We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed ...We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.展开更多
Hydrogen has been identified as one of the most promising sustainable and clean energy. Developing hydrogen evolution reaction(HER) catalyst with high activity is essential for satisfying the future requirements. Cons...Hydrogen has been identified as one of the most promising sustainable and clean energy. Developing hydrogen evolution reaction(HER) catalyst with high activity is essential for satisfying the future requirements. Considering novel advantages of two-dimensional materials and high catalytic activity of atomic transition metal, in this study, using density functional theory calculation, the HER on single transitionmetal(23 different TM atoms) doped phosphorus carbide monolayer(α-PC) has been investigated. The Volmer–Tafel and Volmer–Heyrovsky reaction mechanisms, and the stability of the most promising HER catalyst are also included. The results show that Ir-αPC with high physical and thermal stability has the most optimal value of Gibbs free adsorption energy for H atom. The relationship of d band center and the HER activity shows a volcano-like curve. The calculation of reaction energy barrier indicates that the Volmer-Heyrovsky step is more favorable than the Volmer-Tafel step.展开更多
Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a hi...Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.展开更多
Group IV element Pb has been selected as the dopant to dope at the Sr site of Sr_(2)IrO_(4). It is exciting to find that the single-phase crystal structure could be maintained with a high Pb doping level of up to x=0....Group IV element Pb has been selected as the dopant to dope at the Sr site of Sr_(2)IrO_(4). It is exciting to find that the single-phase crystal structure could be maintained with a high Pb doping level of up to x=0.3 in Sr_(2-x)Pb_(x)IrO_(4). The mapping data obtained from energy-dispersive x-ray spectroscopy analyses give solid evidence that the Pb ions are uniformly distributed in the Sr_(2)IrO_(4) matrix. The incorporation of Pb leads to a moderate depression of the canted antiferromagnetic ordering state. The electrical conductivity could be greatly enhanced when the Pb doping content is higher than x=0.2.The present results give a fresh material base to explore new physics in doped Sr_(2)IrO_(4) systems.展开更多
Electrical control of magnetism in van der Waals semiconductors is a promising step towards development of two-dimensional spintronic devices with ultralow power consumption for processing and storing information.Here...Electrical control of magnetism in van der Waals semiconductors is a promising step towards development of two-dimensional spintronic devices with ultralow power consumption for processing and storing information.Here, we propose a design for two-dimensional van der Waals heterostructures(vdWHs) that can host ferroelectricity and ferromagnetism simultaneously under hole doping. By contacting an In Se monolayer and forming an InSe/In_(2)Se_(3) vd WH, the switchable built-in electric field from the reversible out-of-plane polarization enables robust control of the band alignment. Furthermore, switching between the two ferroelectric states(P_↑ and P_↓)of hole-doped In_(2)Se_(3) with an external electric field can interchange the ON and OFF states of the nonvolatile magnetism. More interestingly, doping concentration and strain can effectively tune the magnetic moment and polarization energy. Therefore, this provides a platform for realizing multiferroics in ferroelectric heterostructures,showing great potential for use in nonvolatile memories and ferroelectric field-effect transistors.展开更多
Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electr...Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electronic state starting from the Mott insulator, we dose the surface of the parent phase Ca_(2)CuO_(2)Cl_(2) by depositing Rb atoms, which are supposed to donate electrons to the CuO_(2) planes underneath. We successfully achieved the Rb sub-monolayer thin films in forming the square lattice. The scanning tunneling microscopy or spectroscopy measurements on the surface show that the Fermi energy is pinned within the Mott gap but close to the edge of the charge transfer band. In addition, an in-gap state appears at the bottom of the upper Hubbard band(UHB), and the Mott gap will be significantly diminished. Combined with the Cl defect and the Rb adatom/cluster results, the electron doping is likely to increase the spectra weight of the UHB for the double occupancy. Our results provide information to understand the electron doping to the parent compound of cuprates.展开更多
Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion ...Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.展开更多
The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface def...The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.展开更多
Controlling collective electronic states hold great promise for development of innovative devices. Here, we experimentally detect the modification of the charge density wave(CDW) phase transition within a 1T-TaS_(2) l...Controlling collective electronic states hold great promise for development of innovative devices. Here, we experimentally detect the modification of the charge density wave(CDW) phase transition within a 1T-TaS_(2) layer in a WS_(2)/1T-TaS_(2) heterostructure using time-resolved ultrafast spectroscopy. Laser-induced charge transfer doping strongly suppresses the commensurate CDW phase, which results in a significant decrease in both the phase transition temperature(T_(c)) and phase transition stiffness. We interpret the phenomenon that photoinduced hole doping, when surpassing a critical threshold value of ~ 10^(18)cm^(-3), sharply decreases the phase transition energy barrier. Our results provide new insights into controlling the CDW phase transition, paving the way for optical-controlled novel devices based on CDW materials.展开更多
Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and...Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.展开更多
The development of semiconductors is always accompanied by the progress in controllable doping techniques.Taking AlGaN-based ultraviolet(UV)emitters as an example,despite a peak wall-plug efficiency of 15.3%at the wav...The development of semiconductors is always accompanied by the progress in controllable doping techniques.Taking AlGaN-based ultraviolet(UV)emitters as an example,despite a peak wall-plug efficiency of 15.3%at the wavelength of 275 nm,there is still a huge gap in comparison with GaN-based visible light-emitting diodes(LEDs),mainly attributed to the inefficient doping of AlGaN with increase of the Al composition.First,p-doping of Al-rich AlGaN is a long-standing challenge and the low hole concentration seriously restricts the carrier injection efficiency.Although p-GaN cladding layers are widely adopted as a compromise,the high injection barrier of holes as well as the inevitable loss of light extraction cannot be neglected.While in terms of n-doping the main issue is the degradation of the electrical property when the Al composition exceeds 80%,resulting in a low electrical efficiency in sub-250 nm UV-LEDs.This review summarizes the recent advances and outlines the major challenges in the efficient doping of Al-rich AlGaN,meanwhile the corresponding approaches pursued to overcome the doping issues are discussed in detail.展开更多
Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batt...Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.展开更多
Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high perfo...Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.展开更多
Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium si...Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).展开更多
A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation abili...A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.展开更多
Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Comp...Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.展开更多
To address the low conductivity and easy agglomeration of transition metal sulfide nanoparticles,FeCoS_(4) nanoparticles embedded in S-doped hollow carbon(FeCoS_(4)@S-HC)composites were successfully fabricated through...To address the low conductivity and easy agglomeration of transition metal sulfide nanoparticles,FeCoS_(4) nanoparticles embedded in S-doped hollow carbon(FeCoS_(4)@S-HC)composites were successfully fabricated through a combination of hydrothermal processes and sulfidation treatment.The unique bowlshaped FeCoS_(4)/S-HC composites exhibit excellent structural stability with a high specific surface area of 303.7 m^(2)·g^(-1) and a pore volume of 0.93 cm^(3)·g^(-1).When applied as anode material for lithium-ion batteries,the FeCoS_(4)@S-HC anode exhibits efficient lithium storage with high reversible specific capacity(970.2 mA·h·g^(-1) at 100 mA·g^(-1))and enhanced cycling stability(574 mA·h·g^(-1) at 0.2 A·g^(-1) after 350 cycles,a capacity retention of 84%).The excellent lithium storage is attributed to the fact that the bimetallic FeCoS_(4) nanoparticles with abundant active sites can accelerate the electrochemical reaction kinetics,and the bowl-shaped S-HC structure can provide a stable mechanical structure to suppress volume expansion.展开更多
Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) un...Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_12_12_1.Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.展开更多
Manipulating emergent quantum phenomena is a key issue for understanding the underlying physics and contributing to possible applications.Here we study the evolution of insulating ground states of Ta_(2)Pu_(3)Te_(5) a...Manipulating emergent quantum phenomena is a key issue for understanding the underlying physics and contributing to possible applications.Here we study the evolution of insulating ground states of Ta_(2)Pu_(3)Te_(5) and Ta_(2)Ni_(3)Te_(5) under in-situ surface potassium deposition via angle-resolved photoemission spectroscopy.Our results confirm the excitonic insulator character of Ta_(2)d_(3)Te_(5).Upon surface doping,the size of its global gap decreases obviously.After a deposition time of more than 7 min,the potassium atoms induce a metal-insulator phase transition and make the system recover to a normal state.In contrast,our results show that the isostructural compound Ta_(2)Ni_(3)Te_(5) is a conventional insulator.The size of its global gap decreases upon surface doping,but persists positive throughout the doping process.Our results not only confirm the excitonic origin of the band gap in Ta_(2)Pd_(3)Te_(5),but also offer an effective method for designing functional quantum devices in the future.展开更多
SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish ...SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.展开更多
基金National Research Foundation of Korea,Grant/Award Numbers:2019H1D3A1A01071209,2021R1I1A1A01060380,2022R1A2C2010686,2022R1A4A3033528Korea Basic Science Institute,Grant/Award Numbers:2019R1A6C1010042,2021R1A6C103A427。
文摘We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.
基金Erwin Edward Hart Professorship, Natural Sciences and Engineering Research Council of Canada (NSERC, RGPIN-2018-04642)University of Toronto for financial supports, and China Scholarship Council under Grant No. 201906270124。
文摘Hydrogen has been identified as one of the most promising sustainable and clean energy. Developing hydrogen evolution reaction(HER) catalyst with high activity is essential for satisfying the future requirements. Considering novel advantages of two-dimensional materials and high catalytic activity of atomic transition metal, in this study, using density functional theory calculation, the HER on single transitionmetal(23 different TM atoms) doped phosphorus carbide monolayer(α-PC) has been investigated. The Volmer–Tafel and Volmer–Heyrovsky reaction mechanisms, and the stability of the most promising HER catalyst are also included. The results show that Ir-αPC with high physical and thermal stability has the most optimal value of Gibbs free adsorption energy for H atom. The relationship of d band center and the HER activity shows a volcano-like curve. The calculation of reaction energy barrier indicates that the Volmer-Heyrovsky step is more favorable than the Volmer-Tafel step.
基金the Natural Science Foundation of China(Grant Nos.21871065,22209129,and 22071038)the Heilongjiang Touyan Team(HITTY-20190033)+3 种基金High-Level Innovation and Entrepreneurship(QCYRCXM-2022-123)the Talent Project of Qinchuangyuan and Interdisciplinary Research Foundation of HIT(IR2021205)Professor Li acknowledges the financial support from the“Young Talent Support Plan”of Xi'an Jiaotong University(HG6J024)the“Young Talent Lift Plan”of Xi'an city(095920221352).
文摘Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.
基金Project supported by the National Key R&D Program of China (Grant Nos.2022YFA1403203 and 2021YFA1600201)the National Natural Science Foundation of China (Grant Nos.11974356 and 12274414)+1 种基金the Joint Funds of the National Natural Science Foundation of Chinathe Chinese Academy of Sciences Large-Scale Scientific Facility (Grant No.U1932216)。
文摘Group IV element Pb has been selected as the dopant to dope at the Sr site of Sr_(2)IrO_(4). It is exciting to find that the single-phase crystal structure could be maintained with a high Pb doping level of up to x=0.3 in Sr_(2-x)Pb_(x)IrO_(4). The mapping data obtained from energy-dispersive x-ray spectroscopy analyses give solid evidence that the Pb ions are uniformly distributed in the Sr_(2)IrO_(4) matrix. The incorporation of Pb leads to a moderate depression of the canted antiferromagnetic ordering state. The electrical conductivity could be greatly enhanced when the Pb doping content is higher than x=0.2.The present results give a fresh material base to explore new physics in doped Sr_(2)IrO_(4) systems.
基金supported by the Natural Science Foundation of Shandong Province (Grant Nos. ZR2020MA068, ZR2022MA083, and ZR2023MA018)the Major Basic Research Project of Shandong Province (Grant No. ZR2020ZD28)。
文摘Electrical control of magnetism in van der Waals semiconductors is a promising step towards development of two-dimensional spintronic devices with ultralow power consumption for processing and storing information.Here, we propose a design for two-dimensional van der Waals heterostructures(vdWHs) that can host ferroelectricity and ferromagnetism simultaneously under hole doping. By contacting an In Se monolayer and forming an InSe/In_(2)Se_(3) vd WH, the switchable built-in electric field from the reversible out-of-plane polarization enables robust control of the band alignment. Furthermore, switching between the two ferroelectric states(P_↑ and P_↓)of hole-doped In_(2)Se_(3) with an external electric field can interchange the ON and OFF states of the nonvolatile magnetism. More interestingly, doping concentration and strain can effectively tune the magnetic moment and polarization energy. Therefore, this provides a platform for realizing multiferroics in ferroelectric heterostructures,showing great potential for use in nonvolatile memories and ferroelectric field-effect transistors.
基金supported by the National Natural Science Foundation of China (Grant Nos. 11974171, 12061131001, and 11927809)the National Key R&D Program of China (Grant No. 2022YFA1403201)。
文摘Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electronic state starting from the Mott insulator, we dose the surface of the parent phase Ca_(2)CuO_(2)Cl_(2) by depositing Rb atoms, which are supposed to donate electrons to the CuO_(2) planes underneath. We successfully achieved the Rb sub-monolayer thin films in forming the square lattice. The scanning tunneling microscopy or spectroscopy measurements on the surface show that the Fermi energy is pinned within the Mott gap but close to the edge of the charge transfer band. In addition, an in-gap state appears at the bottom of the upper Hubbard band(UHB), and the Mott gap will be significantly diminished. Combined with the Cl defect and the Rb adatom/cluster results, the electron doping is likely to increase the spectra weight of the UHB for the double occupancy. Our results provide information to understand the electron doping to the parent compound of cuprates.
基金supported primarily by the National Natural Science Foundation of China(Contract No.21975245,51972300,62274155,and U20A20206)the National Key Research and Development Program of China(Grant No.2018YFE0204000)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB43000000)the National Natural Science Foundation of China under Grant No.62175231.Prof.Kong Liu appreciates the support from the Youth Innovation Promotion Association,the Chinese Academy of Sciences(No.2020114)the Beijing Nova Program(No.2020117).
文摘Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.
基金financially supported by the Technion V.P.for Research Fund(No.2023320)。
文摘The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.
基金supported by the National Key Research and Development Program of China (Grant No. 2021YFA1400201)the CAS Project for Young Scientists in Basic Research (Grant No. YSBR059)+5 种基金the Beijing Natural Science Foundation (Grant No. 4191003)the National Natural Science Foundation of China (Grant No. 11774408)the Scientific Instrument Developing Project of the Chinese Academy of Sciences (Grant No. GJJSTD20200005)the Strategic Priority Research Program of Chinese Academy of Sciences (Grant Nos. XDB36000000 and XDB30000000)the International Partnership Program of Chinese Academy of Sciences (Grant No. GJHZ1826)CAS Interdisciplinary Innovation Team。
文摘Controlling collective electronic states hold great promise for development of innovative devices. Here, we experimentally detect the modification of the charge density wave(CDW) phase transition within a 1T-TaS_(2) layer in a WS_(2)/1T-TaS_(2) heterostructure using time-resolved ultrafast spectroscopy. Laser-induced charge transfer doping strongly suppresses the commensurate CDW phase, which results in a significant decrease in both the phase transition temperature(T_(c)) and phase transition stiffness. We interpret the phenomenon that photoinduced hole doping, when surpassing a critical threshold value of ~ 10^(18)cm^(-3), sharply decreases the phase transition energy barrier. Our results provide new insights into controlling the CDW phase transition, paving the way for optical-controlled novel devices based on CDW materials.
基金financially supported by the National Natural Science Foundation of China (52172192)the Young Top-Notch Talent of National Ten Thousand Talent Program (W03070054)。
文摘Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.
基金This work was supported by the National Key Research and Development Program of China(No.2022YFB3605100)the National Natural Science Foundation of China(Nos.62234001,61927806,61974002,62135013,and 62075081)+1 种基金the Key-Area Research and Development Program of Guangdong Province(No.2020B010172001)the Major Scientific and Technological Innovation Project(MSTIP)of Shandong Province(No.2019JZZY010209).
文摘The development of semiconductors is always accompanied by the progress in controllable doping techniques.Taking AlGaN-based ultraviolet(UV)emitters as an example,despite a peak wall-plug efficiency of 15.3%at the wavelength of 275 nm,there is still a huge gap in comparison with GaN-based visible light-emitting diodes(LEDs),mainly attributed to the inefficient doping of AlGaN with increase of the Al composition.First,p-doping of Al-rich AlGaN is a long-standing challenge and the low hole concentration seriously restricts the carrier injection efficiency.Although p-GaN cladding layers are widely adopted as a compromise,the high injection barrier of holes as well as the inevitable loss of light extraction cannot be neglected.While in terms of n-doping the main issue is the degradation of the electrical property when the Al composition exceeds 80%,resulting in a low electrical efficiency in sub-250 nm UV-LEDs.This review summarizes the recent advances and outlines the major challenges in the efficient doping of Al-rich AlGaN,meanwhile the corresponding approaches pursued to overcome the doping issues are discussed in detail.
基金the support of the National Natural Science Foundation of China(Grant No.51472074).
文摘Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,and 22379080Major Basic Research Program of the Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09+1 种基金the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059the Postdoctoral Program in Qingdao under No.QDBSH20220202019。
文摘Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.
基金supported by the National Natural Science Foundation(52232009)the National Natural Science Foundation for Distinguished Young Scholar(52125404)+1 种基金the National Youth Talent Support Program,“131”First Level Innovative Talents Training Project in Tianjinthe Tianjin Natural Science Foundation for Distinguished Young Scholar(18JCJQJC46500).
文摘Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).
基金Funded by National Key Research and Development Program of China (No.2021YFA1600203)。
文摘A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.
基金financial supports from National Natural Science Foundation of China(22005174 and 52271133)。
文摘Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.
基金financially supported by the National Natural Science Foundation of China(22379056,52102260)the Project funded by China Postdoctoral Science Foundation(2022M711545)the Carbon Peak and Carbon Neutrality Project(Breakthrough for Industry Prospect and Key Technologies)of Zhenjiang City(CG2023003)。
文摘To address the low conductivity and easy agglomeration of transition metal sulfide nanoparticles,FeCoS_(4) nanoparticles embedded in S-doped hollow carbon(FeCoS_(4)@S-HC)composites were successfully fabricated through a combination of hydrothermal processes and sulfidation treatment.The unique bowlshaped FeCoS_(4)/S-HC composites exhibit excellent structural stability with a high specific surface area of 303.7 m^(2)·g^(-1) and a pore volume of 0.93 cm^(3)·g^(-1).When applied as anode material for lithium-ion batteries,the FeCoS_(4)@S-HC anode exhibits efficient lithium storage with high reversible specific capacity(970.2 mA·h·g^(-1) at 100 mA·g^(-1))and enhanced cycling stability(574 mA·h·g^(-1) at 0.2 A·g^(-1) after 350 cycles,a capacity retention of 84%).The excellent lithium storage is attributed to the fact that the bimetallic FeCoS_(4) nanoparticles with abundant active sites can accelerate the electrochemical reaction kinetics,and the bowl-shaped S-HC structure can provide a stable mechanical structure to suppress volume expansion.
基金supported by the National Natural Science Foundation of China (Grant No. 12304072)Program for Science and Technology Innovation Team in Zhejiang (Grant No. 2021R01004)+1 种基金Natural Science Foundation of Ningbo(Grant No. 2021J121)supported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_12_12_1.Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.
基金Project supported by the Ministry of Science and Technology of China (Grant No. 2022YFA1403800)the National Natural Science Foundation of China (Grant Nos. U2032204,12188101, and U22A6005)+2 种基金the Chinese Academy of Sciences (Grant No. XDB33000000)the Synergetic Extreme Condition User Facility (SECUF)the Center for Materials Genome。
文摘Manipulating emergent quantum phenomena is a key issue for understanding the underlying physics and contributing to possible applications.Here we study the evolution of insulating ground states of Ta_(2)Pu_(3)Te_(5) and Ta_(2)Ni_(3)Te_(5) under in-situ surface potassium deposition via angle-resolved photoemission spectroscopy.Our results confirm the excitonic insulator character of Ta_(2)d_(3)Te_(5).Upon surface doping,the size of its global gap decreases obviously.After a deposition time of more than 7 min,the potassium atoms induce a metal-insulator phase transition and make the system recover to a normal state.In contrast,our results show that the isostructural compound Ta_(2)Ni_(3)Te_(5) is a conventional insulator.The size of its global gap decreases upon surface doping,but persists positive throughout the doping process.Our results not only confirm the excitonic origin of the band gap in Ta_(2)Pd_(3)Te_(5),but also offer an effective method for designing functional quantum devices in the future.
基金National Natural Science Foundation of China,Grant/Award Number:51971065Innovation Program of Shanghai Municipal Education Commission,Grant/Award Number:2019-01-07-00-07-E00028。
文摘SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.