to provide favorable paths for K-ion transport.This modification significantly inhibited dendrite formation and improved the cycling stability of K metal batteries.Full-cells with perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA)cathodes showed the clear superiority of the K@GDY anodes over bare K anodes in terms of performance,stability,and cycle life.The K@GDY maintained a stable voltage plateau and gave an excellent capacity retention after 600 cycles with nearly 100%Coulombic efficiency.This work not only provides a scalable and efficient way for GDY synthesis but also opens new possibilities for its use in energy storage and other advanced technologies.
文摘In comparison with traditional anthraquinone methods or electrocatalytic approaches,piezocatalysis for H_(2)O_(2)generation has garnered extensive attention as an environmentally friendly strategy.It is highly anticipated to develop piezocatalysts with strong piezoresponse,high stress sensitivity and high catalytic activity.Here,we present few-layer Bi_(2)O_(2)(OH)NO_(3)(BON)nanosheets(~3-4 unit-cell layers)with oxygen vacancies,synthesized via a one-step method,as an efficient piezoelectric catalyst for dual-channel H_(2)O_(2)production from H_(2)O and air.The few-layer structure endows BON with exceptional mechanical energy harvesting capabilities,while the larger specific surface area facilitates amplifying the modification effects induced by oxygen vacancies.The introduced vacancies boost surface structure asymmetry,creating localized polarization fields and strengthening piezoelectric potential.Simultaneously,the intrinsic effect of oxygen vacancies efficiently facilitates the adsorption and activation of O_(2),H_(2)O,and intermediates,thereby enhancing the piezoelectric catalytic activity.Thus,the optimized BON exhibits a H_(2)O_(2)yield of 1345.24μmol·g^(-1)from pure water and air via two-electron oxygen reduction and two-electron water oxidation reactions,approximately five times higher than the original BON and surpassing the majority of reported piezoelectric catalysts.This work highlights the importance of microstructure control and defect engineering,and emphasizes the crucial role of structure and oxygen vacancy concentration regulation in enhancing the performance of piezoelectric catalysis for H_(2)O_(2)production.It provides valuable guidance for designing high-performance catalysts tailored for sustainable environmental remediation.
基金financially supported by the National Natural Science Foundation of China(No.51472177)the China-EU Science and Technology Cooperation Project(No.SQ2013ZOA100006)
文摘Carbon and few-layer MoS2 nanosheets co- modified TiO2 nanocomposites （defined as MoS2-C@TiO2） were prepared through a facile one-step pyrolysis reaction technique. In this unique nanostructure, the TiO2 nanosh- eets with stable structure serve as the backbones, and carbon coating and few-layer MoS2 tightly adhere onto the surface of the TiO2. It needs to be pointed out that the carbon coating improves the overall electronic conductivity and the few-layer MoS2 facilitates the diffusion of lithium ions and offers more active sites for lithium-ion storage. As a result, when evaluated as lithium-ion battery anodes, the MoS2-C@TiO2 nanocomposites exhibit markedly enhanced lithium storage capability compared with pure TiO2. A high specific capacity of 180 mA.h.g-1 has been achieved during the preliminary cycles, and the specific capacity can maintain 160 mA.h.g-1 at a high current density of 1C （1C=167 mA.g-1） even after 300 discharge/ charge cycles, indicating the great potential of the MoS2- C@TiO2 on energy storage.
基金the National Natural Science Foundation of China(Grant No.51901206,51822104)the Training Program of Major Basic Research Project of Provincial Natural Science Foundation of Guangdong(2017B030308001).
文摘MXenes have attracted great interest in various fields,and pillared MXenes open a new path with larger interlayer spacing.However,the further study of pillared MXenes is blocked at multilayered state due to serious restacking phenomenon of few-layered MXene nanosheets.In this work,for the first time,we designed a facile NH4+method to fundamentally solve the restacking issues of MXene nanosheets and succeeded in achieving pillared few-layered MXene.Sn nanocomplex pillared few-layered Ti3C2Tx(STCT)composites were synthesized by introducing atomic Sn nanocomplex into interlayer of pillared few-layered Ti3C2Tx MXenes via pillaring technique.The MXene matrix can inhibit Sn nanocomplex particles agglomeration and serve as conductive network.Meanwhile,the Sn nanocomplex particles can further open the interlayer spacing of Ti3C2Tx during lithiation/delithiation processes and therefore generate extra capacity.Benefiting from the“pillar effect,”the STCT composites can maintain 1016 mAh g^?1 after 1200 cycles at 2000 mA g^?1 and deliver a stable capacity of 680 mAh g^?1 at 5 A g^?1,showing one of the best performances among MXene-based composites.This work will provide a new way for the development of pillared MXenes and their energy storage due to significant breakthrough from multilayered state to few-layered one.
基金financially supported by the Fundamental Research Funds for the Central Universities (No. 2019XKQYMS16)
文摘Both MXene and zeolitic imidazolate framework(ZIF)derivatives are tend to agglomerate during the compound process,which adversely affects their electrochemical properties.To alleviate this phenomenon,fewlayer MXene was stripped by mechanical method,and electrostatic self-assembly with ZIF-67 in the presence of cationic surfactants.Furthermore,CoNi_(2)S_(4)/MXene composite was synthesized by the facile hydrothermal reaction.CoNi_(2)S_(4)well retained the cube frame structure of the ZIF-67 with the sagging outer frame and rough surface.In the composite,CoNi_(2)S_(4)nanocubes were interlinked by MXene nanosheets,which can effectively improve the structural stability and make full use of the active surface.CoNi_(2)S_(4)/MXene composite electrode exhibits an outperforming specific capacitance(751 C·g^(-1)at 1 A·g^(-1)),far higher than that of pure CoNi2S4(600 C·g^(-1)at 1 A·g^(-1)).An asymmetric supercapacitor(CoNi_(2)S_(4)/MXene//reduced graphene oxide(RGO))assembling delivers high energy density of 33.8 Wh·kg^(-1)and excellent cycling performance.This study indicates the potential of MXene/ZIF derivatives in the application of supercapacitor.
基金financially supported by the National Natural Science Foundation for Excellent Young Scholars of China (No. 51522402)the National Postdoctoral Program for Innovative Talents of China (No. BX20180034)+2 种基金the National Natural Science Foundation of China (No. 51902020)the Fundamental Research Funds for the Central Universities (No. FRF-TP-18-045A1)the China Postdoctoral Science Foundation (No. 2018M641192)
文摘Currently,developing supercapacitors with robust cycle stability and suitability for wide-temperature-range operations is still a huge challenge.In the present work,few-layer hexagonal boron nitride nanosheets(h-BNNSs)with a thickness of 2−4 atomic layers were fabricated via vacuum freeze-drying and nitridation.Then,the h-BNNSs/reduced graphene oxide(rGO)composite were further prepared using a hydrothermal method.Due to the combination of two two-dimensional(2D)van der Waals-bonded materials,the as-prepared h-BNNSs/rGO electrode exhibited robustness to wide-temperature-range operations from−10 to 50℃.When the electrodes worked in a neutral aqueous electrolyte(1 M Na2SO4),they showed a great stable cycling performance with almost 107%reservation of the initial capacitance at 0℃ and 111% at 50℃ for 5000 charge−discharge cycles.
基金This work is supported partially by the project of the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Nos.LAPS21004,LAPS202114)National Natural Science Foundation of China(Nos.52272200,51972110,52102245 and 52072121)+6 种基金Beijing Science and Technology Project(No.Z211100004621010)Beijing Natural Science Foundation(Nos.2222076,2222077)Hebei Natural Science Foundation(No.E2022502022)Huaneng Group Headquarters Science and Technology Project(No.HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,China Postdoctoral Science Foundation(No.2022M721129)the Fundamental Research Funds for the Central Universities(Nos.2022MS030,2021MS028,2020MS023,2020MS028)the NCEPU“Double First-Class”Program.This research was also supported by Brain Pool program funded by the Ministry of Science and ICT through the National Research Foundation of Korea(No.2021H1D3A2A01100019).
文摘High-performance and low-cost gas sensors are highly desirable and involved in industrial production and environmental detection.The combination of highly conductive MXene and metal oxide materials is a promising strategy to further improve the sensing performances.In this study,the hollow SnO_(2)nanospheres and few-layer MXene are assembled rationally via facile electrostatic synthesis processes,then the SnO_(2)/Ti_(3)C_(2)T_(x)nanocomposites were obtained.Compared with that based on either pure SnO_(2)nanoparticles or hollow nanospheres of SnO_(2),the SnO_(2)/Ti_(3)C_(2)T_(x)composite-based sensor exhibits much better sensing performances such as higher response(36.979),faster response time(5 s),and much improved selectivity as well as stability(15 days)to 100ppm C2H5OH at low working temperature(200°C).The improved sensing performances are mainly attributed to the large specific surface area and significantly increased oxygen vacancy concentration,which provides a large number of active sites for gas adsorption and surface catalytic reaction.In addition,the heterostructure interfaces between SnO_(2)hollow spheres and MXene layers are beneficial to gas sensing behaviors due to the synergistic effect.
基金supported by the National Natural Science Foundation of China(52171207,51762021)the Natural Science Foundation of Jiangxi province(20212BAB204031,20192ACB21009)。
文摘Transition metal nitrides have become the focus of research in sodium ion batteries(SIBs)due to their unique metal properties and high theoretical capacity.However,the low actual capacity is still the main bottleneck for their application.Herein,using Mo-aniline frameworks as precursors,the carbon encapsulated nitrogen-rich Mo_(x)N is decorated by few-layered MoSe_(2) nanosheets(MoSe_(2)@Mo_(x)N/C-I)after the facile calcinating,selenizing,and nitriding.The carbon encapsulation can effectively strengthen the structural stability of Mo_(x)N.The nitrogen-rich Mo_(x)N and decoration of few-layered MoSe_(2) can create rich heterointerfaces and extra active sites for rapid sodium-ion storage,thus promoting reaction kinetics and improving actual capacity.The MoSe_(2)@Mo_(x)N/C-I as an anode achieves a large reversible capacity of 522.8 mAh g^(-1)at 0.1 A g^(-1),and 254.3 mAh g^(-1)capacity is obtained after 6000 cycles at 5.0 A g^(-1),showing signally improved sodium-ion storage properties.The storage mechanisms and kinetic behaviors are described systematically via the advanced testing techniques and density functional theory(DFT)calculations.It is found that the nitrogen-rich Mo_(x)N as the substrate is the basis of long cycling stability,and the few-layered MoSe_(2) are the key to improving actual capacity.This work indicates that the decoration of few-layered selenides has a broad application prospect in high-performance metal-ion batteries.
基金supported by the National Basic Research Program of China(Grant No.2012CB921300)the National Natural Science Foundation of China(Grant Nos.11074005 and 91021007)the Chinese Ministry of Education
文摘Few-layer graphene grown on Ni thin films has been studied by scanning tunneling microscopy. In most areas on the surfaces, moir6 patterns resulted from rotational stacking faults were observed. At a bias lower than 200 mV, only one sublattice shows up in regions without moir6 patterns while both sublattices are seen in regions with moir6 pattens. This phenomenon can be used to identify AB stacked regions. The scattering characteristics at various types of step edges are different from those of monolayer graphene edges, either armchair or zigzag.
基金The UK Catalysis Hub for support provided via the membership of the UK Catalysis Hub Consortium and funded by EPSRC (portfolio grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/I019693/1).
文摘In this study,we aim to contribute an understanding of the pathway of formation of Fe species during top-down synthesis of dispersed Fe on N-functionalized few layer graphene,widely used in electrocatalysis.We use X-ray absorption spectroscopy to determine the electronic structure and coordination geometry of the Fe species and in situ high angle annular dark field scanning transmission electron microscopy combined with atomic resolved electron energy loss spectroscopy to localize these,identify their chemical configuration and monitor their dynamics during thermal annealing.We show the high mobility of peripheral Fe atoms,first diffusing rapidly at the trims of the graphene layers and at temperatures as high as 573 K,diffusing from the edge planes towards in-plane locations of the graphene layers forming three-,four-coordinated metal sites and more complexes polynuclear Fe species.This process occurs via bond C-C breaking which partially reduces the extension of the graphene domains.However,the vast majority of Fe is segregated as a metal phase.This dynamic interconversion depends on the structural details of the surrounding graphitic environment in which these are formed as well as the Fe loading.N species appear stabilizing isolated and polynuclear Fe species even at temperatures as high as 873 K.The significance of our results lies on the fact that single Fe atoms in graphene are highly mobile and therefore a structural description of the electroactive sites as such is insufficient and more complex species might be more relevant,especially in the case of multielectron transfer reactions.Here we provide the experimental evidence of the formation of these polynuclear Fe-N sites and their structural characteristics.
基金supported by the National Natural Science Foundation of China(No.21776041 and No.21875028)the Cheung Kong Scholars Programme of China(T2015036)。
文摘Assembly of the top-down graphene units mostly results in 3D porous structure with randomly organized pores.The direct bottom-up synthesis of macroscopic 2D graphene sheets with organized pores are long sought in materials chemistry field,but rarely achieved.Herein,we present a self-catalysisassisted bottom-up route usingL-glutamic acid and iron chloride as starting materials for the fabrication of the millimeter-sized few-layer graphene sheets with aligned porous channels parallel to the 2D direction.The amino-and carboxyl-functional groups inL-glutamic acid can coordinate with iron cations,thus allowing an atomic dispersion of iron cations.The pyrolysis thus initiated the growth of graphene catalyzed by in-situ generated iron nanoparticles,and a dynamic flow of iron nanoparticles eventually led to the formation of millimeter-sized few-layer graphene sheets with aligned channels(60-85 nm in diameter).Used as anodes in lithium-ion batteries,these graphene sheets showed a good rate capability(142 m A h g^(-1) at 2 A g^(-1))and high capacity retention of 93%at 2 A g^(-1) after 1200 cycles.Kinetic analysis revealed that lithium ions storage was dominated by diffusion behavior and capacitive behavior together,in that graphene sheets with aligned channels could accelerate electron transfer and shorten lithium ions transport pathway.This work provides a novel approach to prepare unique porous graphene materials with specific structure for energy storage.
基金Supported by the National Natural Science Foundation of China under Grant Nos 61474027 and 61774041
文摘A capping layer for black phosphorus（BP） field-effect transistors（FETs） can provide effective isolation from the ambient air; however, this also brings inconvenience to the post-treatment for optimizing devices. We perform low-temperature hydrogenation on Al2 O3 capped BP FETs. The hydrogenated BP devices exhibit a pronounced improvement of mobility from 69.6 to 107.7 cm2 v-1 s-1, and a dramatic decrease of subthreshold swing from8.4 to 2.6 V/dec. Furthermore, high/low frequency capacitance-voltage measurements suggest reduced interface defects in hydrogenated BP FETs. This could be due to the passivation of interface traps at both Al2 O3/BP and BP/SiO2 interfaces with hydrogen revealed by secondary ion mass spectroscopy.
基金the financial support from the Innovative Research Groups of the National Natural Science Foundation of China(No.51621001)National Natural Science Foundation of China(No.51671088,51671089)
文摘To develop anode materials with superior volumetric storage is crucial for practical application of lithium/sodium-ion batteries.Here,we have developed a micro/nanostructured Sn S/few-layer graphene(Sn S/FLG)composite by facile scalable plasma milling.Inside the hybrid,SnS nanoparticles are tightly supported by FLG,forming nanosized primary particles as building blocks and assembling to microsized secondary granules.With this unique micro/nanostructure,the Sn S/FLG composite possesses a high tap density of 1.98 g cm^(-3)and thus ensures a high volumetric storage.The combination of Sn S nanoparticles and FLG nanosheets can not only enhance the overall electrical conductivity and facilitate the ion diffusion greatly,but alleviate the large volume expansion of Sn S effectively and maintain the electrode integrity during cycling.Thus,the densely compacted Sn S/FLG composite exhibits superior volumetric lithium and sodium storage,including high volumetric capacities of 1926.5/1051.4 m Ah cm^(-3)at 0.2 A g^(-1),and high retained capacities of 1754.3/760.3 m Ah cm^(-3)after 500cycles at 1.0 A g^(-1).With superior volumetric storage performance and facile scalable synthesis,the Sn S/FLG composite can be a promising anode for practical batteries application.
基金Project supported by the National Natural Science Foundation of China(Grant No.11504266)the Tianjin Natural Science Foundation,China(Grant No.17JCQNJC02300)the National Key Foundation for Exploring Scientific Instrument,China(Grant No.2014YQ120351)
文摘The hexagonal boron nitrides （BNs） with different morphologies are synthesized on a large scale by a simple route using a two-step synthetic process. The morphology of h-BN can be easily controlled by changing the heat-treatment atmosphere. The whiskers with 0.5-10 μm in diameter and 50-100 μm in length consist of few-layers nanosheets in the NH3 gas. The BN nanosheets can be dissociated from the whiskers by ultrasonic treatment, which are less than 5 nm in thickness and even only two layers thick. The concentration and activity of N play an important rule, and abundant N and higher activity are conducive for refining grain in reaction. The H3BO3 and C3N6H6 molecules form a layer-like morphology with the interlinked planar triangle by a hydrogen-bonded structure.
基金the China National Natural Science Foundation of China (Nos. 21722604, 21576122, 21376111)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)+1 种基金a scholarship from the China Scholarship Council (CSC)the Postgraduate Innovation Project of Jiangsu Province (NO. KYLX15_1067)
文摘High-quality graphene flakes have long been desirable for numerous applications including energy stor- age, printable electronics, and catalysis. In this contribution, we report a green, efficient, facile gas-driven exfoliation process for the preparation of high-quality graphene in large scale. The gas exfoliation process was realized by the interplay between the expansion of interlayer at high temperature and the gasifi- cation of liquid nitrogen within the interlayer. Detailed experiments demonstrated that the higher tem- perature was critical to the formation of fewer layers. The exfoliated graphene was proved to be of high quality. We further investigated the electrochemical behavior of this exfoliated graphene. As a result, this few-layered graphene demonstrated an enhanced capability as a supercapacitor, much higher than its counterpart parent material.
基金the funding support from the National Natural Science Foundation of China(Grant No.22278404).
文摘Graphene materials like turbostratic graphene exhibit remarkable promise for an array of applications,spanning from electronic devices to aerospace technologies.It is essential to develop a fabrication method that is not only economical and efficient,but also environmentally sustainable.In this study,the molten salt-assisted magnesiothermic reduction(MSAMR)method is proposed for the synthesis of few-layer turbostratic graphene.K_(2)CO_(3)serves as both the carbon source and the catalyst for graphitization,facilitating the formation of the graphene structure,while in-situ generated MgO nanoparticles exert confinement and templating effects on the growth of graphene.The molten salts used effectively prevent the aggregation and the Bernal stacking of graphene sheets,ensuring the few-layer and turbostratic structure.The synergistic effects of K 2CO 3,in-situ generated MgO,and molten salts guarantee the formation of few-layer turbostratic graphene at a relatively low temperature,characterized with 4–8 stacking layers,a mesopore-dominated microstructure,and a high degree of graphitization.
基金supported by the National Key R&D Program of China(No.2018YFB1502401)the National Natural Science Foundation of China(Nos.91961111,U20A20250,and 21901064)+3 种基金the Natural Science Foundation of Heilongjiang Province(No.ZD2021B003)the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2020004)the Basic Research Fund of Heilongjiang University in Heilongjiang Province(No.2021-KYYWF-0039)Open Project of Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education.
文摘The Pt-free photocatalytic hydrogen evolution(PHE)has been the focus in the photocatalytic field.The catalytic system with the large accessible surface and good mass-transfer ability,as well as the intimate combination of co-catalyst with semiconductor is promising for the promotion of the application.Here,we have reported the design of the two-dimensional(2D)porous C_(3)N_(4)nanosheets(PCN NS)intimately combined with few-layered MoS_(2)for the high-effective Pt-free PHE.The PCN NS were synthesized based on peeling the melamine–cyanuric acid precursor(MC precursor)by the triphenylphosphine(TP)molecular followed by the calcination,mainly due to the matched size of the(100)plane distance of the precursor(0.8 nm)and the height of TP molecular.The porous structure is favorable for the mass-transfer and the 2D structure having large accessible surface,both of which are positive to promote the photocatalytic ability.The few-layered MoS_(2)are grown on PCN to give 2D MoS_(2)/PCN composites based on anchoring phosphomolybdic acid(PMo_(12))cluster on polyetherimide(PEI)-modified PCN followed by the vulcanization.The few-layered MoS_(2)have abundant edge active sites,and its intimate combination with porous PCN NS is favorable for the faster transfer and separation of the electrons.The characterization together with the advantage of 2D porous structure can largely promote the photocatalytic ability.The MoS_(2)/PCN showed good PHE activity with the high hydrogen production activity of 4,270.8μmol·h^(−1)·g^(−1)under the simulated sunlight condition(AM1.5),which was 7.9 times of the corresponding MoS_(2)/bulk C_(3)N_(4)and 12.7 times of the 1 wt.%Pt/bulk C_(3)N_(4).The study is potentially meaningful for the synthesis of PCN-based catalytic systems.
基金supported by the National Key R&D Program of China(No.2022YFA1404201)the National Natural Science Foundation of China(Nos.62305200,U22A2091,62127817,and 62075240)the Fundamental Research Program of Shanxi Province(No.202203021222001).
文摘Optical modulation is significant and ubiquitous to telecommunication technologies,smart windows,and military devices.However,due to the limited tunability of traditional doping,achieving broadband optical property change is a tough problem.Here,we demonstrate a remarkable transformation of optical transmittance in few-layer graphene(FLG)covering the electromagnetic spectra from the visible to the terahertz wave after lithium(Li)intercalation.It results in the transmittance being higher than 90%from the wavelengths of 480 to 1040 nm,and it increases most from 86.4%to 94.1%at 600 nm,reduces from∼80%to∼68%in the wavelength range from 2.5 to 11μm,has∼20%reduction over a wavelength range from 0.4 to 1.2 THz,and reduces from 97.2%to 68.2%at the wavelength of 1.2 THz.The optical modification of lithiated FLG is attributed to the increase of Fermi energy(E_(f))due to the charge transfer from Li to graphene layers.Our results may provide a new strategy for the design of broadband optical modulation devices.
文摘Considering the high safety,low-cost and high capacity,aqueous zinc ion batteries have been a potential candidate for energy storage ensuring smooth electricity supply.Herein,we have synthesized inverse opal manganese dioxide constructed by few-layered ultrathin nanosheets by a solution template method at mild temperature.The ultrathin nanosheets with the thickness as small as 1 nm are well separated without obvious aggregation.Used as cathode material for aqueous zinc ion batteries,the few-layered ultrathin nanosheets combined with the inverse opal structure guarantee excellent performance.A high specific discharge capacity of 262.9 mAh·g^-1 is retained for the 100th cycle at a current density of 300 mA·g^-1 with a high capacity retention of 95.6%.A high specific discharge capacity of 121 mAh·g^-1 at a high current density of 2,000 mA·g^-1 is achieved even after 5,000 long-term cycles.The ex-situ X-ray diffraction (XRD) patterns,selected-area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM) results demonstrate that the discharge/charge processes involve the reversible formation of zinc sulfate hydroxide hydrate on the cathode while in-plane crystal structure of the layered bimessite MnO2 could be maintained.This unique structured MnO2 is a promising candidate as cathode material for high capacity,high rate capability and long-term aqueous zinc-ion batteries.
